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The Free Library > Date > 2017 > January > 1 > International Journal of Polymer Science
Facile TEMPO Immobilization onto Poly(acrylic acid)-Modified Magnetic Nanoparticles: Preparation and Property.
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Green catalysis for synthetic protocols and reactions is a fascinating and a major challenge in sustainable chemistry. There has been an explosion of interest in development of various methods to improve catalyst efficiency [1]. One popular route is to immobilize catalyst to enable the reuse of catalyst and simplify the purification process [2]. Immobilizing catalyst onto different support materials not only improves catalyst productivity but also prevents hazardous catalysts from leaking into the environment [3].
Recently, different types of catalyst support materials such as polymer supports [4-10], ionic liquid supports [10-12], inorganic supports [13-18], metal organic frame supports [19], and nanocomposite supports [20-22] have been invented for immobilizing catalysts on beads, surfaces, and membranes, and so forth [23]. Of these, magnetic iron oxide nano-composites have been the most widely used support material [2] because they offer enormous surface area with more binding sites; this reduces the disadvantages of heterogeneous catalysis [24].
Typically, organocatalyst TEMPO can utilize harmless and friendly oxidants [25, 26] such as molecular oxygen, hydrogen peroxide, or air for alcohols/aldehydes or ketones stoichiometric transformation. Immobilizing TEMPO on magnetic nanocomposites heightens catalyst-recycling efficiency; however magnetic nanoparticles are inorganic, and it is challenging to directly immobilize organic catalysts. This can lead to low catalyst loading efficiency. Currently, different methods have been successfully used to immobilize TEMPO on magnetic nanoparticles, such as "click" chemistry [27,28], amine reduction [29-31], and encapsulation and polymer/ nanoparticle blends [32]. The design and synthesis of magnetic nanoparticles with polymer chains on its surface [33] for specific catalyst immobilization not only improves immobilization efficiency but also avoids the use of potential harmful substances such azides or cyanoborohydrides that are employed in previous works [27-32]. The polymer chains on the magnetic nanoparticles surface offer pendant functional groups for organocatalyst anchoring reaction.
Here, we synthesized magnetic iron oxide nanoparticles with surface vinyl groups and employed reverse emulsion polymerization for surface polymerization of acrylic acid on the nanoparticle. This approach combines a poly(acrylic acid) chain grafted from magnetic iron oxide nanoparticles and forms an ideal support material for 4-hydroxy-2,2',6,6'-tetramethylpiperidinyl- 1-oxy (H-TEMPO). This novel method uses simple approaches and avoids potential harmful substances [27-31]; hence it is a facile and green approach to prepare iron oxide-based magnetic nanocomposite materials with efficient immobilization of TEMPO. The product was investigated as catalyst for alcohols/aldehydes or ketone transformation under both the Anelli [34] and Minisci [35] protocols.
2.1. Raw Materials. All reagents and solvents were of analytical grade and used as received without further purification unless otherwise noted. The organic catalyst 4-hydroxy2,2',6,6'- tetramethylpiperidinyl-1-oxy (H-TEMPO) and trichlorovinylsilane were purchased from Energy Chemical (China). Dicyclohexylcarbodiimide was purchased from J&K Scientific. Monomer acrylic acid was carefully distilled to remove inhibitor and preserved in refrigerator before use.
2.2. Characterization. Elemental analysis was performed on a CE instruments EA 1110 elemental analyzer. The infrared spectroscopy of all products was recorded in the range 4000-400 [cm.sup.-1] with Bruker Tensor 27 FT-IR spectrometer. Transmission electron microscopy (JEM 2100) was operated at 200 kV for morphological analysis. Magnetic properties of synthesis materials were studied with vibrating sample magnetometer (9600 VSM, BOJ Electronics, Troy, MI) at RT. Gas chromatography analysis was measured on Agilent GCMS chromatograph (model type: 7890A-5975C).
2.2.1. Preparation of Silica-Coated Magnetite Nanoparticles (Si-[Fe.sub.3][O.sub.4]). Bare iron oxide ([Fe.sub.3][O.sub.4]) nanoparticles were prepared by coprecipitation method with minor modifications [36]. In a typical process, ferric chloride hexahydrate (11.70 g) and ferrous chloride tetrahydrate (4.28 g) were dissolved in 120 mL deionized water at room temperature under nitrogen inert atmosphere with vigorous stirring until the salts were completely dissolved; the temperature was then raised to 60[degrees]C. Next, aqueous ammonia (25%, 80 mL) was quickly poured into the solution and the temperature was increased to 90[degrees]Cwith continual stirring for 30 minutes with a mechanical stirrer. Bare [Fe.sub.3][O.sub.4] nanoparticles were carefully collected with a neodymium magnet and washed with deionized water until they were neutralized.
Bare [Fe.sub.3][O.sub.4] nanoparticles from the previous step were directly suspended in a solution of ethanol and deionized water (V/V = 4/1, 200 mL) and sonicated for 15 min. Next, 5 mL of tetraethoxysilane (TEOS) was added slowly to the mixture and sonicated for 10 min. The reaction mixture was transferred to a single-neck flask equipped with a mechanical stirring device. Aqueous ammonia (25%, 18 mL) was added within 10 min. The mixture reacted at room temperature for 12 h. Iron oxide nanoparticles coated with silica ([Fe.sub.3][O.sub.4]@ Si[O.sub.2]) were collected and washed three times with water and ethanol using a neodymium magnet and then dried for 24 hours.
2.2.2. Preparation of Magnetic Nanoparticles Coated with Vinyl Group (Vinyl-MNPs). Dry Si-[Fe.sub.3][O.sub.4] powder (3.0 g) and 6 mL of trichlorovinylsilane were suspended in 150 mL dry toluene under inert atmosphere followed by sonication of the mixture for 30 minutes. The products reacted on a 105[degrees]C oil bath and for 10 hours. The product powder was separated using a neodymium magnet, washed with ethanol three times and dried under vacuum.
2.2.3. Surface Polymerization Acrylic Acid on Vinyl-MNPs to Prepare Poly(acrylic acid)@ Si[O.sub.2]@ [Fe.sub.3][O.sub.4] (PAA-MNPs). We prepared a mixture of vinyl-MNPs (0.2 g) and acrylic acid (3.0 g) in a 50 mL beaker followed by 10.0 mL of deionized water. This was sonicated for 20 minutes. The suspension was slowly added dropwise to Span-80 cyclohexane solution (20 g Span-80 in 250 mL cyclohexane) with stirring. This was stirred for another hour to preemulsify under an inert atmosphere. The temperature was adjusted to 60[degrees]C for 15 min, and then the initiator 2,2'-azobisisobutyronitrile (AIBN, 0.1 g) was added. To ensure complete conversion of the monomers, the reaction proceeded for another 4 hours. Methanol was added for demulsification after the reaction was over. The nanocomposite product was refluxed in ethanol for 2 hours before using a neodymium magnet to collect and wash with methanol; the product was then dried under vacuum.
2.2.4. Immobilization of TEMPO on PAA-MNPs Magnetic Nanoparticles (TEMPO-MNPs). The PAA-MNPs (1g) and H-TEMPO (2g) and N,N'-dicyclohexylcarbodiimide (DCC, 1.2 equivalent to H-TEMPO) were suspended in dry THF (100 mL). The reaction mixture was refluxed for 8 hours. The target product was collected using a neodymium magnet and washed three times with ethanol and dried under vacuum.
2.2.5. Determination of Catalysis Activity and Recycling Test
