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Archive for the tag "Phillip II"
Does this later case explain Henry Pole the Younger's fate?
In the years from 1518, before he left England again in 1536, Reginald Pole occupied a number of ecclesiastical ranks, including that of Dean of Exeter. During the early 1530s, just as Henry VIII sought his first annulment, Eustace Chapuys was pressing Reginald to marry Princess Mary, the cousin he eventually served from Lambeth Palace. By the end of 1536, Reginald was created a Cardinal and was under holy orders, whether he had been earlier or not. The plot that he, together with his brothers Henry Lord Montagu and Sir Geoffrey, is supposed to have launched against Henry VIII needed a credible marital candidate or two for Mary. This, as we have pointed out before, meant Henry Pole the Younger, Montagu's son, and Edward Courtenay, son of the Marquis of Exeter. Either or both of these teenage boys could have been viewed, by Henry VIII, as threats so both were consigned to the Tower. Pole was never seen after 1542, whilst Courtenay was only released in 1553.
Reginald Pole, as a Cardinal, was bound by clerical celibacy but could this be reversed? Not if this later case is anything to go by, although Phillip II, Mary's eventual husband and Catherine of Aragon's great-nephew, had a hand in it: Sebastian, the young King of Portugal died without issue at the 1578 battle of Alcacer Quibir and only his great-uncle Henry, Manuel of Beja's son, remained from the legitimate House of Aviz, that almost provided spouses for Richard III and Elizabeth of York in the previous century. Henry, however was a Cardinal and Gregory XIII, at Phillip's behest, would not release him from his vows. Henry ruled alone for nearly a year and a half before dying on his 68th birthday. The strongest claimant to succeed him was … Phillip II, who ruled Portugal, followed by his son and grandson, for a total of sixty years, although Antonio, a Prior and Sebastian's illegitimate cousin, tried to reign.
This explains the various claimants, including the House of Braganza, which supplied Charles II's wife.
Posted by super blue in anniversaries, battles, genealogy, religion and tagged Antonio of Portugal, Archbishop of Canterbury, Battle of Alcacer Quibir, Catherine of Aragon, clerical celibacy, Elizabeth of York, Eustace Chapuys, Gregory XIII, Henry Courtenay Marquis of Exeter, Henry Lord Montagu, Henry of Portugal, Henry Pole the Younger, House of Aviz, Joanna, Manuel, Mary I, Phillip II, Portugal, Reginald Cardinal Pole, Richard III, Sebastian, Sir Geoffrey Pole, Spain, Thomas Courtenay Earl of Devon
Ten medieval scandals….!
Pope Stephen VI had the body of his predecessor, Pope Formosus, exhumed and put on trial.
"….What are the scandals that made headlines in the Middle Ages? Kings and Popes would be involved in some of the craziest stories of sex and corruption that would make today's news seem quite tame. From a cross-dressing prostitute to the trial of a dead Pope, here are ten almost-unbelievable medieval scandals…."
Well, you'll find these "gems" at this site I imagine they're all true, although some of them beggar belief. Especially the rather gruesome episode illustrated above.
Posted by viscountessw in anniversaries, law, religion and tagged Alice Perrers, Bal des Ardents, Banquet of Chestnuts, Benedict IX, Borgias, Cadaver Synod, Charles VI, Charles VIII, cross-dressing, Edward II, Edward III, Formosus, France, Heloise, Ingeborg of Denmark, Isabella de Valois, Italian Wars, Italy, John Rykener, Louis d' Orleans, Medici bank, Papacy, Peasants' Revolt, Peter Abelard, Phillip II, Phillip IV, Piero de Medici, prostitution, Richard Lyons, scandals, Stephen VI, Tour de Nesle, Vatican City, William Latimer | Leave a comment
A new interpretation of 1580s events
We all know that Mary Stuart was beheaded at Fotheringhay on 8 February 1587 and that the Spanish Armada sailed to facilitate a Catholic invasion of England in the following year, leaving Lisbon on 28 May and fighting naval battles in late July, at Plymouth and Port land. The traditional view is that Mary Stuart's execution and Elizabeth I's support for the revolt in the Spanish Netherlands provoked Phillip II's wrath.
It is quite possible that this was not the case and that Phillip had
sought to overthrow his quondam sister-in-law much earlier. Mary, as the daughter of Marie de Guise and widow of Francis II was the French-backed Catholic candidate for the English throne and Franco-Spanish rivalry ensured that Phillip, great nephew of Catherine of Aragon and a Lancastrian descendant proper+, would not act in concert with any of her plots; however her death cleared the way for him, especially as the French Wars of Religion were still to resolve themselves.
We can compare this with the England of 1685-8, as William of Orange allowed the Duke of Monmouth to attempt an invasion first and only asserted his stronger semi-marital claim against James VII/II afterwards. In 1483-5, by contrast, the Duke of Buckingham was legitimately descended from Edward III when he rebelled against Richard III, only for Henry "Tudor", of dubious lineage, to benefit.
h/t Jeanne Griffin
+ See The Wars of The Roses, Ashdown-Hill, part 4.
Posted by super blue in anniversaries, battles, genealogy, religion and tagged Armada, Battle of Bosworth, Battle of Sedgemoor, Buckingham rebellion, Duke of Medina Sidonia, Duke of Parma, Elizabeth I, executions, Fotheringhay, France, French Wars of Religion, Glorious Revolution, Henry of Buckingham, Henry VII, James of Monmouth, James VII/II, John Ashdown-Hill, John Hawkins, Lisbon, Lord Howard of Effingham, Marie de Guise, Mary II, Mary Stuart, Monmouth Rebellion, naval battles, Netherlands, Phillip II, Plymouth, Portland, Richard III, Scotland, Sir Francis Drake, Spain, Tilbury speech, William III
You will have seen him if you have been to Richard III's final resting place. There are eight small statues on the main entrance (the Vaughan Porch, left) of St. Martin's Cathedral but only one of them is wearing a doublet and hose, showing him to have lived a century later than the others. This is Lord Henry Hastings, as he was during his education alongside Edward VI and participation, with Northumberland's daughter Lady Catherine Dudley in the triple marriage of May 1553. He was still Lord Henry as he served in the household of his great-uncle Reginald Cardinal Pole, travelling to Calais and Flanders and escorting Phillip II to England for his marriage to Mary I, whose succession had been aided by Lord Henry's father, Francis, despite the family's overt Protestant beliefs .
In 1562, two years after succeeding to the Earldom of Huntingdon, he was considered by some for the throne had Elizabeth I not recovered from a bout of smallpox. By 1576, on the death of his mother Catherine (nee' Pole) he was the senior post-Plantagenet, barred from the succession maternally only by the Clarence attainder but he had a junior claim through his grandmother Anne Stafford, w hose father and brother both had their attainders posthumously reversed.
From 1572 to his death in 1595, Huntingdon was Lord President of the Council of the North, a position previously held by Richard as Duke of Gloucester and then by the Earl of Lincoln, in which he ruled the part of England north of the Trent from the King's Manor (above), formerly home to the Abbot of York. During this tenure, he re-established royal authority in the region after the Northern Earls' Rebellion failed, attended Mary Stuart's trial, ensured good relations with James VI and his regents, the Earl of Morton in particular, also helping to prepare defences against the Armada. For his long service for more than half the reign of the last "Tudor", Huntingdon deserves to be remembered alongside Lord Burleigh and his brother-in-law the Earl of Leicester, although his Calvinist beliefs set him apart from them and their Queen. During his time, in 1586, the recusant Margaret Clitherow was pressed to death at York.
As Claire Cross points out in her iconic biography The Puritan Earl, Huntingdon took his role as head of the family seriously. We can read how his assets shrank during his lifetime and how his 42 year marriage was childless, such that his brother Sir George succeeded him as Earl, with senior descendants still alive in Australia, as Jones has shown. He died eleven days before Christmas 1595 and was connected to all four later "Tudor" monarchs but his strongest connection was to Elizabeth I. Just like her, he had been imprisoned at the outset of Mary I's reign, probably because he was Northumberland's son-in-law, although his father's loyalty soon extricated him from this.
Posted by super blue in anniversaries, buildings, genealogy, religion and tagged Anne Stafford, Armada, Ashby St Ledgers, attainder, Calais, Calvinism, Catherine Dudley, Catherine Pole, Claire Cross, Earl of Leicester, Edward of Buckingham, Edward VI, Elizabeth I, fashion, Flanders, Francis Baron Hastings, George Duke of Clarence, Henry Earl of Huntingdon, Henry of Buckingham, James Earl of Morton, Jane, John Dudley Duke of Northumberland, John Earl of Lincoln, Leicester cathedral, Margaret Clitherow, Mary I, Mary Stuart, Michael K Jones, Northern Earls' Rebellion, Phillip II, Plantagenet descent, recusants, Reginald Cardinal Pole, Scotland, Sir George Hastings, smallpox, statues, Vaughan porch, William Cecil
A truncated reign and a truncated monarch
Right at the start of this series, Helen Castor (left) takes a black marker pen and illustrates the cause of the 1553 crisis on a large sheet of paper. Beginning with Henry VII, very few of his legitimate male descendants were alive at the start of that year – eliminating the obvious illegitimate cases, we have Henry Stuart, Lord Darnley, aged seven (a Catholic in Scotland) and Edward VI, aged fifteen, whose health took a turn for the worse at that time. There were, however, nine healthy legitimate female descendants: Lady Margaret Douglas, Mary Stewart who was Lady Margaret's niece of ten and already crowned in Scotland (but living as a Queen consort in France), Henry VIII's two bastardised, but included by law, daughters Mary and Elizabeth, Lady Frances Grey (nee' Brandon, Duchess of Suffolk in suo jure) and her three daughters Jane, Catherine and Mary together with Frances' niece Lady Margaret Clifford. In short, the "Tudor" male line was on the propinquity of its termination, although a medical explanation for this was not given.
In the first programme, Castor showed how Edward's "devise for my succession" developed during that fateful year. First, he hopes that one of the Protestant Grey sisters will have a male heir to succeed him with Frances as the new King's grandmother and Regent. Then his illness accelerated and there are crossings out on the devise, such that "the Lady Jane's heires male" becomes "the Lady Jane AND HER heires male", in the hope that he will live long enough for Parliament to enact this document and supersede Henry VIII's own legislation, which named the Catholic Mary as heir after Edward, although the Greys would be preferred to the Stewarts. On the left is the "Streatham Portrait", previously thought to have been of Jane, but not commissioned until half a century later.
During the first half of 1553, Lady Jane was married to Lord Guildford Dudley, son of the Duke of Northumberland who was Lord Protector at the time. Lady Catherine Grey also married, as did Guildford's sisters, one to Lord Henry Hastings, later Earl of Huntingdon. In the event, fate overtook Edward's plans and his devise, as letters patent, had no legal status at his death on 6 July. Darnley's claim as the last "Tudor" male was to be ignored and England was to have a Queen Regent, as Northumberland took his son and new daughter-in-law from Bradgate in Leicestershire, via Sion House to the Royal Apartments in the Tower for her reign to be proclaimed on 10 July, although Jane took the fateful decision that her husband was to be created Duke of Clarence and not King.
In the second programme, Castor explains how the Privy Council erred by sending Northumberland to East Anglia to arrest Mary, removing the realm's best military commander from the capital, where the professional soldiers and their weapons were. Mary moved from Kenninghall in Norfolk to Framlingham Castle to strengthen her position and gathered support from those who still adhered to her Catholic faith and who had "known" her from afar for her whole life. There was to be no arrest of Mary, nor was there to be a pitched battle as Henry VIII's first-born child outmanoeuvred Northumberland, at his Cambridge base, in order to march upon London.
The third episode begins with a naval mutiny ensuring that Mary had some artillery to enforce her claimand the Privy Council officially dethroning Jane. Mary took the Tower, Jane, Guildford and their fathers became prisoners and Mary was proclaimed. For Jane, there could be no return to her earlier life at Bradgate. Except for Northumberland, there was to be no trial until November and even then Jane, Guildford and Suffolk had their sentences of death suspended – until Thomas Wyatt rebelled in the Protestant interest in mid-January, in protest at Mary's plans to marry Phillip II. Mary then signed the three death warrants, the teenage couple went to the block on February 12th and Jane's father eleven days later. Cranmer, who had been part of her Privy Council, was attainted and deprived but lived to face Mary's further wrath at a later date. Darnley married the other Queen Mary and was killed a year or two later in his own realm. For nearly fifty years from that July day when Edward VI's eyes closed for the last time, England had no male claimant descended from Henry VII and the throne was disputed solely by Queens Regnant.
Castor concludes by pointing out that Jane, proclaimed Queen by the Privy Council who had served Edward VI, should be reckoned as a real monarch of England, even though she had been illegally proclaimed and then dethroned. In some ways, her turbulent final year taught her cousin Elizabeth a valuable lesson – not to take a husband, especially as the most likely such candidate was her fellow survivor: Lord Guildford Dudley's younger brother, Robert.
On the right is Paul Delaroche's highly inaccurate painting of Jane's end, painted as late as 1834. His version of her execution takes place indoors but we know that she died on Tower Green, as did most beheaded women.
For those of us more focused on the fifteenth century, we will be familiar with the concepts of a king Edward whose death was not announced for several days whilst a faction sought to establish control (1483) and of prisoners being executed to clear the way for a Spanish marriage (1499).
Posted by super blue in anniversaries, art, genealogy, law, religion, television reviews and tagged "Perkin", "Tudor" genealogy, Acts of Succession, Archbishop Cranmer, BBC, coups d'etat, Dukedom of Clarence, Earl of Leicester, Edward IV, Edward of Warwick, Edward VI, Elizabeth I, Framlingham Castle, France, Greys, Helen Castor, Henry Earl of Huntingdon, Henry Lord Darnley, Henry VII, Henry VIII, Jane, John Dudley Duke of Northumberland, John of Gloucester, Kenninghall, Kirk o'Fields, Lady Catherine Grey, Lady Frances Brandon, Lady Margaret Clifford, Lady Margaret Douglas, Lady Mary Grey, Legitimacy, Leicestershire, letters patent, Lord Guildford Dudley, Mary I, Mary Stuart, Paul Delaroche, Phillip II, portraits, Scotland, Sion, Spain, Stewarts, Streatham portrait, Tower Green, Tower of London, Wyatt Rebellion, Wydevilles