General Procedure for Catalysis Activity Test under Minisci Protocol. Alcohol (20mmol), TEMPO-MNPs powder (200 mg), Mn[(N[O.sub.3]).sub.2](120 mg, 50% aqueous solution), Co[(N[O.sub.3]).sub.2] (120 mg, 50% aqueous solution), and 208.3 mg internal standard (acetophenone) in 15 mL of C[H.sub.3]COOH were stirred in a two-necked flask at 40[degrees]C. The atmosphere of flask was then replaced with pure oxygen (balloon filled). The resulting suspension was stirred at 50[degrees]C under this normal atmosphere pressure. Samples were regularly removed for GC-MS analysis.
General Procedure for Catalysis Activity Test under Anelli Protocol. A 25 mL reaction flask was charged with alcohol (20 mmol), 1.0 mL KBr solution (1.0 M) 10 mL dichloromethane, 208.3 mg internal standard (acetophenone), and 150 mg supported TEMPO-MNPs material. The resulting suspension was stirred in an ice-water bath for 10 min before gradual addition of NaClO (0.35 M, pH 8.7,1.2 eq to alcohols). Samples were regularly removed with an external magnet followed by [Et.sub.2]O (3 X 5 mL) extraction and direct GC-MS analysis.
Gas chromatography (GC) results for all catalysis experiments were included in the supporting information (see Supplementary Material pages 1 and 2 available online at https:// doi.org/10.1155/2017/9621635).
2.2.6. Procedure for Catalysis Recycling Property of Supported TEMPO-MNPs Material. Recycling of supported TEMPOMNPs materials used a Minisci oxidation method without an internal standard. After the oxidation reaction was complete, the TEMPO-MNPs were magnetically separated and washed subsequently with ethyl dichloromethane, acetone, and [H.sub.2]O and directly used for subsequent catalysis without further purification. A new reaction was then performed with fresh reactants under the same conditions.
Gas chromatography-mass spectrometry (GC-MS) results of recycling test were included in supporting information (see Supplementary Material page 3).
The synthetic route for the nanocomposite materials and TEMPO anchoring procedure are illustrated in Scheme 1. The key step was polymerizing acrylic acid onto the magnetic particle surface. In the first step, relatively monodisperse bare ([Fe.sub.3][O.sub.4]) nanoparticles were synthesized by coprecipitation of iron (II) and iron (III) salts under basic solution at 90[degrees]C using Huang et al.'s method [36]. There are diverse routes for obtaining magnetic iron oxide particles. The simplest and most efficient chemical pathway is probably coprecipitation. Fortunately, particles prepared by this method contain extra surface hydroxyl (-OH) groups for chemical modification. Tetraethyl orthosilicate (TEOS) was used to coat the bare magnetic particles. The silica shell prevents [Fe.sub.3][O.sub.4] nanoparticle self-oxidation and leaching of ferric ions from the material core under severe conditions. The outer layer of the shell also provides many more Si-OH units for derivatization with silane coupling agent [37]. In the third step, the silica-coated [Fe.sub.3][O.sub.4] nanoparticles were dispersed in dry toluene and a trichlorovinylsilane mixture solution and vigorously stirred. This resulted in a surface containing vinyl groups. The vinyl-coated nanocomposite particles were further modified with acrylic acid via an inverse emulsion polymerization resulting in polymer-magnetic support material (Scheme 2).
Reverse emulsion polymerization takes place in latex particles, in which the surface containing vinyl group nanocomposite particles was confined. Vinyl silane compounds are traditionally used in the coating industry to improve adhesiveness on glass product; hence, surface vinyl groups on nanoparticle surrounded by the monomer could react with radical reactive center to form an acrylic acid polymer chain. Versus bulk polymerization and suspension polymerization, this synthesis procedure can efficiently prevent acrylic acid from crosslinking to form an insoluble magnetized gel. This novel support material has many carboxylic acid groups on the surface because of every side chain of poly(acrylic acid) (PAA) and is well-suited for TEMPO immobilization. The anchoring of TEMPO onto magnetic supports was easily and mildly conducted using N,N'-dicyclohexylcarbodiimide (DCC)/4-dimethyl-amino-pyridine (DMAP) and esterification catalysis in tetrahydrofuran solution.
3.1. FT-IR Analysis and Elemental Analysis. FT-IR spectroscopy was used to verify the conversion of organic functional groups on the particle surface. The inorganic nature of the iron oxide nanoparticle changed the polymer's composite nature. FT-IR data at each modification step clearly revealed this shift in the inorganic to organic composite. The FT-IR spectra of PAA/Si[O.sub.2]/[Fe.sub.3][O.sub.4] (Figure 1(4)) showed characteristic saturated hydrocarbons stretching vibration absorption (3000-2900 [cm.sup.-1], C-H stretching) and a band at 1710 [cm.sup.-1] (carbonyl). These data confirmed PAA segment bonding to the surface of magnetic nanoparticles.
After esterification, the anchoring of TEMPO onto the polymer chains of magnetic supports enhanced the organic absorption peaks. Comparison before and after the anchoring of TEMPO (Figure 1(4, 5)) shows a red shift in the carboxyl group peak (1710 [cm.sup.-1]-1718 [cm.sup.-1]) further indicating that the TEMPO was successfully immobilized onto the magnetic carrier.
Elemental analysis confirmed TEMPO loading was approximately 2.5 mmol/g (elemental results were provided in Table 1 and catalyst loading was calculated according to nitrogen content). This result also indicated that TEMPO was simply and conveniently attached to the particle surface polymer chain with respect to the carboxyl group. Previous studies have immobilized TEMPO on solid surfaces via "click" reactions, amide reduction reactions, and so forth. Recently, Karimi and coworkers showed that TEMPO was linked to the surface of the aminopropyltriethoxysilane-modified magnetic nanoparticles through amide reduction using sodium cyanoborohydrides [29-31]. Another previously known example reported by Schatz et al. [27] and Tucker-Schwartz and Garrell [28] is through "click" reaction using azide modified nanoparticles with TEMPO derivatives. However, those synthesis procedures require harsh reaction conditions or expensive catalysts. In contrast to the reports, our method requires no unstable azide compounds or toxic cyanoborohydrides substances but also increases catalyst loading to 2.5mmol/g (0.1mmol/g in the literature [28]). Hence, this synthetic route is simple and efficient.
3.2. Magnetic Properties and TEM Analysis. Transmission electron microscopy (TEM) (Figure 2) characterization of the magnetic materials indicated that bare nanoparticles were relatively uniform with an average size range of 10~30 nm. The image also revealed that the [Fe.sub.3][O.sub.4] nanoparticles were coated with mesoporous organic compound shells. Room-temperature magnetization curves (Figure 2(c)) showed that, after several modifications, the nanoparticle remained super-paramagnetic.
3.3. Catalyst Activity and Recycling Test. With the TEMPOMNPs in hand, catalytic application and selective oxidation of alcohol were further investigated along with its recycling efficiency. There are many catalytic systems employing nitroxides as an active catalyst in cooperation with metal or metal-free cocatalysts for alcohol oxidation. They can catalyze alcohols to the corresponding aldehydes/ketones in high yield and with chemoselectivity [34, 35, 38-40]. For example, Anelli [34] first used TEMPO as a catalyst in cooperation with hypochlorite and bromide for benzyl alcohols selective oxidation. The Anelli protocol proposed by Montanari and Anelli used a two-phase (C[H.sub.2][Cl.sub.2]/[H.sub.2]O) system and sodium hypochlorite as the oxidant. This convenient approach then uses bromide ion as a cocatalyst for selective oxidation of alcohols. Minisci and coworkers (Minisci protocol) used an environmentally friendly oxidant such as oxygen or air and reported aerobic oxidation catalyzed by TEMPO in cooperation with trace amounts of Mn[(N[O.sub.3]).sub.2] and Co[(N[O.sub.3]).sub.2] in acetic acid solution with excellent conversion and chemoselectivity [34]. Thus, the catalysis procedures based on TEMPO present a practical method for the selective transformation of alcohols to aldehydes/ketones. To determine if the TEMPO-MNPs retained their catalytic activity of small molecular catalysts, we investigated catalysis test under Minisci and Anelli protocols (Table 2).
This approach catalytically transformed alcohols to the corresponding carbonyl compounds (Table 2) using the insoluble magnetically supported TEMPO. Under the Anelli oxidation protocol, primary benzyl alcohols were quickly and efficiently converted into the aromatic aldehydes (5 min) (Table 2, entries 1-3). Secondary alcohols can also be transformed to ketones almost as quickly as the benzyl alcohol (entry 4, Table 2) with TEMPO catalysis.
Analogously, aldehydes were prepared by the selective transformation of primary alcohols under mild conditions proposed by Minisci; the yield was good. The catalytic activity of supported TEMPO materials combining cocatalysts Mn(II)-Co(II) nitrates was also applied to the aerobic oxidation of alcohols/aldehydes with excellent yields (entries 5-7, Table 2). The catalytic oxidation experiments under two well-known procedures showed that the organic catalyst TEMPO was successfully immobilized on the nanocomposite material while still maintaining good catalytic ability throughout the synthesis process.
Encouraged by these results, we next investigated TEMPOMNPs recyclability and reusability via oxidation of 4-methoxylbenzyl alcohol under the Montanari oxidation procedure. TEMPO-MNPs (150 mg scale) recyclability was achieved via separation through successive magnetic decantation as shown in Figure 3(a). After washing thoroughly with C[H.sub.2][Cl.sub.2], acetone, and [H.sub.2]O, successively, TEMPO-MNPs continued in the next run. The recycling and reuse demonstrated the efficiency of magnetic separation of the prepared material. The reusability of TEMPO-supported material was illustrated by GC conforming 4-methoxylbenzyl alcohol conversion in the 7th cycle. Oxidation conversion of 7th run was 97% after a reaction time of 5 min and with a selectivity of >96% (Figure 3(b), cycle 7). GC-MS analysis of the separated supernatant (as shown in Figure 3(a)) indicated no trace of TEMPO residue during oxidation. TEMPO remained stable under variety of catalytic environments despite being attached to a poly(acrylic acid) chain through an ester bond TEMPO-MNPs.
In conclusion, we developed a novel method to prepare magnetic polymer nanoparticles as an ideal support material for immobilizing organic catalysts 2,2',6,6'-tetramethylpiperidinyl-1-oxy (TEMPO). According to characterization results, acrylic acid is efficiently polymerized onto the silica-coated magnetic particles by applying inverse emulsion polymerization, and TEMPO is immobilized onto the particles. The synthesis procedures are simple and facile. They efficiently immobilized TEMPO. TEMPO-MNPs still retained the advantages of magnetic materials (simple separation with no mechanical loss) and showed excellent catalytic capabilities in alcohols for selective oxidation under the Anelli and Minisci procedures. The recyclability study on TEMPO-MNPs shows neither significant loss of activity nor selectivity dropping after 7 consecutive cycles.
Additional Points
Supporting Information. Gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) results for catalysis experiments are included in the supporting information.
https://doi.org/10.1155/2017/9621635
The authors declare that there are no conflicts of interest regarding the publication of this paper.
This work was financially supported by the National Nature Science Foundation of China (Grant nos. 51403041 and 51641302) and China Postdoctoral Science Foundation (2014M562183). The authors thank LetPub (www.letpub.com) for its linguistic assistance during the preparation of this manuscript.
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Guohui Huang, (1) Xiaoxuan Liu, (1) Yiling Bei, (2) and Huiqing Ma (2)
(1) School of Materials and Energy, Guangdong University of Technology, Guangzhou, Guangdong 510006, China
(2) School of Chemistry and Chemical Engineering, Shandong University, Jinan, Shandong 250100, China
Correspondence should be addressed to Xiaoxuan Liu; p-xxliu@gdut.edu.cn and Yiling Bei; beiyiling@sdu.edu.cn
Received 20 March 2017; Revised 11 April 2017; Accepted 19 April 2017; Published 30 May 2017
Academic Editor: Mehdi Salami-Kalajahi
Caption: SCHEME 1: Synthetic procedure.
Caption: SCHEME 2: Schematic illustration for the inverse emulsion polymerization.
Caption: FIGURE 1: FT-IR spectra of prepared [Fe.sub.3][O.sub.4] materials.
Caption: FIGURE 2: TEM images of bare [Fe.sub.3][O.sub.4] materials (a); TEMPO- MNPs material (b); magnetization curves of the resulting [Fe.sub.3][O.sub.4] materials (c).
Caption: FIGURE 3: (a) Image for the magnetic separation of the nanoparticles in the Montanari oxidation of benzyl alcohol. (b) Recyclability of TEMPO supported on nanocomposite particles in the Montanari oxidation of benzyl alcohol.
TABLE 1: Elemental analysis results and catalyst loading calculation.
Sample                           C       H       N     TEMPO loading
(wt%)   (wt%)   (wt%)
Bare [Fe.sub.3][O.sub.4]         0       0       0           0
Si-[Fe.sub.3][O.sub.4]           0       0       0           0
Vinyl-[Fe.sub.3][O.sub.4]       0.2    0.01      0           0
PAA-[Fe.sub.3][O.sub.4]        9.83    1.10      0           0
TEMPO-MNPs                     32.2    3.55    3.51     2.5 mmol/g
TABLE 2: TEMPO-MNPs mediated oxidation of alcohols to
aldehydes/ketones.
ENTRY         Alcohol         Conversion    Yield    Selectivity
(c) [%]     (c) [%]     (c) [%]
1 (a)      Benzyl alcohol         99         99         99.0
2 (a)      4-Chlorobenzyl         98         98         98.0
3 (a)     4-Methoxylbenzyl        99        84.8        85.6
4 (a)    4-Phenyl-2-butanol       99        95.1        96.1
5 (b)      Benzyl alcohol         99        96.9        97.8
6 (b)      4-Chlorobenzyl         99        83.1        84.0
7 (b)     4-Methoxylbenzyl        99         99         99.0
(a) Alcohol (1 mmol) in DCM, potassium bromide solution (1.0 M, 1 mL),
4-methoxyacetophenone (208.0 mg, internal standard), and TEMPO-MNPs
(150 mg) were added to a round-bottom flask. The suspension was
stirred in ice-water bath before addition of NaClO solution (0.35 M,
pH 8.7,1.05 eq). Sample aliquots were regularly taken and analyzed by
GC. (b) A 25 mL Schlenk-flask was charged with a solution of 1 mmol
alcohol, TEMPO-MNPs (200 mg), Mn[(N[O.sub.3]).sub.2] (50%, 120 mg),
and Co[(N[O.sub.3]).sub.2] x 6[H.sub.2]O (0.4 mmol, 100 mg) and in 15
mL of acetic acid was stirred at 40[degrees]C under [O.sub.2] at
atmospheric pressure. Sample aliquots were regularly taken and
analyzed by GC. (c) Conversion, yield, and selectivity were calculated
according to GC or GS-MS results in the supporting information.
COPYRIGHT 2017 Hindawi Limited
Huang, Guohui; Liu, Xiaoxuan; Bei, Yiling; Ma, Huiqing
International Journal of Polymer Science
Method Validation for Progesterone Determination in Poly(methyl methacrylate) Nanoparticles Synthesized via Miniemulsion Polymerization.
Effect of Polymer Binder on the Transparent Conducting Electrodes on Stretchable Film Fabricated by Screen Printing of Silver Paste.
Magnetic properties