You only reign twice?
Edward of Caernarvon, who was born in 1284, was king of England for nearly twenty years from 1307 as Edward II. What of his childhood?
In about October 1289, he was contracted to Margaret, known as the Maid of Norway and Queen of Scotland since 1286 when her grandfather Alexander III died. She was a year older than Edward and then travelled towards her own realm but died of seasickness in the Orkneys during September 1290 and was buried in Bergen. Negotiations took place under the Treaty of Salisbury, signed by Edward I, Robert Bruce and some other Guardians of the Realm for Scotland. A dispensation was issued by Nicholas IV, because Margaret's grandmother was Henry III's daughter, Henry also being Prince Edward's grandfather.
Let us examine some of the circumstances:
i) Edward and Margaret were both under fourteen, but so were Richard of Shrewsbury and Anne Mowbray, Duchess of Norfolk and "The Princess in the Police Station", when they married. She also died under that age of majority. Such a marriage was valid, however, although it could not yet be consummated.
ii) Edward and Margaret never actually met, but Mary I and Phillip II married by proxy before he moved to England.
iii) As late as the sixteenth century in England or Scotland, a male consort was styled as "King". Phillip II was such, as was Henry Lord Darnley, as the contemporary coinage attests. After this, William III was a joint monarch, as James VII/II's nephew, but George of Denmark was not.
So, if the Treaty of Salisbury included an actual contract of marriage, Edward of Caernarvon had already been King of Scotland for a year before he succeeded his father in England. Between summer 1284 and 1300, he was Edward I's only surviving legitimate son, so the treaty would have united the two kingdoms three centuries earlier than actually happened.
This post explains a little more about the Maid, among others, emphasising that Alexander saw Edward as a future grandson-in-law almost from birth.
Posted by super blue in anniversaries and tagged Alexander III, Anne, Anne Mowbray, anniversaries, canon law, coinage, consorts, dispensations, Edward II, George of Denmark, Guardian of Scotland, Henry III, Henry Lord Darnley, Kathryn Warner, Margaret of Norway, Mary I, Mary II, Mary Stuart, Norway, Orkneys, Phillip II, Richard of Shrewsbury, Scotland, Sean Connery, Treaty of Salisbury, William III
An award for masochism?
The 1538 plot first saw Sir Geoffrey Pole arrested that autumn and compelled, by a threat to torture his servants, to give evidence about the activities of his exiled brother Reginald and other relatives. Henry Pole Lord Montagu and Henry Courtenay Marquess of Exeter were arrested next, together with Montagu's son Henry the Younger and brother-in-law Sir Edward Neville, Exeter's wife Gertrude Blount and their son Edward. Montagu was, of course, George of Clarence's grandson and Exeter was Edward IV's. Reginald and Henry the Younger had both been considered as husbands for Princess Mary.
Henry Pole the Younger and Thomas Courtenay are both likely to have been under age in 1538 because almost all of the adult prisoners here – Montagu, Neville and Exeter – were attainted and executed, as was Montagu's mother the Countess of Salisbury, eventually. Gertrude Blount was released, as was Sir Geoffrey Pole, but unlike Henry Pole, who disappeared by the end of 1542, Edward Courtenay was held until Mary's accession. In some ways, the most interesting phase of his short life was about to start.
On his release from the Tower after almost fifteen years, Courtenay was restored to the family's Earldom of Devon. He was in favour with Mary and may have been another suitor In the following year, he was returned to the Tower along with Princess Elizabeth, the Queen's sister, for suspected complicity in the Wyatt rebellion and he is thought to have planned marriage to her. Both were soon released: she to a form of house arrest and he to exile in Padua, Venice.
Mary finally married Phillip II of Spain later in 1554. She only lived for four more years and Thomas died mysteriously without issue in 1556, although he is rumoured to have found a bride in Padua: one Laurana de Medici. He was probably not thirty, being the younger son of parents married in 1519, and had lived half of that time in the Tower of London. He could have married either of Henry VIII's daughters but was probably fortunate to have failed in this respect.
Posted by super blue in buildings, genealogy and tagged Edward IV, Elizabeth I, executions, exiles, George Duke of Clarence, Gertrude Blount, Henry Courtenay Marquess of Exeter, Henry Lord Montagu, Henry Pole the Younger, Henry VIII, Italy, Margaret of Salisbury, Mary I, Padua, Phillip II, Reginald Cardinal Pole, Sir Edward Neville, Sir Geoffrey Pole, Thomas Courtenay Earl of Devon, Tower of London, Wyatt Rebellion
THE MALIGNED RICARDIANS
Part 1 – Sir William Cornwallis the younger
" His virtues I have sought to revive, his vices to excuse"
(The Encomium of Richard III, Sir William Cornwallis)
It is conceivable that historians do not take the early revisionist histories of king Richard III seriously owing to an assumption that the authors were not themselves serious. If so, they are probably mistaken about Sir William Cornwallis (1579-1614) the author of the 'Encomium of Richard III', the earliest extant defence of the last Plantagenet king and the subject of this post. And they are definitely wrong about Sir George Buck, the author of a second and more substantial defence of Richard entitled 'The History of King Richard the Third'. My purpose in this post and a further one about Buck is to draw attention to these undervalued and misunderstood revisionists, whose pioneering works have provided the template for subsequent defences of king Richard.
Sir William Cornwallis the younger (so called, to distinguish him from his uncle) was probably born at Fincham, Norfolk. He was the eldest child of Sir Charles Cornwallis a diplomat and court official. The Cornwallis' were well known recusants and too prominent during catholic Mary's time to prosper much under protestant Elizabeth: they were always under suspicion. Within that parameter the young Cornwallis' upbringing was gratifyingly orthodox. He studied at Queen's College, Oxford. In 1595 he married Katherine Parker; they had thirteen children, eight of whom survived him. In 1599 he saw action in the earl of Essex's Irish campaign, and was knighted by the earl for his service . On his return to England he lived quietly during the remainder of Elizabeth's reign.
In 1603 on the accession of James I he was appointed a member of the king's Privy Chamber. In 1604 he was elected MP for Orford in Suffolk in support of the union between England and Scotland, and in 1605 was sent on a minor diplomatic mission to Spain. His extravagant lifestyle resulted in considerable debt and despite a gift of £2000 from the king he died in penury in 1614, leaving his widow and eight children destitute.
Cornwallis' literary career was that of a gentleman amateur writing 'familiar' paradoxical essays at the turn of seventeenth century. According to Kincaid "His style is fluent but incursive, his periods short but balanced. Illustrative examples are drawn from his own experience, though with evident modesty. He is concerned with self-improvement, particularly for statesman, stressing stoic virtues such as resolution, fortitude and endurance. His method is influenced by Montaigne, his ethics by Seneca . The paradoxes range from satirical praise of misfortune (e.g. 'The French Pox' and 'Debt') to what seem, at least partly, serious defences of historical figures (e.g. Julian the Apostate and Richard III)." Even though the contemporary essays of Sir Francis Bacon and John Donne overshadowed Cornwallis' own literary achievement, the paradoxical essay tradition as it re-emerged in the eighteenth and nineteenth centuries owes more to his method than to theirs.
The Encomium of King Richard III – Background
It was commonplace for the original manuscripts of familiar essays to circulate among groups of literary friends. It was also commonplace for the author and for others to copy the manuscript: sometimes adding further comments, sometimes correcting errors. The Encomium of Richard III was no exception to the rule; there are ten surviving manuscript copies of it, each being different from the earliest and from each other. Although many of the changes are minor and stylistic, there are some important 'political' interpolations in later versions.
Cornwallis' original manuscript is a mixture of the serious and the paradoxical. It does not sit easily in the form of a paradox. However, later additions indicate crude attempts to formalize it as a conventional paradox. Efforts have also been made to de-personalize it; whereas Cornwallis attacks a single 'corrupt chronicler', later versions change that to 'our corrupt chroniclers'. The most interesting additions are those that are politically motivated. These additions though ostensibly enhancing Richard's defence are really political propaganda linked to the Essex plot of 1600, and have wrenched Cornwallis' original Encomium out of context. It is not surprising, therefore, that so many literary scholars regard the Encomium as a rather poor paradoxical essay and so many historians disregard it as a serious defence of king Richard III. It is also unfortunate that the latest version was published in 1616, as it is the one most commonly known and it distorts Cornwallis' own views. It is in this context that we should assess the worth of the 'Encomium'. In this post I am concentrating on three aspects of the Encomium. First the questions of authorship and motive, second an overview of Cornwallis' technique for defending king Richard's reputation, and finally the influence of late Elizabethan and early Jacobean politics on later versions of the Encomium.
In the first half of the twentieth century, Professor W Gordon Zeeveld argued that 'The Encomium of Richard III' was in response to a manuscript account of king Richard's reign written by Cardinal John Morton soon after Bosworth. This manuscript had been circulating amongst Tudor intellectuals for many years. According to Zeeveld it was copied by Sir Thomas More and published by his nephew John Rastell as More's 'History of King Richard III. Zeeveld argues that the traces of personal hatred towards Morton contained in early versions of the Encomium are evidence that it was inspired by Morton's tract.
Zeeveld also believed that the Encomium was a palimpsest concealing an earlier defence of Richard, with Cornwallis as the continuator rather than the originator of that work. He postulates that an anonymous contemporary supporter of Richard took it upon himself to defend his dead master from Morton's tract. Unfortunately there is no evidence that this earlier defence existed; neither does it follow that the personal bitterness evident in the Encomium places the author in the 1490's. As Dr Kincaid points out, it could just as easily result from intellectual stimulus affecting somebody in the 1590's.
Nobody knows why Cornwallis wrote this essay or why he chose to do so in a hybrid form. His animosity towards one Tudor chronicler suggests an emotional involvement that is at odds with his otherwise reasoned and intellectual approach. However, the editors of Kincaid's excellent edition of the Encomium have conducted a careful and minute study of all ten original manuscripts and they are perfectly satisfied about two things: first, the Encomium is not a palimpsest, it is Cornwallis' original work; second, Morton wrote a tract about Richard that was still extant in the 1590's.Notwithstanding these conclusions, the evidence of a link between Cornwallis and Morton's tract is circumstantial at best; it does no more than establish the possibility that Cornwallis had access to the tract.
Last on this aspect, the suggestion that Morton wrote a tract which was still in circulation well into Elizabeth I's reign has wider significance, particularly regarding the authorship of More's 'History' and its impact on Sir George Buck 'History of King Richard the Third'. I hope to address both these issues in a future post.
The defence of king Richard
Cornwallis' defence of Richard is unique in pro Ricardian literature in that generally he does not challenge the traditional Tudor version of the facts. The importance of the Encomium to the Ricardian narrative is simply that it is the first reasoned defence of Richard. The absence of an evidence base to accompany Cornwallis' reasoning does not damage his contribution to that narrative, since Buck and others have been well able to supply that evidence. Although largely ignored by academics and historians, the Encomium has had a significant influence on future revisionists. For example, Buck structured his first three books around the Encomium (though he was working from a later manuscript) and Walpole adopted a similarly reasoned approach. The Encomium contains most, if not all, of the reasoned, logical defensive arguments that we see in modern Ricardian literature to this day.
Cornwallis makes four broad points. First, some of the accusations against Richard are so frivolous that they must have been prompted by malice (e.g. his physical appearance, born with teeth etc.). Second, there is no objective evidence that he committed many of the offences alleged against him (e.g. the murder of Henry VI and the allegation that he 'commanded' Dr Shaw's sermon on the 22 June 1483, for which others are clearly implicated). Third, he is not guilty of usurpation or of regicide by reasons of state. It is only the third point that I want to explore in a little detail since the allegation of regicide is by far the most serious charge laid against king Richard III.
In 1601 Cornwallis (and not the later interpolators) wrote this about the disappearance of the two Princes: "In this time chanced the death of his two young nephews in the Tower, whose deaths promising quiet unto him, are wholly imposed upon him, how truly I have reason to doubt, because his accusers are so violent and impudent, that those virtues which in other men are embraced, for which they are esteemed as gods, they impute to him to be rather enablers of vices than really virtues. His humility they term pride, his liberality prodigality, his valour cruelty and bloodthirstiness and so through malice, not truth turn all things to their contrary. But if it were so that he contrived and consented to their deaths the offence was to God and not to the people, for the depriving of their lives freed them (the people) from dissention and how could he demonstrate his love more amply than to venture his soul for their quiet, But who knows whether it were not God's secret judgement to punish the father's transgressions on the children, and if so complain their fate, not his cruelty."