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A shaken but defiant Saddam Hussein was sentenced to hang on Sunday for crimes against humanity, sparking joy for Shi'ites he oppressed and resentment among his fellow Sunnis across Iraq's violent sectarian divide. Saddam, 69, initially refused to stand when brought in to hear the verdict from Kurdish chief judge Raouf Abdul Rahman, at a quickfire, 45-minute hearing. When he did, visibly shaken, he yelled the defiant Arab battle cry "Allahu Akbar!" (God is Greatest) and "Long live Iraq" as the judgement was read. "The court has decided to sentence Saddam Hussein al-Majid to be hanged until he is dead for crimes against humanity," Abdul Rahman said, ignoring Saddam's earlier bombastic plea that he should face a military firing squad, not the noose.


text:
Corporate Access Conflicts of Interest Survey
A pan-European survey conducted by Phoenix-IR confirms that while institutional investors value highly the provision of corporate access, they are also critical of the process because of the inherent conflicts of interest. These distort the market for access to companies. Not all investors are treated fairly – some get good access to issuers and some don't.
Access to the management of publicly listed companies clearly favours the largest most powerful institutional investors and the most active short-term traders who are the generators of the biggest trading commissions. Medium and smaller sized institutional investors suffer, as do longer-term investors such as pension funds which do not frequently turn their portfolios.
This survey shows that, on average, each investor uses only 9 brokers to provide corporate access. A very low number compared to >100 brokers providing corporate access and the number of meetings taking place each day of the week.
The other key findings of this survey of professional money managers reveal that:
71% pay for corporate access indirectly through bundled dealing commissions
56% want listed companies to pay for corporate access rather than investors
43% believe they have been discriminated against in the provision of access
55% feel the sell-side has a conflict of interest when providing access
This pan-European survey was undertaken over a 10 day period from 15-25 February, 2013 and responses were received from 120 portfolio managers in: London (47 portfolio managers), Edinburgh (6), Zurich (11), Geneva (10), Paris (9), Frankfurt (8), Copenhagen (7), Brussels (5), Vienna (4), Amsterdam (4), Stockholm (4), Dublin (3), Milan (1) and Madrid (1). The total assets managed by these institutions ranges from approximately $150 million up to $500 billion with an average around $45 billion.
Background context
Following the November 2012 publication of the FSA's "Dear CEO letter": Conflicts of interest between asset managers and their customers: Identifying and mitigating the risks; the investor relations consultancy Phoenix-IR surveyed institutional asset managers to gain a better understanding of their views towards corporate access.
As defined by the FSA; access to company management (sometimes also referred to as 'corporate access') means, in this context, the practice of third parties (typically investment banks) arranging for asset managers to meet with the senior management of corporations in which the asset manager invests, or might subsequently invest, on behalf of customers.
Many large cap corporations undertake around 200 such meetings per year.
According to the Thomson Reuters Extel Survey 2012, the proportion of dealing commissions used to pay for corporate access increased to 29% in 2012, compared with 27% in 2011 and 21% in 2010.
Corporate access is now the largest component of services provided by the sell-side, overtaking trading and execution (28%) and research (26%) for the first time.
Greenwich Associates estimates that investors give $1.4 billion annually to their brokers to arrange for corporate access. Investors often pay brokers directly or indirectly $5,000-$10,000 per meeting, depending on the level of management being accessed. But a one-on-one with a marquee CEO could be worth as much as $20,000.
120 portfolio managers responded to this survey answering the following questions:
Q. How important is corporate access to you?
68% of the investors in this sample described corporate access as very important and only 7% described it as slightly important or not important. The vast majority of corporate access is provided by investment banks through non-deal roadshows or conferences. Less than 20% of corporate access is provided by other non-broking 3rd parties.
Q. How do you pay for corporate access?
71% of respondents report paying for corporate access indirectly through bundled dealing commissions while only 29% pay through unbundled CSAs.
Q. Who should pay for corporate access?
When brokers provide access, companies don't pay; the investor does. And investors are prepared to pay large sums for access because in today's highly regulated markets they feel meeting company management directly is one of the most important ways to gain an advantage in selecting stocks.
However, 56% of portfolio managers responding to this survey actually believe listed companies should pay for corporate access "because it is part of the cost of capital".
Q. Do investors feel they pay too much for corporate access?
Even though most investors in this sample believe companies should pay the bill, one indication of how much value they place on corporate access is that only 14% believe they are paying too much at the moment.
Corporate access has become the single most important part of many investors' investment process.
Q. Does the sell-side have a conflict of interest providing corporate access?
55% of investors feel the sell-side has a conflict of interest when providing access.
Q. Have you been discriminated against in the provision of corporate access?
57% of investors do not believe they have been discriminated against in the provision of corporate access. However, 43% feel they have been discriminated against in some way and they cite the broker's conflict of interest as the main reason.
"Brokers always go to their highest paying clients first. I have seen this from both the positive and negative sides."
Pension fund manager, London
"Brokers favour high frequency traders vs. fundamental investors."
Long-term investor, London
"Brokers run tiered categories of customer. 'Level one' clients routinely get better access to corporates."
Large investment management firm, London
"Funds with large AUM or good relationships with the broker are given access. Even though we may be large/significant shareholders, if we do not have a relationship with the broker, we have no way of getting access on roadshows."
"Whilst our AuM is a reasonable size (c.$9bn) our turnover is low and hence we are not that attractive a client for brokers in terms of commissions. It seems that high commission clients get preferential access, in our view."
Investment management firm, London
"Brokers give priority to larger fee generating clients."
"Based on your value to the broker, you may or not get a seat around the table."
Hedge fund manager, London
"Discrimination is a function of size. Brokers give better access to largest clients."
Investment management firm, Geneva
"After continual rude demands for increased commission from one multinational brokerage firm we stopped dealing with them after they threatened to cut us off from corporate access. We still tend to see the companies they bring around however generally only get last minute invites and only to group meetings."
Investment management firm, Edinburgh
"The major conflict of interest for the sell-side is that their main direct financial incentive is to organize meetings with investors that generate a lot of commissions, i.e. short-term oriented investors with short holding periods, rather than long-term oriented investors that don't trade a lot but could become long-term shareholders in companies."
Long-term sustainability investor, London
"Corporate access is best provided by independent 3rd parties. The broker involvement muddies the waters and creates conflicts of interest and bias. The system of broker-driven access is flawed from many angles."
"Companies need to make an effort to communicate with all interested parties and not only the larger holders of shares."
Specialist investment manager, Edinburgh
"Companies should be more aggressive with investment banks when poorly informed hedge fund investors are given meetings in preference to well informed longer term investors."
Leading investment management firm, London
"I am always surprised – but effectively positively – if a company uses an external corporation to get in contact with us as investors as it seems to be more independent."
Investment Management firm, Frankfurt
This entry was posted in Corporate Access / MiFID II / FCA on February 26, 2013 by Phoenix Investor Relations.
Conflicts of Interest – Corporate Access
The Investment Management Association (IMA) has published a paper Recommendations on Corporate Access and is asking for public comment by 26 February 2013 on the use of dealing commission to pay for corporate access.
The paper records the IMA's commitment to consider wider aspects of the corporate access and research market. The IMA has said it intends to undertake a wider investigation of the "barriers to engagement that may exist between investors and investee companies".
IMA reignites debate over bundled commissions
Source: Financial News, 14 Feb 2013
The Investment Management Association wants to look at the way the costs of corporate access, research and trading are bundled together by brokers – bringing the issue of corporate access into the unbundling debate for the first time.
The IMA, the UK trade body for asset managers, issued a statement this week in which it said it wants to investigate the way brokers charge asset managers for access to their corporate clients, and research, through commission payments bundled up with trading costs.
The statement is its official response to a letter that the Financial Services Authority wrote to the chief executives of asset management companies in November. The FSA letter said there was a potential conflict of interest within so-called "bundled commissions". It called on fund managers to confirm that the commissions were not being used to pay for access to companies.
The debate follows one that took place 10 years ago over the way brokers provided computers and other services to asset managers through soft commissions paid by the clients of managers. The FSA took steps to restrict the acceptance of soft commissions, but left in place commission payments for research and corporate access.
In its latest letter to asset management chief executives, the FSA said: "We found few governing bodies regularly reviewed whether the products and services purchased using client commissions were eligible to be paid for with customers funds."
The FSA added that firms were failing to organise commission payments properly. It pointed to a range of issues that need addressing. It called on the chief executives to confirm in writing by the end of this month that they are not vulnerable to conflicts of interest over commissions, and other issues.
IMA director Guy Sears said he wanted to see greater accuracy over the way access to company executives is charged.
Referring to the debate on the acceptance of soft commissions, Sears said: "It is 10 years since we had the last analysis of bundled commissions by the FSA. I believe the time for new scrutiny has arrived."
According to an IMA statement: "The IMA intends to embark on a wider programme of work during 2013 to consider the barriers to engagement that may exist between investors and investee companies and the challenges faced by asset managers in getting bundled services and research."
The FSA has highlighted the way in which company brokers arrange visits for investors to their clients. It said that 29% of access is paid via dealing commissions.
In its response, the IMA disputed this 29% figure: "The figure is not supported by information from members with which the IMA has spoken, appearing very large compared to the experience of these members," it said.
In its statement, the IMA said investors should not expect to pay when companies are brought round to see them outside periods where deals are taking place. According to one manager: "Payments by companies are more often than not the case."
The IMA added, however, that managers should pay when they approach a broker for access. In cases where analysts provided research on, say, events at a corporate meeting, payments could quality for research commissions.
The IMA said these would require different invoicing rules with costs to be broken down: "In the absence of this, it must be expected that many managers will feel unable to attribute any dealing commission to interactions with companies."
Sears said the quality of research should also be broken into appropriate categories, each commanding a different fee: "We need greater transparency and a review of the bundled pricing system."
Corporate Access – How Important Is It? (TradeTech)
Greenwich Associates estimates that investors give $1.4 billion annually to their brokers to arrange for corporate access. Investors place a premium on the chance to talk to company officers, particularly officers in high-growth companies or industries. Access to corporate officers may mean the inside track on investing information. However, access tends to favor large investors and to stretch the boundaries of Regulation Fair Disclosure.
Corporate access sessions typically take place at investment conferences. Large investors get private meetings or small group meetings with corporate officers thanks to the brokerage firms who organize the conferences. In a survey, 47 percent of investors claimed to receive "material" information during these meetings. A study by professors from the University of Pennsylvania, the University of New York, and the University of Michigan showed that trade sizes increased significantly after these sessions, particularly when the company's CEO was present. The study also found that over three to 30-day spans, these brokerage firms experienced significantly greater potential trading gains.
Investors tend to think that access provides more value. However, investors aren't getting access for free. Brokers have traditionally bundled corporate access into execution and proprietary research expenses. Integrity Research Associates chairman Michael Mayhew notes that investors tend to perceive access as part of the research product. Investors pay between $5,000 and $20,000 per meeting in the form of broker commissions. Therefore, access means that investors keep less of their profits.
Concerns arise over the level of influence that access to corporate officers has on investment analysts. Investment analysts, for instance, may be influenced by the level of access that companies provide to their executives. Analysts may also be influenced by whether or not these executives are willing to attend their brokerage's conference. Also, because a small number of traders realize large benefits from these meetings, smaller investors may lose confidence in market fairness. If investors believe that markets are unfairly biased toward large traders, then they may stop participating altogether.
Corporate officers may also stand to lose from offering access. For companies that are experiencing extreme stock volatility, access meetings may only increase the instability of the shareholder base. However, corporate officers can choose which brokerage company conferences they want to attend. This means that corporate officers are deciding which investors get access to their valuable insights. Many conclude that this directly violates the spirit of fair disclosure.
IMA offers corporate access guidance ahead of FSA deadline
Source, The Trade, Feb 13, 2013
UK buy-side trade body the Investment Management Association (IMA) has published a paper to guide institutional investors through corporate access rules in response to efforts from the regulator to separate out different broker services
The core issue in using dealing commissions to pay for corporate access is its classification as research, a point the Financial Services Authority (FSA) has sought to clarify through attestation letters. CEOs of UK asset managers must reply to the letter by 28 February stating that their firm abides by the current rules.
Buy-side firms looking to pay for corporate access through dealing commissions or commission sharing agreements (CSAs) risk infringing FSA rules if these services do not include direct broker research.
While the push for a clearer separation of broker services – execution, research and corporate access – is in line with wider efforts to make the financial ecosystem more transparent, smaller buy-side firms risk losing a key service provided by brokers to meet with corporate managers of firms they wish to invest in.
Guy Sears, director of institutional at the IMA, who helped author the paper, has called for wider debate on how corporate access is arranged and priced.
"Corporate access for buy-side firms overseas can reflect sheer commercial size – if you're a large asset manager an issuing corporate firm will welcome a meeting, but for smaller buy-side firms they need brokers to provide access," he commented. In the short-term, however, Sears said buy-side firms must ensure they meet the FSA rules.
The IMA paper sets out a number of scenarios whereby corporate access is not classed as research and as such cannot be paid for from dealing commissions.
"There are so many component activities that can fall under the heading of corporate access that buy- and sell-side firms need to unpack the details and look at exactly what is occurring and check it is classed as research according to the FSA rules," Sears said.
In November, the FSA published a damning report on broker services, claiming only two out of 15 asset managers randomly assessed complied with current FSA rules on conflicts of interest.

redpajama_set_name: RedPajamaCommonCrawl


"Ray Charles has been here for so long it's hard to remember when he wasn't around. I've always thought of him as an "Uncommon Denominater" in popular music. For 50 years, he exposed the World to the Blues…was the soul of Rock and Roll…and brought an African-American voice to country music.
My own life was soothed, rocked, and sometimes explained by Ray Charles. Isn't it funny how we don't appreciate someone fully until they're gone? Fortunately, Ray knew how much he was loved while he was with us.
I only met him once, on a plane back to L.A.from the Tokyo music festival. I felt more like a fan, than an exec at Warner Bros.Music, and became a little flustered. I introduced myself, and told him that I gave his producer a song he'd recorded," Go On Home" by Hugh McCracken…Ray smiled and sang a few bars back to me.


text:
Police review criticises Project Champion spy camera scheme in Birmingham
An independent review has criticised West Midlands Police over its scheme to install more than 200 surveillance cameras in two largely Muslim areas of Birmingham.
The cameras, some of which were hidden, sparked anger from civil liberties campaigners and residents in Sparkbrook and Washwood Heath in Birmingham, where they were predominantly installed.
A review, conducted by Thames Valley Police, into West Midlands Police's handling of the Project Champion scheme found "little evidence of thought being given to compliance with the legal or regulatory framework" before the cameras were put up.
The review concluded that: "The consultation phase was too little too late, and the lack of transparency about the purpose of the project has resulted in significant community anger and loss of trust."
The scheme was organised by the Safer Birmingham Partnership, an initiative including West Midlands Police, Birmingham City Council and other agencies.
The partnership has acknowledged it should have been more explicit about the role of the city's Counter Terrorism Unit in setting up the network of 218 cameras.
The number plate recognition (ANPR) and CCTV cameras were financed under a counter-terrorism initiative but were marketed to locals as a general crime prevention measure.
Following angry public meetings in July, the Safer Birmingham Partnership issued a statement pledging a full and in-depth public consultation and West Midlands Police asked the Thames Valley force to conduct an independent review.
The cameras have not been switched on and have been covered with plastic bags to provide reassurance to local communities that footage is not being captured.
A Home Office spokesman said: "This project was agreed under a previous administration. Work is already under way on CCTV and ANPR (Automatic Number Plate Recognition) regulation and the Government will be bringing forward proposals on it."
Commercial PropertyTower block to 'visually state' the intentions for new development area in central CardiffThe development company believe the new 25-storey tower south of Cardiff Central Station would be the first step of the ongoing redevelopment of the Dumballs Road area
Professional ServicesTop PR agency celebrates major client winsDCA Public Relations signs up leading firms and organisations after award win
North EastCentre Square developers invite interested businesses to check out facilitiesThe development in Middlesbrough will boast Grade A office facilities as well as a restaurant and coffee shops
West MidlandsComment: Is the UK financial system ready for the challenges ahead?Graeme Chaplin from the Bank of England assess what the future might hold for UK banks and how they should be prepared for stormy waters ahead


Augustine - 'happiness is indeed the chief end of man'.
The intention of sinful actions.
Augustine's seriousness about seeking righteousness.
Augustine's Confessions are built upon the twin poles of a search for God and a search for self. These twin poles are also twining poles because Augustine proclaims that one can only understand self in light of God and that one can only find God through self-knowledge. In one of his sermons, Augustine described the act of confession as, ?accusation of oneself; praise of God.? This act of confession results from the search. The search itself, as I have described elsewhere , is descent to an interiority of unfathomable depth and discovery of a God of incomprehensible immutability. In this essay, I will examine the part of confession involving ?accusation of oneself? by analyzing the origins, development, nature, and implications of Augustine's self-accusation.