Turning his attention to the grim realities of medieval power politics, Cornwallis continues: "…yet in policy princes never account competitors however young or innocent since the least colour of right provokes innovating humours to stir-up sedition, which once being kindled threatens both the subversion of princes and people. Therefore, the removing (of) such occasions of civil wars is well governed. (The) commonwealth is most profitable, most commendable, being no cruelty but pity a jealousy of their subjects and a regard for their own safety". However, king Richard does not entirely escape Cornwallis' censure: "If for this action he ought to be condemned, it is for indiscretion in the managing; for as safely might he have had the realms general consent in disposing of their lives, as in disposing them from the crown, and had he held a secret execution best he might have effected it more secretly…"
Cornwallis eschews a substantive defence of king Richard; instead, he emphasizes his personal virtues and his good works, and excuses his actions as being in the public interest and done from a high sense of public duty. Albeit we cannot establish a firm link between Cornwallis and Morton's tract it seems that the Encomium was indeed a response to More/Morton account. For instance, when condoning Richard's seizure of the crown, Cornwallis refers to Edward IV's betrothal to 'Elizabeth Lucy'. That is a name he can only have found in the work(s) of More/Morton.
Cornwallis had ' high views of the royal prerogative and his Encomium shows no exception.' For example, he writes "…chroniclers should not criticise kings because kings are accountable only to a jury of kings and to God." In Kincaid's edition of the Encomium, the editors identify four distinct ways in which later additions of the British Museum manuscript turned this essentially pro-monarchist work into a revolutionary text.
The first change is subtle alteration to the notion of divine authority. The most obvious example of this occurs in the extract I have referred to above. At the point where Cornwallis suggests that the death of the Princes might be God's judgement on the sins of their father we get this interpolation (highlighted): "…if so complain of their fate, not his cruelty (FOR IN THESE FATAL THINGS IT FALLS OUT THAT HIGH WORKING POWERS MAKE SECOND CAUSES, UNWITTINGLY ACCESSORY TO THEIR DETERMINATION) yet in policy princes…" This insertion introduces a controversial, political tone; though the point being made is hardly new or novel. The notion that temporal kings were subject to God's law, which upholds truth and justice against deceit and injustice, was argued by the Yorkists in the 1450's to justify their rebellion against the misuse of royal authority. It follows that if God's law forbids tyranny it must be His will that subjects should resist and even overthrow tyrants, by force if necessary. This interpolation reflects the seventeenth century's revolutionary agenda whereby the exponents of change rejected the divine right of king, in favour of the principle, enshrined in Magna Carta, that the king was subject to the common law of the land. Rex is not lex; lex is rex (The king is not law; the law is king.).
Second, the text was changed to show the Tudors in a much worse light than hitherto. For example, Cornwallis praises Richard for abolishing forced loans. However, this is altered slightly with the insertion " THOUGH HE CAME TO MANAGE A STATE WHOSE TREASURE WAS EXCEEDINGLY EXHAUSTED." It is a comment that would strike a cord with late Elizabethans struggling under an inequitable tax system. The costs of the continuing Spanish war and the troubles in Ireland had increased the parliamentary subsides granted to the Crown fourfold between 1589 and 1601, with a disproportionate burden falling on the poor. Indeed, the demand for increased subsidy in 1589 was so onerous for the rich that Sir Francis Bacon declared in parliament: "Gentlemen must sell their plate, farmers their brass pots ere this will be paid". In desperation the Queen resorted to levying forced loans and benevolences on the wealthy through the privy seal. She also imposed ship money on inland towns; yet still the exchequer was in deficit. In 1601 parliament debated the plight of the poor. There were calls for the wealthy to pay more: "Some thought that three-pound men should be spared; others that four-pound men should pay double, with a corresponding increased charge on the rest upwards." The tendency of Stuart monarchs to raise taxes without the consent of parliament through forced loans, increased custom duties and ship money was an issue (there were others) that eventually led the king to kill his subjects and his subjects to kill their king.
Third, Cornwallis defends Richard's seizure of the throne on the basis that Edward V was too young to govern himself, much less the realm; anyhow, he would be too much under the bad influence of his mother and maternal uncles who were "…the duke's mortal enemies such as through the lowness of their birth had never been inured to government, whose new nobility was more likely to ruinate than to fortify the Ancient, could not but draw a true discerning spirit to favour himself to maintain the ancient nobility to commiserate the people much wasted by dissensions…" This can certainly be interpreted as a veiled criticism of William and Robert Cecil, who between them controlled the queen and the government in the 1590's. However, the later insertion of the words " AND OPPRESSED" between 'wasted and 'by' in the above extract is a much more explicit reproach of the Cecil's. A reproach that becomes even more obvious in the interpolation at the point where Cornwallis justifies Richard's execution of Rivers and Grey: "…jealous of his own preservation OF THE SAFETY OF THE COMMONWEALTH AND OF THE ANCIENT NOBILITY with great reason and justice he executed them." The reference to the safety of the realm is an allusion to England's Cecil-inspired foreign policy . The criticism is even more explicit in an insertion at the point when Cornwallis is defending the summary execution of William Lord Hastings, which he says was just because Hastings was in the pay of the French king; furthermore, it was he who persuaded Edward IV not to support Burgundy against the French: "WHEREAS NOW IN A FEW YEARS IT IS DEVOLVED TO A PROUD AND INSOLENT NATION (Spain) WHO HAVE GRIEVOUSLY OPPRESSED THOSE NETHERLANDS WITH EXECRABLE CRUELTIES AND ARE AT THIS DATE CAPITAL ENEMIES OF OUR STATE…"
At the turn of the seventeenth century England was in turmoil; people were uncertain about the future, confused and frightened. The queen was ageing and various political factions were jockeying for power and influence in preparation for her demise. Poor harvests had brought famine, the war with Spain dragged on accompanied by genuine war weariness and the economy was a shambles. Militarily and diplomatically England was weaker in 1600 than it had been in1588, whilst Spain was stronger.The Spanish army occupying Holland was a direct threat to England's flank and her independence. On top of all this the protestant reformation was not secured, nor the succession settled. Of the two foreign candidates, one was a Roman Catholic and the other a protestant flirting with Catholicism . The Cecil clique, pacific by inclination, wanted peace with Spain, which was abhorrent to the protestants. In 1601 Robert Devereux the earl of Essex accused Robert Cecil of favouring the succession of the Spanish Infanta to the English throne. It was dismissed as nonsense at the time. However, with the benefit of five hundred years of hindsight and official correspondence we can see that at best, Cecil's behaviour was disingenuous.
Fourth, and perhaps most significantly, is the insertion of an unambiguous appeal to force against legitimacy. Cornwallis is writing of the necessity for Richard to assume the crown for the common good and in particular to prevent another civil war, then this paragraph is inserted into Cornwallis' narrative: "…THE DUTY WE OWE OUR COUNTRY EXCEEDS ALL OTHER DUTIES, SINCE IN ITSELF IT CONTAINS THEM ALL. THAT FOR RESPECT THEREOF NOT ONLY ALL TENDER RESPECTS OF KINDRED, OR WHATSOEVER OTHER RESPECTS OF FRIENDSHIP ARE TO BE LAID ASIDE, BUT THAT EVEN LONG HELD OPINIONS (RATHER GROUNDED ON SECRET GOVERNMENT THAN ANY GROUNDS OF TRUTH) ARE TO BE FORSAKEN SINCE THE END WHERETO ANYTHING IS DIRECTED IS EVER TO BE OF MORE NOBLE RECKONING THAN THE THING THERETO DIRECTED, THAT THEREFORE THE PUBLIC WEAL IS MORE TO BE REGARDED THAN A PERSON OR MAGISTRATE THAT THEREUNTO IS ORDERED…IF ANY MAN SHOULD OBJECT TO THIS COURSE LET HIM KNOW THAT NECESSITIES REQUIRE NEW REMEDIES AND FOR HIM (Richard) THERE WAS NO REMEDY BUT THIS ONE." It is a sentiment that needs no explanation.
Kincaid and Ramsden argue that this insertion was probably aimed at Sir Henry Neville who had an ambiguous role in Essex's attempted coup of 1600 and who was related to Robert Cecil. They postulate that Henry Wriothesley, earl of Southampton sent this amended copy of the Encomium to Neville to reassure him that he could disregard ties of kinship since it was God's will that the Cecil's should be overthrown. It is, they say, the only explanation for this insertion, which is so contrary to Cornwallis' own philosophy.
[1] Elizabeth I was furious with Essex for personally knighting so many of his officers in the wake of his shameful truce with the Irish rebels; the queen called these officers 'idle knights' and there is no suggestion that Cornwallis' preferment suggested a softening of attitude towards him. The Cornwallis' – we are told – 'were always under suspicion'.
[2] Michel Eyquem Montaigne (1533-1592) was an influential French renaissance philosopher who wrote anecdotally on the human condition. His stated objective was to describe humanity and especially himself 'with utter frankness'.
[3] Seneca the Younger (BC1-AD65) was a Roman stoic philosopher. He was forced to commit suicide after being implicated in a plot to assassinate the Emperor Nero.
[4] Arthur Kincaid – Oxford Dictionary of National Biography (online edition, ref:odnb/6345) (DNB)
[5] Arthur Noel Kincaid- The History of King Richard the Third by Sir George Buck (Alan Sutton 1979) at pp.civ-cv: Kincaid writes: 'Rosalie L Colie in her study of paradox's gives Cornwallis' Encomium as an example that fails because it does not surprise of dazzle by its incongruities, for it strikes the reader as an all but serious defence. Instead of appearing skillful many of its arguments give the impression of being sincere but lame…" (See Rosalie L Collie – Paradoxia Epidemica (Princeton 1966) at p8)
[6] Arthur Kincaid and J A Ramsden – The Encomium of Richard III by Sir William Cornwallis the Younger (Turner and Devereux 1977) at p.5 (Kincaid)
[7] Kincaid at pv
[8] Kincaid at p20: interestingly, this was Charles I's grounds for refusing to recognize the jurisdiction of the court appointed by Parliament to try him for crimes against the State in 1649. In 2001 Slobodan Milosevic also pleaded sovereign immunity when arraigned for war crimes (See Geoffrey Robertson – The Tyrannicide Brief (Vintage 2006) for an illuminating discussion on the powers of the law to bring tyrants to book for their crimes.)
[9] Kincaid at p17
[10] Kincaid p14
[11] Professor J B Black – The Reign of Elizabeth I (Oxford 1987) pp. 228-234.
[12] Black at p231
[13] Kincaid p9
[16] It was Philip II's ambition to launch an invasion of England from the Netherlands
[17] Christopher Hill – God's Englishman (Penguin 1972) at pp.20-25: Dr Hill suggests that the Elizabethan golden age was long past: if it ever existed. The legend of a time "…when parliament and crown worked in harmony, in which the Church was resolutely protestant, in which bishops were subordinated to secular power and protestant sea dogs brought gold and glory back from the Spanish Main…owed more to a criticism of what was happening (or not happening) under Stuarts than anything that had really existed under Elizabeth."
[18] James VI was a Protestant and his apparent willingness to convert to Roman Catholicism was only a diplomatic/political ploy to unsettle Elizabeth and the English: it worked.
[19] Black at pp.445-451: Professor Black refers to correspondence, which suggests that Robert Cecil sounded out the feasibility of the Infanta and her husband the Archduke Albert succeeding Elizabeth. He certainly seems to have considered the ditching James VI of Scotland as heir to the throne.
Posted by zenonian in Uncategorized and tagged "Princes", "Tudors", Anthony Woodville, Charles II, Earl of Essex, Earl of Southampton, Elizabeth I, Elizabeth Lucy, forced loans, George Buck, Henry VI, Horace Walpole, Ireland, James VI/I, John Morton, Kincaid, Lord Hastings, Magna Carta, Mary I, Netherlands, Norfolk, Orford, Phillip II, Privy Chamber, Ralph Shaa, recusants, Richard III, Robert Cecil, Seneca, ship money, Sir Henry Neville, Sir Thomas Grey, Sir William Cornwallis, Slobodan Milosevic, Spain, The Encomium of Richard III, Thomas More, War, William Cecil
They died on the same day …
15 November 1558 – Deaths of Queen Mary I, known as Bloody Mary for her executions of Protestants, and her Archbishop of Canterbury, Cardinal Reginald Pole.
Mary's accession marked a return to Catholicism for England after her father Reformation and her brother's passion for Protestantism. Many Protestants were executed, including Thomas Cranmer, Henry VIII's Archbishop of Canterbury.
As the first Queen Regnant in English history, Mary faced several problems, not least who to marry. Marrying a subject meant that he might be seen to hold more power than her and would give him huge authority. A match with a foreign prince was seen as an invitation to a foreign king to rule England. Her union with Phillip II of Spain was carefully constructed to deny him power but was deeply unpopular.
Reginald Pole was the grandson of George, Duke of Clarence. His mother had been controversially executed by Henry VIII as had his oldest brother. Pole lived much of his life in exile being courted by the Catholic powers of Europe.
One Papist plot revolved around marrying Pole to Mary and deposing Henry VIII with the couple to join the remnants of the House of York to the House of Tudor. Because of this, Reginald was viewed as a dangerous threat by Henry.
Mary and Reginald coincidentally died on the same day, closing a chapter in English history as the country would never again return to Catholicism. Their deaths also finally ended the last plot of the Wars of the Roses. Was this the real end date of a hundred years of civil war?
https://mattlewisauthor.wordpress.com/2014/10/12/the-fate-of-the-house-of-york/
http://www.amazon.co.uk/The-Wars-Roses-Struggle-Supremacy/dp/1445646358
Incidentally, Sir Geoffrey Pole also died that November.
Posted by super blue in religion and tagged Archbishop Cranmer, de heretico comburendo, executions, George Duke of Clarence, Henry Lord Montagu, Henry VIII, Margaret of Salisbury, Mary I, Phillip II, plots, Reginald Cardinal Pole, Sir Geoffrey Pole, Wars of the Roses