text:
Audio Sciences
Digital Audio Modulation in the PAL and NTSC Laservision Video Disc Coding Formats
KE. A.. Immink, AD. H.. Hoogendijk, and JO. A.. Kahlman, "Digital Audio Modulation in the PAL and NTSC Laservision Video Disc Coding Formats," Paper 1997, (1983 October.). doi: KE. A.. Immink, AD. H.. Hoogendijk, and JO. A.. Kahlman, "Digital Audio Modulation in the PAL and NTSC Laservision Video Disc Coding Formats," Paper 1997, (1983 October.). doi:
Abstract: The authors present an extension of the current LaserVision video disc format that includes a digital audio signal. We show the feasibility of a combined digital audio signal according to the Compact Disc Digital Audio format and the current analog audio signals in the NTSC video format, enabling the realization of a compatible system. For the PAL and SECAM video formats we show the feasibility of digital audio, but unfortunately it cannot be combined with the analog audio carriers.
@article{immink1983digital,
author={immink, kees a. and hoogendijk, ad h. and kahlman, joost a.},
journal={journal of the audio engineering society},
title={digital audio modulation in the pal and ntsc laservision video disc coding formats},
pages={},
doi={},
month={october},} @article{immink1983digital,
month={october},
abstract={the authors present an extension of the current laservision video disc format that includes a digital audio signal. we show the feasibility of a combined digital audio signal according to the compact disc digital audio format and the current analog audio signals in the ntsc video format, enabling the realization of a compatible system. for the pal and secam video formats we show the feasibility of digital audio, but unfortunately it cannot be combined with the analog audio carriers.},}
TY - paper
TI - Digital Audio Modulation in the PAL and NTSC Laservision Video Disc Coding Formats
SP - EP -
AU - Immink, Kees A.
AU - Hoogendijk, Ad H.
AU - Kahlman, Joost A.
JO - Journal of the Audio Engineering Society
IS -
VO -
VL -
Y1 - October 1983 TY - paper
Y1 - October 1983
AB - The authors present an extension of the current LaserVision video disc format that includes a digital audio signal. We show the feasibility of a combined digital audio signal according to the Compact Disc Digital Audio format and the current analog audio signals in the NTSC video format, enabling the realization of a compatible system. For the PAL and SECAM video formats we show the feasibility of digital audio, but unfortunately it cannot be combined with the analog audio carriers.
The authors present an extension of the current LaserVision video disc format that includes a digital audio signal. We show the feasibility of a combined digital audio signal according to the Compact Disc Digital Audio format and the current analog audio signals in the NTSC video format, enabling the realization of a compatible system. For the PAL and SECAM video formats we show the feasibility of digital audio, but unfortunately it cannot be combined with the analog audio carriers.
Authors: Immink, Kees A.; Hoogendijk, Ad H.; Kahlman, Joost A.
Affiliation: Philips Research Laboratories, Eindhoven, The Netherlands
AES Convention: 74 (October 1983) Paper Number: 1997
Publication Date: October 1, 1983 Import into BibTeX
Subject: Digital Recording and Broadcasting
Permalink: http://www.aes.org/e-lib/browse.cfm?elib=11765
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Catch the bullet train to Guilin, then transfer to Yangshuo, nestled amongst the limestone karsts jutting out of the Li River.
Travel to Tiger Leaping Gorge and start on the famous hike. The route follows the stunning scenery of the Yangtze as it cuts through the gorge.
Cath an express bus to Dali. Take an orientation walk then explore the old town on our own.
Fly from Dali to the vibrant, modern city of Chengdu.


The Wisam Khamees Scholarship Fund for Arabs and Jews is dedicated to supporting Israelis - both Arabs and Jews alike - in their pursuit of higher education. The Fund is the only Israeli non-profit organization to award scholarships for higher education to both Arabs and Jews, symbolizing the Fund's commitment to academic advancement as well as co-existence in Israel. In 1999, 17.5-year old Wisam Khamees was tragically killed in an accident, just months before he was to begin his academic career. Prior to his death, Wisam was an active leader in a non-profit organization which promotes co-existence between Jews and Arabs. Upon his death, the money he had saved over the years towards his higher education was used as the first scholarships the Fund awarded. Since then, the Fund has continued to award hundreds of scholarships each year. A call for equality and co-existence among Arabs and Jews: From the onset, the Fund has been guided by its strong belief in awarding scholarships to both Israeli Arabs and Jews alike and awards scholarships equally. The Fund's scholars, the future leaders of Israel, are proud recipients of scholarships that carry the spirit of equality and democracy. The Fund serves as a model of equal treatment and fairness in the face of a society still tainted with discrimination. The successful, egalitarian policies of the Fund are a call to the government of Israel that co-existence among Arabs and Jews is possible. Profound devotion to higher education: The Wisam Khamees Scholarship Fund for Arabs and Jews was made possible by Wisam-s dream and investment in education from a very early age. The Fund believes that higher education supports the backbone of a modern and progressive society in the State of Israel.


text:
Anatolia College, Merzifon
Anatolia College, Merzifon was a high school, theological seminary, orphanage and hospital founded in 1864 in the town of Merzifon in the Amasya province of Asia Minor (today Turkey). The origins of the college can be traced to Bebek, a suburb of Constantinople, where in 1840 the original school was started by American missionary Cyrus Hamlin.
Initially, the school trained young men to become pastors and teachers among Greeks and Armenians living in Turkey, but the high quality of the academic program and the ever increasing desire to learn English attracted more students wanting a general education. So in 1864 the school was divided into two separate institutions.
Anatolia College and Hospital (to the right). Marsovan (Merzifon). Source
The school at Bebek became known as Robert College and concentrated on the liberal arts while the theological seminary of the Mission moved to Merzifon (Marsovan) in the interior of Turkey. In 1893 a Girls' school was founded within the college.
Anatolia College Marsovan. Source
At Merzifon, as had occurred at Bebek, more and more students wanted a general education, so in 1886 the school was expanded to include a 4 year liberal arts curriculum and it became known as Anatolia College.
The Anatolia College campus was enclosed by a mud brick wall about ten feet high and three gates. At the two main gates, gatemen were on duty night and day and no boarding student could leave the campus without a pass signed by the dean.
Anatolia College Marsovan, North Building.
The main feature of the campus was the Boys' college. It included four years of high school and four years of a degree-granting liberal arts college. It also included athletics clubs and literary societies. The Pontus Club was one such club and it met every Saturday night and many of the Greek students at Anatolia were members.
Just prior to the school's closure on March 18, 1921, the campus was filled to overflowing with some two hundred Greeks, two hundred Armenians, and about twenty Turks. About forty of the Greek students were from Greek settlements on the Russian side of the Black Sea. A Russian teacher was provided for them.
Anatolia College Hospital, Marsovan. Source
Most of the buildings were made of mud brick plastered over and white-washed. The offices and library were made of stone. At one end of the campus, Union Hall was under construction, and the foundation had been laid and a stone wall had risen three or four feet, however the project had to be abandoned because of unsettled conditions in Turkey.
The Girls' Campus was a finishing school of approximately high school level with about two hundred students divided ethnically in about the same proportions as the college itself.
Anatolia College Orchestra, Merzifon c. 1909-1910. Professor Daghlian is holding the claxon; Mr. Elmas is at his night; Bottom far right is Harhanres Jenogian; Next to Mr. Jenogian are Hippocrates Kyriakides (Kyprianides) and Dr. Kyprie Daltrait. Source
In between the two schools was the School for the Deaf which at that time was the only such school in Turkey. Across the road from the college was a large hospital then being completed. In addition to the hospital itself, which attracted patients from all over Asia Minor, was one of the few nurses' training schools in the whole of Turkey. At the lower end of the main campus was the Theological Seminary which prepared young men to become pastors in the Protestant churches throughout Turkey. There was also a book bindery and a well equipped carpenter shop providing services both for the campus and the whole community.
"At first glance, these children look like they're doing something we've all done in the past but might not admit to – singing into a handheld mirror and pretending to be a popstar. Except that this is a lesson in speech – these deaf children in Anatolia are perfecting their mouth shapes using a mirror." - Neil Bates Photograph from Anatolia College (Public Domain)
One of the main features of the campus was the Swiss clock in a tower above the largest building, which rang out the time every quarter hour. The clock served as time keeper for much of the city, as it followed the modern system of timing used in the rest of Europe.
The Hellenic Athletic club 'Pontos' , Marsovan (Merzifon). c 1906/7. Source
The school's motto was known as 'The Morning Cometh'. The college emblem incorporated a view from the campus of the sun rising over the Akdag mountain at the eastern end of the Merzifon plain.
Following the forced closure of the Merzifon campus by the Turkish government in 1921, the School relocated to Greece in 1924.
Guards from the Greek Association Pontos, 1910.
Carl C. Compton, The Morning Cometh, 45 years with Anatolia College.
George E. White, Charles Chapin Tracy, Pilgrim Press 1918.


Peacock, in our Guinea fowl flock.
The African Wild Cat, while pruning.
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text:
Hatfield and the North (1974) è l'album di debutto dell'omonimo gruppo musicale britannico.

Tracce
Lato A

Lato B

Tracce extra edizioni in CD

(*) Solo nelle edizioni in CD dal 2009 in poi.

Musicisti
Gruppo
 Phil Miller – chitarra
 Dave Stewart – tastiere, sintetizzatore
 Richard Sinclair – basso, voce
 Pip Pyle – batteria
Ospiti
 Robert Wyatt – voce (traccia: 4)
 Geoff Leigh – sassofono tenore (traccia: 5), flauto (tracce: 5, 13)
 Didier Malherbe – sassofono tenore (traccia: 7)
 Jeremy Baines – pixifono (traccia: 5), flauto (traccia: 13)
 The Northettes: – cori (tracce: 5, 13, 17)
 Barbara Gaskin
 Amanda Parsons
 Ann Rosenthal
 Jimmy Hastings - flauto (CD – traccia: 17)

Note

Collegamenti esterni

redpajama_set_name: RedPajamaWikipedia


PLEASE NOTE THE LATER START FOR THE DROP-OFF TIME. DUE TO CONSTRUCTION AND NEW DROP-OFF LOCATION, WE MUST WAIT FOR THE SCHOOL BUSES TO DEPART BEFORE WE MAY RECEIVE YOUR DONATIONS. FOR NHS CLASSROOMS ONLY, WE WILL BE AVAILABLE IN THE HS THEATER TO RECEIVE YOUR GIFTS BY 2 PM.
DUE TO CONSTRUCTION AT NH-S HIGH SCHOOL, THE GIFT DROP-OFF LOCATION HAS BEEN CHANGED TO THE THEATER SIDE OF THE HIGH SCHOOL. THE DOOR WILL BE MARKED.
Our Adopt a Child for the Holidays "elves" will greet you by the theater to help you carry the gifts in so you can begin the check-in process at the labeled tables. You will need to come in yourself for the check-in process.
It is very important that each and every gift is labeled with the child's name and unique ID number.
You will find this information on the wish list that was emailed to you. You may also go to My Account to review your list(s).
Please DO NOT WRAP any gifts. Feel free, however, to include wrapping paper or gift bags if you like!
Gift Drop-Off is a very busy, exciting and much anticipated day!
Thanks for all that you do to make sure each holiday gift is delivered safely into the hands of a child.
If you are unable to have your gifts brought to the NHS theater for Drop-Off, please reference our FAQ tab.


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Years ago, when one man took a step to further his studies in the United States of America and then decided to call it quits after only completing the first semester, it was no doubt a flip-flop decision on his part. But it was also the beginning of greater things to come for Jack Lim, entrepreneur extraordinaire, who has established the Fipper brand of flip-flops through his footwear company, Fipper Marketing SDN BHD in Malaysia and has since expanded into various parts of Asia. The passionate and visionary entrepreneur speaks to us about his humble beginnings, his endeavours and hopes for the future.
Humble beginnings did nothing to quench the spirit of Jack Lim – a man with a mission. He was born in Penang and later moved to Kuala Lumpur at the age of four. "I grew up in a rather modest environment. My father worked as an accounts executive while my mother was a housewife. Life was tough back then but it was also a memorable time for me," says Lim, the brainchild of the Fipper brand of footwear.
After completing his secondary school education in 1996, Lim got an opportunity to pursue his education in Computer Science in the United States of America.
However, deep down inside him was the passion to be an entrepreneur. "Though I was young and somewhat naïve back then, I was aware that I needed big bucks to realise my dream. I had no idea about the kind of business that I would start but I was pretty determined. Thus, after completing my first semester, I made up my mind to quit school and started doing odd jobs as a first step towards realising my dream," shares Lim. He went through the mill as a bus boy, a waiter and subsequently became a restaurant manager. Lim believed in going the extra mile in the jobs that he was in and he worked hard to achieve excellence.
As time went by, he discovered that commitment and responsibility is the key to success in anything and everything a person does in life. "Having the correct working attitude is essential for one to succeed," he says. When Lim returned to Malaysia, he set about realising his dream and not long afterwards, he started his footwear business under the Fipper brand through Fipper Marketing Sdn Bhd.
"Back in 2008, there were only a handful of flip-flops players in the market and among them are iPanema, Riders and Havaianas. But all of them are selling their products at premium prices. I then saw the huge demand for affordable flip-flop footwear. This led me to venture into this business with three of my childhood good friends," says Lim. Thereafter, they wasted no time in getting to Thailand to source for flip-flops materials and finally, natural rubber was chosen.
Fipper flip-flops are completely made out of natural rubber which is free from biphenol-A, an endocrine disruptor which can mimic the body's own hormones and may bring about negative health effects for the foetus and infants. The footwear is comfortable, anti-microbial and has anti-slip properties. It is also environmental friendly as it is biodegradable, recyclable and washable.
Lim laments that during the early years not many were aware of the benefits of all natural rubber footwear and did not appreciate it. "We started off by getting the local vendors to distribute our products but that turned out to be our first challenge. Many turned us down due to the low profit margin as we controlled the selling prices for our Fipper flip-flops. But as time passed by, the demand for our products grew and in 2009, we managed to penetrate into the Carrefour hypermarket chain," recalls Lim. In the following year, he set up the first Fipper retail outlet in 2010 in Sungei Wang Plaza, a large shopping complex in the heart of Kuala Lumpur. Currently, there are some 52 Fipper retail outlets in Malaysia that are also found in East Malaysian states of Sabah and Sarawak.
"Initially, there was only the Fipper's classic range but due to the high demand we now have more than 20 different ranges with hundreds of colour combinations to choose from," says Lim.
Fipper has indeed grown dynamically into a brand that has expanded its exposure across Asia within its seven years of establishment and Lim takes pride in it being a Malaysian homegrown brand. "At first, our footwear products were supposed to be known as 'Flipper' but I found that to be quite a mouthful. After some thought, I decided to change it to 'Fipper' in the hope that it will become a household name for 'slipper' one day," chuckles Lim. He reveals that Fipper has been embarking on an expansion plan to penetrate into other parts of Asia since 2011.
Lim also adds that Fipper's expansion plans carried out in Cambodia, Singapore, Vietnam, Brunei and Indonesia have been very encouraging. It is especially so in Bali, Indonesia where Fipper has opened eight retail outlets within a year. In view of the great demand, Lim is planning to set up Fipper's Indonesia corporate office and warehouse in Bali to oversee all distribution channels in that country.
Fipper's growing success that includes having won The World's SMEs Best Brands Award for 2013, has not taken away the one quality that has enhanced Lim's leadership effectiveness in the organisation – humility.
The company allows for, and promotes, creative and analytical thinking as Lim himself strongly believes that it is the only sure way for the company to progress meaningfully. "We encourage our staff to think out of the box and come up with innovative and cutting-edge ideas as their personal growth will spell success for the company as well," he says.
Besides his work, Lim has a passion for surfing. "I adore surfing! There is no greater feeling than that of being a part of the ocean. I feel like I'm on top of the world," he says with a sparkle in his eyes.
When asked about his role model in life, Lim was quick to point out that it is his father. "My father definitely played a major role in my life. His family was a big one and my father was expected to fend for himself during his growing up years. He was perseverant, smart, hardworking and had led a principled simple life," he says.
"I guess the apple doesn't fall far from the tree. I have definitely picked up after my father and I must say that without his guidance and advice, I won't be where I am today." Besides his father, Lim is also grateful for the support given to him by his friends and family ever since he began his journey to make his dream come true.
Lim believes that the greatest achievement of Fipper does not just lie in the success of the business itself, but also in the trust and confidence among the very committed teams and business partners who have believed in the dream and come alongside to realise it. Confident and passionate about what he does, Lim aims to emulate the success of Havaianas within the next 10 years.
"From a business perspective, I look forward to Fipper establishing its very own production lines soon and also more extensive regional distribution channels too. Nobody can predict the future but this I am sure – whatever happens, I am ever ready to move forward and keep the fire burning brighter than ever before," he says with an unmistakeable note of determination in his tone.