What kind of relation is defined between models A and B by invoking ForeignKey(A) in the class definition for model B?
One to one: each instance of A corresponds to a unique instance of B.
One to many: each instance of B belongs to an instance of A.


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A country star looking for a comeback has one last shot at fame—and he might just have one last shot at love.
Naomi Mallard is a fixer by nature. And as PR manager for Nashville's Shooting Stars record label, she's facing her biggest fix: redeeming country music bad boy Chance Colburn. But in Naomi's eyes, a police record and a stint in rehab are the least of Chance's sins. He has spent his life running from demons and making tabloid headlines that have sent his career into a tailspin. Now he's struggling to find his muse and maintain his newfound sobriety, all while counting on the woman he once betrayed to repair his tattered reputation.
Naomi is determined to keep their relationship strictly professional, but that's not easy when an unexpected injury forces the former couple into disturbingly close proximity. Will mending their once-broken relationship be Naomi's best save yet? Or will Chance's past wreck any hope for a future together?
Falling Star 5 out of 5 based on 0 ratings. 1 reviews.
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text:
Q: Sonata Admin general roles I wanna use the Role Handler security on my Sonata admin dashboard. I work with Symfony 2.3.
In the doc, I have:

Each permission is relative to an admin: if you try to get a list in
  FooAdmin (declared as sonata.admin.demo.foo service), Sonata will
  check if the user has the ROLE_SONATA_ADMIN_DEMO_FOO_EDIT role.

As I understand, if I have services such as:

*

*sonata.admin.article

*sonata.admin.user

*sonata.admin.tag
Then I need to create an edit role, being a list of those 3 elements:
ROLE_SONATA_ADMIN_ARTICLE_EDIT and ROLE_SONATA_ADMIN_USER_EDIT and ROLE_SONATA_ADMIN_TAG_EDIT
But I would rather like to create access more generals, for example, in my case, simply do: ROLE_SONATA_ADMIN_EDIT instead and of a list of three.
Is there a simple way to do this with this bundle?

A: You can easily do this by overriding the Sonata\AdminBundle\Security\Handler\RoleSecurityHandler class and getBaseRole method:
# AppBundle/Security/Handler/MyRoleSecurityHandler.php

namespace AppBundle\Security\Handler;

use Sonata\AdminBundle\Admin\AdminInterface;
use Sonata\AdminBundle\Security\Handler\RoleSecurityHandler;

class MyRoleSecurityHandler extends RoleSecurityHandler
{

   /**
    * {@inheritDoc}
    */
   public function getBaseRole(AdminInterface $admin)
   {
        return 'ROLE_SONATA_ADMIN_%s';
   }
}

overwrites the sonata service related to this class:
# AppBundle/Resources/config/services.yml
services:
    #...

    sonata.admin.security.handler.role:
        class: AppBundle\Security\Handler\MyRoleSecurityHandler
        public: false
        arguments: [@security.context, [ROLE_SUPER_ADMIN]]

remember declare these roles in your hierarchy:
# app/config/security.yml

security:
    role_hierarchy:
        # ...
        ROLE_SONATA_ADMIN_LIST: ~
        ROLE_SONATA_ADMIN_SHOW: ~
        ROLE_SONATA_ADMIN_EDIT: ~
        ROLE_SONATA_ADMIN_DELETE: ~
        # etc.

once you assign these roles to the user, finally you can to check:
# inside of any admin class

protected function configureListFields(ListMapper $listMapper)
{
    if ($this->isGranted('EDIT')) {
       # ...
    }
}

Warning! The previous sonata roles (ROLE_SONATA_ADMIN_ARTICLE_EDIT, ROLE_SONATA_ADMIN_USER_EDIT, etc.) it will no work. So you could also override the class and the corresponding service of sonata-project/user-bundle/Security/EditableRolesBuilder.php to return only the hierarchy of roles.

redpajama_set_name: RedPajamaStackExchange


text:
Structure formation in binary mixtures of surfactants: vesicle opening-up to bicelles and octopus-like micelles
Hiroshi Noguchi Institute for Solid State Physics, University of Tokyo, Kashiwa, Chiba 277-8581, Japan
Micelle formation in binary mixtures of surfactants is studied using a coarse-grained molecular simulation. When a vesicle composed of lipid and detergent types of molecules is ruptured, a disk-shaped micelle, the bicelle, is typically formed. It is found that cup-shaped vesicles and bicelles connected with worm-like micelles are also formed depending on the surfactant ratio and critical micelle concentration. The obtained octopus shape of micelles agree with those observed in the cryo-TEM images reported in [S. Jain and F. S. Bates, Macromol. 37, 1511 (2004).]. Two types of connection structures between the worm-like micelles and the bicelles are revealed.
Amphiphilic molecules, such as lipids and detergents, self-assemble various structures in aqueous solutions Israelachvili (2011); Safran (1994); Jain and Bates (2003); Seddon et al. (2004); Caffrey (2009); Ujwal and Bowie (2011); Walter et al. (1991); Yamada et al. (2009); Jain and Bates (2004) . In solutions of a single type of simple surfactant, the structure of the aggregates is qualitatively understood by the relative size of their hydrophilic parts Israelachvili (2011); Safran (1994) . Cone-shaped molecules form spherical or worm-like micelles, cylindrical molecules form bilayer membranes, and inverted cone-shaped molecules form inverted hexagonal structures, or inverted micelles. Mixtures of different types of surfactants show more variety of self-assembled structures than single-component systems. The edges of bilayer membranes can be stabilized by cone-shaped surfactants. Hence, discoidal bilayer membranes called bicelles (bilayered micelles) or pores on the membranes are formed Seddon et al. (2004); Caffrey (2009); Ujwal and Bowie (2011); Walter et al. (1991); Yamada et al. (2009) . Recently, an undulating cylinder and a bilayer disk connected with several worm-like micelles, which shape looks like an octopus or jelly-fish, have been observed in binary mixtures of diblock copolymers by cryo-TEM Jain and Bates (2004) . When compared with the structures of single-component systems, multi-component self-assembled structures are not well understood.
Mixtures of lipids and detergents are used for solubilization, reconstruction, and crystallization of membrane proteins Seddon et al. (2004); Caffrey (2009) . In particular, a bicelle is an excellent medium to investigate protein functions Sanders and Prosser (1998); Ujwal and Bowie (2011) . The proteins maintain their functionality in the bicelles Czerski and Sanders (2000) , and magnetically aligned bicelles are used for NMR studies Angelis and Opella (2007) . The structures of several proteins have been determined by the bicelle method Ujwal and Bowie (2011); Faham and Bowie (2002) .
The dynamics of micelle-to-vesicle transitions have been studied experimentally by time-resolved scatting techniques (light, neutron, and X-ray) Leng et al. (2002); Weiss et al. (2005); Bryskhe et al. (2005); Madenci et al. (2011); Gummel et al. (2011) . Typically, the surfactants aggregate into disk-like micelles, which grow and transform into vesicles when their radii exceed a critical size Fromherz (1983) . Since fusion between vesicles is very slow, the size of the first-formed vesicles is maintained in the time scale of experiments. Thus, the vesicle size is determined by kinetics rather than by thermal equilibrium. In the opposite transition from vesicles to micelles, various pathways of the solubilization of liposomes are observed depending on the types of lipids and detergents Nomura et al. (2001); Sudbrack et al. (2011); Tomita et al. (2011); Elsayed and Cevc (2011); Hamada et al. (2012) : Rhythmic shrinkage, bursting, budding, peeling, and inside-out inversion.
Recently, multi-component bilayer membranes have been intensively investigated, since they are believed to play important roles in living cells. Several patterns of phase-separated domains have been observed on giant liposomes Baumgart et al. (2003); Veatch and Keller (2003); Gudheti et al. (2007); Collins and Keller (2008); Yanagisawa et al. (2008); Christian et al. (2009); Bagatolli and Kumar (2009) , and the spontaneous curvature produced by proteins or glycolipids induce a local high curvature such as in a membrane tube Baumgart et al. (2010); Phillips et al. (2009); Shnyrova et al. (2009); Akiyoshi et al. (2003) . The domain formations and morphological changes of the vesicles can be observed by optical microscopy. However, the structure dynamics of micelle formation are much more difficult to investigate; since their size are 10nm scale, electron microscopy has to be used for direct observation.
When molecular simulations are used, the structure formation in molecular scales can be revealed in detail. In contrast to the fact that many simulations have been performed on domain formation in membranes Bagatolli and Kumar (2009); Taniguchi (1996); Kohyama et al. (2003); Laradji and Sunil Kumar (2005); Huang et al. (2011); Hu et al. (2011) , the structure formation of micelles is much less explored. In this paper, we study various structures of binary mixtures using a coarse-grained molecular simulation.
Although computer technology has grown, the typical scale for recent simulations of atomistic models is only 100 ns dynamics of hundreds of lipid molecules. In order to simulate bilayer membranes on longer and larger scales, various types of coarse-grained molecular models have been proposed (see review articles Müller et al. (2006); Venturoli et al. (2006); Noguchi (2009); Marrink et al. (2009) ). Recently, the bottom-up approaches were taken to construct coarse-grained molecular models, where potential parameters are tuned from atomistic simulations Marrink et al. (2004); Izvekov and Voth (2005); Arkhipov et al. (2008); Shinoda et al. (2008); Wang and Deserno (2010); Shinoda et al. (2011) . On the other hand, we choose a top-down approach to construct coarse-grained molecular models, where potentials are based on the continuum theory. Here, one of the solvent-free molecular models Noguchi (2011) is employed. In this model, the membrane properties such as the bending rigidity and spontaneous curvature of the monolayer can be varied over wide ranges.
In Sec. II, the surfactant model and simulation method are described. In Sec. III, the membrane properties of the phase boundary are investigated using the planar membranes with straight edges or pores. The line tension of the phase boundary is estimated in Sec. III.1. The phase segregation around the membrane edges and the pore shapes on the phase boundary are described in Secs. III.2 and III.3, respectively. In Sec. IV, the opening-up of the two-component vesicles are explored. Various structures including octopus-like micelles are obtained. The summary and discussion are given in Sec. V.
Ii Simulation Model and Method
ii.1 Surfactant Model
A solvent-free molecular model Noguchi (2011) is used to simulate two-component surfactant mixtures. We consider NA molecules of type A and NB molecules of type B. The type B molecule is a lipid with a cylindrical shape (the spontaneous curvature of the monolayer C0=0). The type A molecule is a model of a detergent or lipid molecule with a cylindrical or cone shape with a relatively large head (C0≥0).
Each (i-th) molecule has a spherical particle with an orientation vector ui, which represents the direction from the hydrophobic to the hydrophilic part. There are two points of interaction in the molecule: the center of a sphere rsi and a hydrophilic point rei=rsi+uiσ. The molecules interact with each other via the potential,
UkBT = ∑i<jUrep(rsij)+∑iεi Uatt(ρi) (1)
+ ktilt2∑i<j[(ui⋅^rsij)2+(uj⋅^rsij)2]wcv(reij)
+ kbend2∑i<j(ui−uj−Cijbd^rsij)2wcv(reij)
+ εAB∑i<NA,j≥NAUAB(rsij),
where rij=ri−rj, rij=|rij|, ^rij=rij/rij, and kBT is the thermal energy. Here, type A molecules are considered for 0≤i<NA and type B for NA≤i<N=NA+NB.
The molecules have an excluded volume with a diameter σ via the repulsive potential, Urep(r)=exp[−20(r/σ−1)], with a cutoff at r=2.4σ. The second term in Eq. (1) represents the attractive interaction between the molecules. The two types of molecules can have different attractive strengths: εi=εAatt for 0≤i<NA and εi=εBatt for NA≤i<N. An attractive multibody potential Uatt(ρi) is employed to mimic the "hydrophobic" interaction. The potential Uatt(ρi) is given by
Uatt(ρi)=0.25ln[1+exp{−4(ρi−ρ∗)}]−C, (2)
with C=0.25ln{1+exp(4ρ∗)}. The local particle density ρi is approximately the number of particles rsi in the sphere with radius ratt.
ρi=∑j≠ifcut(rsij), (3)
where fcut(r) is a C∞ cutoff function Noguchi and Gompper (2006) ,
fcut(r)={exp{A0(1+1(r/rcut)n−1)}(r<rcut)0(r≥rcut) (4)
with n=6, A0=ln(2){(rcut/ratt)n−1}, ratt=1.9σ (fcut(ratt)=0.5), and the cutoff radius rcut=2.4σ. The density ρ∗ in Uatt(ρi) is the characteristic density, above which the pairwise attractive interaction is smoothly cut off.
The third and fourth terms in Eq. (1) are discretized versions of the tilt and bending potentials of the tilt model Hamm and Kozlov (1998, 2000) , respectively. This type of bending potential was also used in other coarse-grained lipid models Noguchi (2003); Farago and Grønbech-Jensen (2009) . A smoothly truncated Gaussian function Noguchi and Gompper (2006) is employed as the weight function
wcv(r)=⎧⎨⎩exp((r/rga)2(r/rcc)n−1)(r<rcc)0(r≥rcc) (5)
with n=4, rga=1.5σ, and rcc=3σ. The spontaneous curvatures of the monolayer membranes are varied by parameters CAbd and CBbd: Cijbd=(Cibd+Cjbd)/2, Cibd=CAbd for 0≤i<NA, and Cibd=CBbd for NA≤i<N. A single-component monolayer membrane has spontaneous curvature C0≃{kbend/(kbend+ktilt)}Cbd/σ Shiba and Noguchi (2011); Noguchi (2012) . In this paper, we use kbend=ktilt, i.e. C0≃Cbd/2σ.
The last term in Eq. (1) represents the repulsion between the different types of molecules by a monotonic decreasing function: UAB(r)=A1fcut(r) with n=1, A0=1, and rcut=2.4σ, and A1=exp[σ/(rcut−σ)] to set UAB(σ)=1.
ii.2 Simulation Method
The NVT ensemble (constant number of molecules N, volume V, and temperature T) is used with periodic boundary conditions in a box with side lengths Lx, Ly, and Lz. A Langevin thermostat is employed to keep the temperature. The motion of the center of the mass rGi=(rsi+rei)/2 and the orientation ui are given by underdamped Langevin equations:
drGidt = vGi, duidt=ωi, (6)
mdvGidt = −ζGvGi+gGi(t)+fiG, (7)
Idωidt = −ζrωi+(gri(t)+fir)⊥+λLui, (8)
where m and I denote the mass and the moment of inertia of the molecule, respectively. The forces are given by fiG=−∂U/∂rGi and fir=−∂U/∂ui with the perpendicular component a⊥=a−(a⋅ui)ui and a Lagrange multiplier λL to keep u2i=1. According to the fluctuation-dissipation theorem, the friction coefficients ζG and ζr and the Gaussian white noises gGi(t) and gri(t) obey the following relations: the average ⟨gβ1i,α1(t)⟩=0 and the variance ⟨gβ1i,α1(t1)gβ2j,α2(t2)⟩=2kBTζβ1δijδα1α2δβ1β2δ(t1−t2), where α1,α2∈{x,y,z} and β1,β2∈{G,r}.
The results are displayed with a length unit of σ, an energy unit of kBT, and a time unit of τ0=ζGσ2/kBT. The Langevin equations are integrated using the leapfrog algorithm Allen and Tildesley (1987); Noguchi (2011) with m=ζGτ0, I=ζrτ0, ζr=ζGσ2, and Δt=0.005τ0.
ii.3 Membrane Properties of Single-Component Membranes
The potential-parameter dependence of the membrane properties of single-component membranes (bending rigidity κ, area compression modulus, lateral diffusion coefficient, flip-flop rate, line tensions Γedge of membrane edge, and Γbr of branching junction) are investigated in detail in our previous papers Noguchi (2011, 2012) . In this model, these properties can be varied over wide ranges.
The membrane has a wide range of fluid phases, and the fluid-gel transition point can be controlled by ρ∗. The area compression modulus KA can be varied by ktilt. The flip-flop rate can be varied by ktilt and kbend. The bending rigidity κ is linearly dependent on ktilt and kbend as κ/kBT=2.2(ktilt+kbend)+bε(ε) at Cbd=0. The line tension Γedge of the membrane edge can be controlled by varying ε and Cbd. As Cbd increases, the line tension Γedge decreases. Consequently, the bilayer membranes become unstable at Γedge≃0, and instead worm-like micelles are formed.
In this paper, we use kbend=ktilt=4 or 8, ρ∗=14, and CBbd=0, so that type B molecules form a fluid membrane with κ/kBT=26 or 44 for εBatt=2, respectively. We use εBatt=2 except for Sec. III.1 where εBatt is varied with εAatt=εBatt. The monolayer (leaflet) of type B membrane has zero spontaneous curvature. For type A molecules, we use εAatt=1.5 or 2, and various CAbd. For εAatt=2, the molecules have a very low critical micelle concentration (CMC); No or a few isolated molecules are seen in the simulation box. For εAatt=1.5, the molecules have a low but finite value of CMC ∼10−4σ−3, which corresponds to 0.1mM for σ≃2nm. Vesicles and micelles can change their sizes by absorbing and dissolving type A molecules at εAatt=1.5. The simulations with εAatt=1.5 and 2 correspond to typical lipid-detergent mixtures and lipid-lipid mixtures, respectively.
The same number of type A and type B molecules are used for simulations of the planar membranes in Sec. III. In Secs. III.1 and III.3, NA=NB=512 are used. To investigate membrane pores (Sec. III.2), NA=NB=1,024, Lx=38σ, Ly=36σ, εAatt=εBatt=2, and kbend=8 are used. For most simulations of vesicle opening-up, the total number of molecule is fixed as N=4,000, and the number ratio is varied. In a few cases, NA=NB=1,000 are used. For the opening, kbend=ktilt=8 and Lx=Ly=Lz=100σ (N/V=0.004/σ3 for N=4,000) are used. The time unit is estimated as τ0∼0.1μs from the lateral diffusion coefficient ∼10−8cm2/s for phospholipids Wu et al. (1977) . We consider that micelles maintaining their shapes for an interval of 100,000τ0 (∼10ms) are in steady (meta)stable states. The error bars of data are estimated from three simulation runs.
Figure 1: Line tension ΓAB of the phase boundary of membrane domains in tensionless membranes. (a) Dependence on CAbd. The dashed and solid lines represent data for kbend=4 and 8, respectively. The symbols (□,⋄) and (∘,△) represent data for εAB=1 and 2, respectively, at εAatt=εBatt=2. The symbols (×) and (∗) represent data for εAB=1 and 2, respectively, at εAatt=1.5, εBatt=2, and kbend=8. (b) Dependence on εAB at kbend=8, εAatt=εBatt=2, and CAbd=0 (⋄), 0.4 (□), 0.6 (△), or 0.8 (∘). (c) ΓAB for various εBatt at εAatt=εBatt, kbend=8, CAbd=0, and εAB=1 (□) or 2 (∘). The error bars are smaller than the size of the symbols.
Figure 2: Surface tension γ dependence of the line tension ΓAB of the phase boundary at εAB=2, εAatt=εBatt=2, kbend=8, and CAbd=0 (⋄), 0.4 (□), or 0.6 (△). The error bars are smaller than the size of the symbols.
Iii Planar Membranes
iii.1 Line Tension of Phase Boundary
First, we estimate the line tension ΓAB of the boundary between the type A and B membrane domains. Two domains are prepared on the planar membrane along the xy plane, and two lines of the phase boundary are set parallel to the x axis. The line tension ΓAB is given by Tolpekina et al. (2004); Laradji and Sunil Kumar (2005); Reynwar and Deserno (2008)
ΓAB=⟨Pyy−Pxx⟩V/2Lx, (9)
where V=LxLyLz and 2Lx is the total boundary length. The diagonal components of the pressure tensor are given by
Pαα=(NkBT−∑iαi∂U∂αi)/V, (10)
where α∈{x,y,z}. We calculated ΓAB at three length ratios Ly/Lx=1.8, 2, and 2.2; and we checked that their differences were less than the statistical error bars. The membrane surface tension γmb is given by γmb=−⟨Pyy⟩Lz, since Pzz≃0 for solvent-free simulations with low CMC.
The line tension ΓAB can be controlled by εAB (see Fig. 1). It increases with increasing εAB and decreases with increasing CAbd. The CAbd dependence is qualitatively similar to that of the line tension Γedge of the membrane edges. On the other hand, the εatt dependence is different; ΓAB is almost independent of εatt [see Fig. 1(c)], while Γedge increases with increasing εBatt. Noguchi (2011)
The tension ΓAB slightly decreases with increasing surface tension γmb as shown in Fig. 2. The surface tension γmb is varied by changing the projected membrane area in the xy plane. The repulsive interaction between different types of molecules is likely to be reduced by the slightly larger distances of neighboring molecules at larger γmb.
Figure 3: Snapshots of a bilayer membrane with a pore at εAatt=εBatt=2, kbend=8, and CAbd=0.4. (a) εAB=1. (b) εAB=2. The red (yellow) and light blue (light yellow) hemispheres represent the hydrophilic (hydrophobic) parts of type A and type B molecules, respectively.
Figure 4: (a) Schematic representation of a pore on the phase boundary. (b) Pore transverse diameter Lpore and (c) the ratio LB/LA of edge lengths at εAatt=εBatt=2, kbend=8, and CAbd=0 (⋄), 0.2 (□), 0.4 (△), or 0.6 (∘). The solid lines with the symbols represent simulation data. The dashed lines are obtained from Eq. (13). The error bars are smaller than the size of the symbols.
iii.2 Pore on Phase Boundary
As the membrane area increases, increasing surface tension induces a pore opening in the membrane. In the phase-separated membrane, the pore stays on the phase boundary or in the domain with lower Γedge (see Fig. 3). Here, we investigate the pore position and shape in the phase-separated membranes for various CAbd and εAB.
The pore transverse diameter Lpore and edge length ratio LB/LA of type A and type B membranes are estimated as follows. First, the pore area is calculated using a particle-insertion method Tolpekina et al. (2004); Noguchi and Gompper (2006) . In the xy plane, 10,000 ghost particles with a hard-sphere diameter σ are distributed randomly, and then the particle placement is accepted if no overlap with the projections of the hard cores of the membrane particles occurs. Next, the molecules closer than 1.5σ to any ghost pore particle are considered to belong to the membrane edge. The neighbor distance between molecules are assumed to be same for the both domains, so the length ratio is given by the number ratio of molecules on the edge: LB/LA=NBpore/NApore. Two mutual contact points of the domain boundary and membrane edges are defined as the middle points between the nearest neighbor edge molecules of types A and B [see Fig. 4(a)]. The transverse diameter Lpore is given by the length between the two contact points along the x axis. Isolated ghost particles and molecules are not taken into account in the above calculations.
Figure 5: Bilayer membrane strip at εAatt=2, kbend=8, and CAbd=0.4. (a) Snapshot of partially phase-separated membranes at εAB=0.4. (b) Probability distribution in the y direction, which is taken along the eigenvector of the maximum eigenvalue of the 2D gyration tensor. The solid lines represent data for the type A at εAB=0, 0.4, 0.5, and 0.6. The dashed line represents data for the type B at εAB=0. The error bars are shown at several data points for εAB=0, 0.4, and 0.5. For εAB=0.6, the distribution calculated from a single run is shown.
At CAbd=0, the two domains are identical. Thus, the average pore shape is symmetric, and the edge lengths ⟨LA⟩ and ⟨LB⟩ of type A and type B membranes are equal (see Fig. 4). As CAbd increases, the center of the pore moves to the type A domain. As εAB increases, the pore elongates along the phase boundary, and ⟨LA⟩/⟨LB⟩ approaches unity.
Figure 6: Effective line tension Γ of the membrane edge at εAatt=2. (a) The squares (□) and circles (∘) represent data for CAbd=0.4 and 0.8, respectively, at kbend=8. The diamonds (⋄) and triangles (△) represent data for CAbd=0.4 and 0.8, respectively, at kbend=4. The dashed lines with (×) represent Γ=ΓA+ΓAB. (b) The triangles (△) and circles (∘) represent data for kbend=4 and 8, respectively, at CAbd=0. The error bars are smaller than the size of the symbols.
These pore shapes are understood by the Young equation and Laplace pressure. Three line tensions are balanced at the mutual contact points. Safran (1994); de Gennes et al. (2003)
ΓAB = ΓAcos(θA)+ΓBcos(θB),
ΓAsin(θA) = ΓBsin(θB), (11)
where ΓA and ΓB denote the line tensions of the membrane edges of the type A and type B domains, respectively [see Fig. 4(a)]. Therefore, the contact angle θA is written as
cos(θA)=Γ2AB+Γ2A−Γ2B2ΓAΓAB. (12)
The membrane edges of the domains have constant curvature radii rA and rB. The edge line tension is balanced with the two-dimensional Laplace pressure Δγ: ΓA=rAΔγ and ΓB=rBΔγ. The transverse diameter Lpore and edge lengths of each domain are given by
Lpore = 2rAsin(θA)=2rBsin(θB),
LA = 2rAθA, LB=2rBθB. (13)
Thus, the pore lengths are obtained from the line tensions and the surface tension difference Δγ. Since the pore has zero surface tension, Δγ is calculated as Δγ=γmb=−⟨Pyy⟩Lz. These analytical results qualitatively explain the simulation results (see Fig. 4). However, Lpore and LB/LA are underestimated in particular for the parameter sets close to the wetting transition points. These deviations are likely caused by the negligence of the thermal fluctuations in the theory or the finite size effects in the simulations.
In order to form bicelles with membrane edges covered by type A molecules, the complete wetting condition ΓB>ΓAB+ΓA is necessary: εAB≤1 at CAbd=0.4 and εAB≤2 at CAbd=0.6. At CAbd=0.8, a pore is unstable and worm-like micelles grow from the edge of the type A domain.
iii.3 Edge Effects on Phase Separation
Next, we consider a membrane strip, which has two open edges parallel to the x axis [see Fig. 5(a)]. Since the type A domain has low line tension ΓA<ΓB at CAbd>0, the type A molecules prefer to remain at the membrane edges. The probability of type A molecules is higher than that of the type B at the membrane edges even for εAB=0 [compare solid and dashed lines for εAB=0 in Fig. 5(b)]. The free-energy reduction of the edges is balanced with the mixing entropy of the two species. Similar concentrating effects were reported in the cases of the two-component vesicles Góźdź (2006) and a vesicle with a cylindrical micelle Greenall and Gompper (2011) , where components with higher spontaneous curvature are concentrated at the high curvature regions.
The effective line tension Γ of the membrane edge is estimated as
Γ=−⟨Pxx⟩V/2Lx. (14)
For single-component membranes, Γ gives the line tension of the membrane edges. For the phase-separated membranes, Γ gives the sum of the two line tensions: Γ=ΓA+ΓAB [compare dashed and solid lines in Fig. 6(a)]. Surprisingly, Γ decreases with increasing εAB at low εAB, where the two surfactants are in the mixing condition (see Fig. 5). This decrease is caused by the coverage of the membrane edges by type A molecules, which reduces the free energy of the edges. At the phase separation threshold Γ is minimum, and it increases with increasing εAB for completely phase-separated membranes. At εAB=0, Γ is slightly lower than Γedge for the mean spontaneous curvature Cbd=(CAbd+CBbd)/2, because of the high concentration of type A molecules at the edges [see Fig. 6(b)].
Figure 7: Sequential snapshots of bicelle formation from a vesicle at NA=NB=2,000, εAatt=1.5, εAB=1, and CAbd=0.8. (a) t=0. (b) t=1,000τ0. (c) t=1,200τ0. (d) t=4,000τ0. (e) t=5,000τ0. (f) t=12,000τ0. (g) t=28,000τ0. The snapshots in (a-f) are seen from the same viewpoint.
Figure 8: Time development of the bicelle formation at NA=NB=2,000, εAatt=1.5, εAB=1, and CAbd=0.7, 0.8, or 1. (a) The number of molecules ncl, (b) asphericity αsp, and (c) aplanality αpl of the largest cluster. The same data as in Fig. 7 are shown for CAbd=0.8.
Iv Vesicle Opening-Up
As the spontaneous curvature of the monolayer is increased by changing Cbd (C0≃Cbd/2σ), single-component vesicles are ruptured, and these vesicles subsequently transform into branched worm-like micelles Noguchi (2011) . For two-component vesicles, the number ratio of the components and the line tension ΓAB of the phase boundary are also key parameters. First, we describe the vesicle opening-up for εAatt=1.5, where type A molecules have finite CMC. The vesicle rupture occurs by changing CAbd or ΓAB. Next, we describe the case for εAatt=2, where both types of molecules have negligibly small CMC. We call the former and latter mixtures lipid-detergent mixtures and lipid-lipid mixtures, respectively.
Figure 9: Snapshots of a cup-shaped vesicle at NA=400, NB=3,600, εAatt=1.5, εAB=1, and CAbd=0.8. All molecules and type A molecules are shown in (a) and (b), respectively.
Figure 10: Sequential snapshots of bicelle formation from a vesicle at NA=3,000, NB=1,000, εAatt=1.5, εAB=0, and CAbd=1. (a) t=100τ0. (b) t=1,000τ0. (c) t=20,000τ0. (d) t=100,000τ0. All snapshots are seen from the same viewpoint.
iv.1 Lipid-Detergent Mixtures
Typical examples of bicelle formation in lipid-detergent mixtures at NA/NB=1 are shown in Figs. 7 and 8. The vesicle is equalibrated at εAB=0 and subsequently εAB is suddenly changed to εAB=1 at t=0. After the change, the molecules form domains, and then a pore opens in a type A domain [see Figs. 7(a), (b)]. The pore grows along the type A domain and the vesicle opens up [see Figs. 7(c), (d)]. In Fig. 7(d), a bicelle and a worm-like micelle are detached from the largest cluster. The type A domain within the large bicelle diffuses to the membrane edge and fuses the other type A domain surrounding the type B bilayer disk [see Fig. 7(e)]. As consequence of the domain fusion, two worm-like micelles connected with the bicelle are formed [see Fig. 7(f)]. After a while, the worm-like micelles are detached, and a large discoidal bicelle is formed [see Fig. 7(g)]. A movie for another example of the opening dynamics at Cbd=0.8 is provided in ESI (Movie 1). In the movie, closure of a small pore occurs inside a bilayer disk during the bicelle formation.
At larger Cbd, the vesicle opening begins earlier in average, since a pore can open in a smaller domain. The connections between bicelles and worm-like micelles have longer lifetimes at smaller Cbd. The time development of the largest clusters is shown in Fig. 8. The i-th and j-th molecules are considered to belong to the same cluster at rsij<ratt. The number of molecules ncl in the largest cluster decreases in a stepwise manner as the micelles undergo detachment. The shape of the clusters can be characterized by the ratios of the three eigenvalues λ1,λ2,λ3 of the gyration tensors aαβ=(1/ncl)∑i(αsi−αG)(βsi−βG), where the center of the mass αG=(1/ncl)∑iαsi and α,β∈x,y,z. The asphericity αsp Rudnick and Gaspari (1986) and aplanarity αpl Noguchi and Gompper (2006) are defined as
αsp = (λ1−λ2)2+(λ2−λ3)2+(λ3−λ1)22(λ1+λ2+λ3)2, (15)
αpl = 9λ1λ2λ3(λ1+λ2+λ3)(λ1λ2+λ2λ3+λ3λ1), (16)
to quantify the degrees of deviation from a spherical shape and planar shape, respectively. These two quantities are convenient measures to distinguish spherical, discoidal, and cylindrical shapes: (αsp,αpl)=(0,1) for spheres, (αsp,αpl)=(1,0) for thin rods, and (αsp,αpl)=(0.25,0) for thin disks. As a vesicle opens up, αsp and αpl show a rapid increase and decrease, respectively. After the worm-like micelles are detached, the bicelle has a disk shape, (αsp,αpl)≃(0.25,0).
Figure 11: Sequential snapshots of a racket-like bicelle formation at NA=NB=1,000, εAatt=2, εAB=2, and CAbd=0.8. (a) t=8,500τ0. (b) t=9,000τ0. (c) t=10,000τ0. (d) t=48,000τ0. (e) t=60,000τ0.
Figure 12: Time development of (a) asphericity αsp and (b) aplanality αpl at NA=NB=1,000, εAatt=2, εAB=2, and CAbd=0.8. The same data as in Fig. 11 are shown.
When type A molecules are too few to cover the circumference of the bilayer disk, a cup-like vesicle can be formed. Figure 9 shows a stable cup-like vesicle. The chemical potential of type A molecules surrounding the rim is balanced with the bulk chemical potential. Similar stable cup-like vesicles are experimentally observed for liposomes with talins. Saitoh et al. (1998)
When vesicles contain many type A molecules, the vesicles are ruptured even at εAB=0. At NA/NB=3, the rupture begins as soon as a sufficiently high spontaneous curvature is added by changing CAbd=0 to 1 (see Fig. 10). First, a branched worm-like micelle is formed like in the single-component case. Then, however, type B molecules assemble into the branching junctions and form bilayer membranes unlike in the single-component case [see a bicelle with three arms in the top right of Fig. 10(c)]. Finally, bicelles and worm-like micelles without branches are formed. As discussed in Sec. III.3, inhomogeneous curvature inside of micelles induces phase segregation. Furthermore, the segregation induces morphological changes of micelles. Thus, the phase segregation and morphological changes can be coupled in micelle formation.
iv.2 Lipid-Lipid Mixtures
In lipid-lipid mixtures, the number of molecules in surfactant aggregates are changed principally only via fission or fusion of aggregates, since the both surfactants have negligibly small CMC. Figures 11 and 12 show the opening dynamics from a phase-separated vesicle at N=2,000 and CAbd=0.8. First, the opened membrane forms a bicelle. This bicelle maintains its shape for 38,000τ0. Then, a worm-like micelle grows from a bicelle edge, and a racket-like micelle is formed [see Figs. 11(d), (e)]. The excess type A molecules in the bicelle rim move to the worm-like micelle. The bicelle and racket-like micelle can be distinguished by αsp and αpl (see Fig. 12). The worm-like micelle is not detached unlike in the finite CMC simulation at εAatt=1.5. We checked the racket shape is maintained for 100,000τ0. At NA=NB=2,000 and CAbd=0.8, the vesicles are not ruptured. Since higher curvature of smaller vesicles slightly reduces a free-energy barrier of the pore opening, the vesicle rupture occurs more frequently in smaller vesicles.
For vesicles with a high spontaneous curvature at CAbd=1, ruptured membranes transform into bicelles connected with several worm-like micelles (see Fig. 13). Movies 2 and 3 in ESI show the formation dynamics of the octopus-like micelles in Figs. 13(a) and (c), respectively. After the change from εAB=0 to 2, type A molecules assemble to form domains. As the domains become sufficiently large, the membranes in the type A domains are ruptured and the excess molecules form connected worm-like micelles. These processes are similar to those in lipid-detergent mixtures shown in Fig. 7. However, the later processes are different. Type A molecules do not form a circular rim surrounding type B domains. Instead, worm-like micelles are directly connected to the bilayer disk of the type B domains as shown in Fig. 13(a). These worm-like micelles are stable and their lengths are fixed in long simulation runs. At the side of the connection junctions, the membrane edges of the type B domain are locally exposed in vapor (solvent) space.
When multiple pores are opened at the same time, small pores are closed and the worm-like micelles on the pores are detached. If all the pores are closed, polyhedral vesicles are formed [see Fig. 13(b)]. The asymmetric molecular distribution of the inner and outer leaflets can generate a spontaneous curvature of the bilayer in the type A domains. Hence, the type A domains remain at the vertices with higher curvatures. The formation of similar polyhedral vesicles has been reported in experiments Veatch and Keller (2003); Gudheti et al. (2007) and other simulations Huang et al. (2011); Hu et al. (2011) . A large pore often remains and a cup-like vesicle connected with several worm-like micelles is formed as a steady state [see Fig. 13(c) and Movie 3].
Figure 13: Snapshots of various obtained morphologies of surfactant aggregates at NA=NB=2,000, εAatt=2, εAB=2, and CAbd=1.
When the spontaneous curvature of the octopus-like micelles is changed from CAbd=1 to 0.8, type A molecules form the rim of the bilayer disk connected with worm-like micelles like the micelle shown in Fig. 11. The number of connected worm-like micelles decreases gradually because of the length fluctuations due to thermal diffusion. Type A molecules in removed short micelles move to remaining long micelles. a few long worm-like micelles still exist after long simulation runs. The cup-like vesicles with worm-like micelles are opened up into flat bicelles. When the value of CAbd is turned again set as CAbd=1, the connection structure transforms back to that shown in Fig. 13(a). Thus, these are not kinetically trapped structures but local equilibrium structures. For high spontaneous curvature at CAbd=1, the saddle structure at the side of the connection becomes unstable so that the cylindrical structure directly connects to the type B domain despite partial exposure of the type B membrane edges.
V Summary and Discussion
We have found various morphologies of micelles in mixtures of two types of amphiphilic molecules. For lipid-detergent mixtures, bicelle and worm-like micelles without branches are formed in dilute solutions. The detergent-type molecules stabilize the edges of the bilayer disks. On the other hand, for lipid-lipid mixtures, it is found that the worm-like micelles are stably connected with bicelles.
Two types of connection structures between the bicelle and worm-like micelles are found. At a medium spontaneous curvature of the type A monolayer, worm-like micelles of type A molecules are connected with the circular type A domain surrounding the type B domain. At a high spontaneous curvature, worm-like micelles are directly connected with the type B domain. Worm-like micelles are connected with each other though the rim consisting of the type A domain in the first case (the round-shaped connection) while the absent for the direct connection in the second case. These octopus-like morphologies resemble the cryo-TEM images of diblock copolymer mixtures Jain and Bates (2004) . These diblock copolymers have negligibly small CMC, similar to phospholipids. Since the connection points are round in the cryo-TEM images, the structure is likely the former round-type connection structures; the rim and octopus arms are made of one type of copolymer with a relatively longer hydrophilic chain. Our simulation suggests that the octopus-shaped micelles are generally formed in binary mixtures of negligibly-low-CMC surfactants. Hence, similar octopus-like micelles can be constructed in binary mixtures of cone-shaped lipids and cylindrical-shaped lipids.
During the solubilization of vesicles in lipid-detergent mixtures, octopus-like micelles appear as temporal structures. Such temporal structures were considered in some experimental studies Walter et al. (1991); Elsayed and Cevc (2011) . Our simulation results support the existence of these intermediate structures.
To control micelle morphology, several key quantities require to be tuned. The spontaneous curvature of the monolayer or the packing parameter Israelachvili (2011) of the surfactants determines stable local structure of each phase domain. The ratio of line tensions of the phase boundary and membrane edges determines the wetting condition for the membrane edges. The contact angles of a pore on the phase boundary are given by the Young equation. At finite CMC, the excess surfactant can be dissolved from the micelles, and the composition of surfactants can be adjusted to their stable shapes. On the other hand, at negligibly low CMC, the number of surfactant molecules can be conserved in micelles. Hence, discoidal and cylindrical structures can coexist in a single micelle, where the excess amount of cone-shaped molecules to surround the circumference form connected worm-like micelles. The micelle size can be controlled by kinetics as well as the volume fractions of the surfactants. The lipid domain size at the time of vesicle rupture determines the resulting bicelle size.
In this paper, we focus on micelle formation from a vesicle. The size and shape of micelles depend on initial conditions. Self-assembly from molecules randomly dissolved in solutions produces smaller sizes of micelles. Micelle formation by self-assembly or other initial conditions will be explored in further studies.
This study is partially supported by a Grant-in-Aid for Scientific Research on Priority Area "Molecular Science of Fluctuations toward Biological Functions" from the Ministry of Education, Culture, Sports, Science, and Technology of Japan.
Israelachvili (2011) J. N. Israelachvili, Intermolecular and Surface Forces (Academic Press, Burlington, MA, 2011), 3rd ed.
Safran (1994) S. A. Safran, Statistical Thermodynamics of Surfaces, Interfaces, and Membranes (Addison-Wesley, Reading, MA, 1994).
Jain and Bates (2003) S. Jain and F. S. Bates, Science 300, 460 (2003).
Seddon et al. (2004) A. M. Seddon, P. Curnow, and P. J. Booth, Biochim. Biophys. Acta 1666, 105 (2004).
Caffrey (2009) M. Caffrey, Annu. Rev. Biophys. 38, 29 (2009).
Ujwal and Bowie (2011) R. Ujwal and J. U. Bowie, Methods 55, 337 (2011).
Walter et al. (1991) A. Walter, P. K. Vinson, A. Kaplun, and Y. Talmon, Biophys. J. 60, 1315 (1991).
Yamada et al. (2009) N. L. Yamada, M. Hishida, and N. Torikai, Phys. Rev. E 79, 032902 (2009).
Jain and Bates (2004) S. Jain and F. S. Bates, Macromol. 37, 1511 (2004).
Sanders and Prosser (1998) C. R. Sanders and R. S. Prosser, Struct. 6, 1227 (1998).
Czerski and Sanders (2000) L. Czerski and C. R. Sanders, Anal. Biochem. 284, 327 (2000).
Angelis and Opella (2007) A. A. D. Angelis and S. J. Opella, Nat. Protoc. 2, 2332 (2007).
Faham and Bowie (2002) S. Faham and J. U. Bowie, J. Mol. Biol. 316, 1 (2002).
Leng et al. (2002) J. Leng, S. U. Egelhaaf, and M. E. Cates, Europhys. Lett. 59, 311 (2002).
Weiss et al. (2005) T. M. Weiss, T. Narayanan, C. Wolf, M. Gradzielski, P. Panine, S. Finet, and W. I. Helsby, Phys. Rev. Lett. 94, 038303 (2005).
Bryskhe et al. (2005) K. Bryskhe, S. Bulut, and U. Olsson, J. Phys. Chem. B 109, 9265 (2005).
Madenci et al. (2011) D. Madenci, A. Salonen, P. Schurtenberger, J. S. Pedersen, and S. U. Egelhaaf, Phys. Chem. Chem. Phys. 13, 3171 (2011).
Gummel et al. (2011) J. Gummel, M. Sztucki, T. Narayanan, and M. Gradzielski, Soft Matter 7, 5731 (2011).
Fromherz (1983) P. Fromherz, Chem. Phys. Lett. 94, 259 (1983).
Nomura et al. (2001) F. Nomura, M. Nagata, T. Inaba, H. Hiramatsu, H. Hotani, and K. Takiguchi, Proc. Natl. Acad. Sci. USA 98, 2340 (2001).
Sudbrack et al. (2011) T. P. Sudbrack, N. L. Archilha, R. Itri, and K. A. Riske, J. Phys. Chem. B 115, 269 (2011).
Tomita et al. (2011) T. Tomita, T. Sugawara, and Y. Wakamoto, Langmuir 27, 10106 (2011).
Elsayed and Cevc (2011) M. M. A. Elsayed and G. Cevc, Biochim. Biophys. Acta 1808, 140 (2011).
Hamada et al. (2012) T. Hamada, H. Hagihara, M. Morita, M. C. Vestergaard, Y. Tsujino, and M. Takagi, J. Phys. Chem. Lett. 3, 430 (2012).
Baumgart et al. (2003) T. Baumgart, S. T. Hess, and W. W. Webb, Nature 425, 821 (2003).
Veatch and Keller (2003) S. Veatch and S. L. Keller, Biophys. J. 85, 3074 (2003).
Gudheti et al. (2007) M. V. Gudheti, M. Mlodzianoski, and S. T. Hess, Biophys. J. 93, 2011 (2007).
Collins and Keller (2008) M. D. Collins and S. L. Keller, Proc. Natl. Acad. Sci. USA 105, 124 (2008).
Yanagisawa et al. (2008) M. Yanagisawa, M. Imai, and T. Taniguchi, Phys. Rev. Lett. 100, 148102 (2008).
Christian et al. (2009) D. A. Christian, A. Tian, W. G. Ellenbroek, I. Levental, K. Rajagopal, P. A. Janmey, A. J. Liu, T. Baumgart, and D. E. Discher, Nat. Mater. 8, 843 (2009).
Bagatolli and Kumar (2009) L. Bagatolli and P. B. S. Kumar, Soft Matter 5, 3234 (2009).
Baumgart et al. (2010) T. Baumgart, B. R. Capraro, C. Zhu, and S. L. Das, Annu. Rev. Phys. Chem. 62, 483 (2010).
Phillips et al. (2009) R. Phillips, T. Ursell, P. Wiggins, and P. Sens, Nature 459, 379 (2009).
Shnyrova et al. (2009) A. V. Shnyrova, V. A. Frolov, and J. Zimmerberg, Curr. Biology 19, R772 (2009).
Akiyoshi et al. (2003) K. Akiyoshi, A. Itaya, S. M. Nomura, N. Ono, and K. Yoshikawa, FEBS Lett. 534, 33 (2003).
Taniguchi (1996) T. Taniguchi, Phys. Rev. Lett. 76, 4444 (1996).
Kohyama et al. (2003) T. Kohyama, D. M. Kroll, and G. Gompper, Phys. Rev. E 68, 061905 (2003).
Laradji and Sunil Kumar (2005) M. Laradji and P. B. Sunil Kumar, J. Chem. Phys. 123, 224902 (2005).
Huang et al. (2011) C. Huang, H. Yuan, and S. Zhang, Appl. Phys. Lett. 98, 043702 (2011).
Hu et al. (2011) J. Hu, T. Gruhn, and R. Lipowsky, Soft Matter 7, 6092 (2011).
Müller et al. (2006) M. Müller, K. Katsov, and M. Schick, Phys. Rep. 434, 113 (2006).
Venturoli et al. (2006) M. Venturoli, M. M. Sperotto, M. Kranenburg, and B. Smit, Phys. Rep. 437, 1 (2006).
Noguchi (2009) H. Noguchi, J. Phys. Soc. Jpn. 78, 041007 (2009).
Marrink et al. (2009) S. J. Marrink, A. H. de Vries, and D. P. Tieleman, Biochim. Biophys. Acta 1788, 149 (2009).
Marrink et al. (2004) S. J. Marrink, A. H. de Vries, and A. E. Mark, J. Phys. Chem. B 108, 750 (2004).
Izvekov and Voth (2005) S. Izvekov and G. A. Voth, J. Phys. Chem. B 109, 2469 (2005).
Arkhipov et al. (2008) A. Arkhipov, Y. Yin, and K. Schulten, Biophys. J. 95, 2806 (2008).
Shinoda et al. (2008) W. Shinoda, R. DeVane, and M. L. Klein, Soft Matter 4, 2454 (2008).
Wang and Deserno (2010) Z. J. Wang and M. Deserno, J. Phys. Chem. B 114, 11207 (2010).
Noguchi (2011) H. Noguchi, J. Chem. Phys. 134, 055101 (2011).
Noguchi and Gompper (2006) H. Noguchi and G. Gompper, Phys. Rev. E 73, 021903 (2006).
Hamm and Kozlov (1998) M. Hamm and M. M. Kozlov, Eur. Phys. J. B 6, 519 (1998).
Hamm and Kozlov (2000) M. Hamm and M. M. Kozlov, Eur. Phys. J. E 3, 323 (2000).
Noguchi (2003) H. Noguchi, Phys. Rev. E 67, 041901 (2003).
Farago and Grønbech-Jensen (2009) O. Farago and N. Grønbech-Jensen, J. Am. Chem. Soc. 131, 2875 (2009).
Shiba and Noguchi (2011) H. Shiba and H. Noguchi, Phys. Rev. E 84, 031926 (2011).
Noguchi (2012) H. Noguchi, Soft Matter 8, 3146 (2012).
Allen and Tildesley (1987) M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids (Clarendon Press, Oxford, 1987).
Wu et al. (1977) E. S. Wu, K. Jacobson, and D. Papahadjopoulos, Biochemistry 16, 3936 (1977).
Tolpekina et al. (2004) T. V. Tolpekina, W. K. den Otter, and W. J. Briels, J. Chem. Phys. 121, 8014 (2004).
Reynwar and Deserno (2008) B. J. Reynwar and M. Deserno, Bioinerphases 3, FA117 (2008).
de Gennes et al. (2003) P. G. de Gennes, F. Brochard-Wyart, and D. Quere, Capillarity and Wetting Phenomena: Drops, Bubbles, Perls, Waves (Springer, New York, 2003).
Góźdź (2006) W. T. Góźdź, J. Phys. Chem. B 110, 21981 (2006).
Greenall and Gompper (2011) M. J. Greenall and G. Gompper, Langmuir 27, 3416 (2011).
Rudnick and Gaspari (1986) J. Rudnick and G. Gaspari, J. Phys. A: Math. Gen. 19, L191 (1986).
Saitoh et al. (1998) A. Saitoh, K. Takiguchi, Y. Tanaka, and H. Hotani, Proc. Natl. Acad. Sci. USA 95, 1026 (1998).

redpajama_set_name: RedPajamaCommonCrawl