text:
USA Today, 2010
At USA TODAY's request, Zagat.com found the best ones for breakfast in 25 cities — ranging from Boston to San Francisco, Minneapolis to Houston — that are frequently visited by business travelers. At Mama's on Washington Square in San Francisco, diners can feast for $10.50 on the Northwest omelet. It includes smoked salmon and grilled leeks drizzled with sour cream, served with grilled red potatoes and toast. See the full article here!
Michael and Debra taking orders
Served 8am - 3pm. Always Made to Order and Served with Home Fries, Homemade Jam, and Your Choice of Toast: White, Wheat, Rye, or Sourdough Baguette
Food GPS by Joshua Lurie (food writer) 11/8/09
My last meal at Mama's was in 2004, but it's not due to a dip in interest. On the contrary. I've made repeated attempts to eat at the reigning queen of Bay Area breakfast joints, but it all comes down to one factor: timing. On weekends, if you don't join the line a half-hour before the 8 AM opening, you're out of the initial seating and out of luck. This time, we wouldn't be denied.
Frances "Mama" Sanchez opened her scintillating restaurant in 1951 on the northeast corner of Washington Square. Now Debra Sanchez runs the restaurant with husband Michael, the skilled grill man, head baker and Mama's son.
mamas-breads
Once you're granted the privilege of passing through the front door, you're paraded past the sizzling grill and bustling prep counter, where you'll see warm loaves of bread destined for French toast glory, bowls of garden fresh vegetables and lump crab meat, and stacks of jaw-dropping coffee cakes. By the time you get to the register to place your order, a table should be ready, and your stomach should be churning.
mamas-chocolate-crunch-cake
Whatever you order, don't pass up the prized coffee cakes. Chocolate crunch was this visit's grand champion, with a moist base and chocolate-lashed streusel top that was nearly an inch thick.
mamas-blueberry-sour-cream-coffee-cake
Blueberry sour cream was also compelling, with plump berries and a tangy pop from the sour cream.
mamas-french-toast-sampler
Michael Sanchez transforms his fresh loaves of bread into French toast. You can order the toasts individually, but the best way to experience the French toast is by ordering the sampler ($10.95). The trio changes each day. During our visit, we enjoyed tart cranberry-orange-walnut, Swedish cinnamon and banana nut topped with thin-sliced banana. The supple French toast fan was dusted with powdered sugar, scattered with fresh berries (black, rasp and straw) and plated with a tiny pitcher of maple syrup.
If French toast isn't your thing, Mama's also produces buttermilk pancakes, several varieties of fluffy omelettes and a crab benedict that utilizes that pulled crab meat.
In case you need an added jolt, each table hosts a container of homemade ollalie berry jam, which is terrific on just about anything.
mamas-ham-steak
With all the bread-on-bread action, we needed a Dose of Vitamin P to introduce a savory element. Mama's grills thick strips of bacon, but we opted for a slab of char-grilled ham ($3.50) that delivered more than enough salt to cut all the sweetness.
Mama's was well worth the half-hour wait for what remains San Francisco's best breakfast. During the week, customers have to contend with fewer tourists, so it's an even better time to visit.
Note: Closed Mondays
KTVU.com
"...it's still the greatest."
10 best.com
Act fast and early if you're thinking about Mama's – after lunch you're out of luck. And you certainly don't want to miss the array of perfectly prepared breakfast foods. Generous portions are standard, whether you order a fluffy omelet, a stack of hotcakes or light, fragrant French toast. If you need them, Mama's also offers healthy egg white creations. Quick service is a staple, but even so, weekend brunch has been known to generate waits thanks to the cafe's popularity.
tastyr.com
"Whoa Mama! Some people complain about the sometime two hour wait on the weekends, but the trick is going during the week, when the only waiting you have to do is inside, watching the cooks create breakfast masterpieces before your very hungry eyes."
www.boston.com / The Boston Globe
A gourmet brunch and breakfast place serving perfect omelets, freshly baked breads, and exotic daily specials More....
1701 Stockton Street, San Francisco, CA 94133 • (415) 362-6421 • Open daily 8am-3pm, Closed Mondays
Welcome to Mama's home away from home!
We are a breakfast and lunch spot proudly serving San Francisco's North Beach neighborhood for over 40 years.
From traditional favorites to unique creations, everything's fresh, made to order, and delicious; just like Mama used to make. Our fresh baked goods and homemade jams make all the difference, so come on in–you'll be glad you did!
"Every great breakfast spot has a line out the door..."
Zagat San Francisco, 2008
Wake "really early" or expect a "long, long line" at this "cozy" North Beach American where locals and tourist alike "belly up to the counter" to order what many call "the best brunch" and breakfast in town (no dinner); fans consider it the "ultimate comfort food" and "well worth" the crazy waits - just bring "reading material and a dose of patience."
Los Angeles-citysearch.com
It's true the ingredients are fresh the fruit delicious. The wait however can be UNBELIEVABLE as it is More....
Words cannot describe!!!
But you must get there early on weekends More....
Digital Restaurant Guide
Good basic California foods, omelet, veal, chicken, Great setting for big weekend breakfasts. Large windows look out on to Washington Square area. Omelet More....
sweetandsourspectator.org
As far as I can tell people stand in a long line for a long time for one of two reasons: 1) they are at a government facility and they are told to stand there, or 2) they know there is something really good waiting when then finally get to the front. The line at Mama's for weekend brunch is obviously a type #2 line. It looks incredibly long... but, once you get inside, you will be greeted by a bright sunny room with jazz playing in the background and an impressive list of breakfast items to choose from.
Besides the standard menu, there is a blackboard with the day's specials. They have every type of omelette (m'omelettes), French toast, pancake, florentine, and benedict that the mind of man can invent. It may be hard to choose between the cinnamon, butter, apples, maple syrup, cranberries, oranges, walnuts, pecans, kugelpuph, baguettes, brioche, & etc. but it really doesn't matter, as far as I can tell, it is all good.
You have to go to Mama's because it makes the most amazing french toast with fresh fruit ever...
1701 Stockton Street, San Francisco, CA 94133 • (415) 362-6421 • open daily 8am–3pm, closed Mondays
1701 Stockton St. (at Filbert St.), San Francisco, CA 94133
open daily 8am - 3pm, closed Mondays (cash only please)
Fresh Squeezed Orange
or Grapefruit juice
small: $2.95, large: $3.95
or Cranberry Juice $2.75
Lemonade $2.50
Health Shake $4.95
orange juice, protein powder, yogurt, berries, eggs, banana, and honey
Berry Calistoga $2.75
Sparkling Water $2.75
Soda $1.95
Coke, Sprite, Diet Coke
Beer $3.95
Wine $5.25
Mimosas $7.75
Bloody Marys $5.50
Screwdrivers $6.50
Coffee $1.75
Espresso $2.25
Cappuccino $2.25
Hot Chocolate $2.50
Latte $2.75
Mocha $3.25
Hot Tea $1.75
Iced Tea $2.50
Iced Lattes $2.75
Homemade Olallieberry Jam
A relative of the blackberry, loganberry, and raspberry (to name a few), olallieberries are a rare treat, made even more so by their short growing season.
(16 oz jar)
Classic carrot cake with cream cheese frosting.
Kugelhupf Brioche
Kugelhupf Brioche filled with golden raisins, dates, and cinnamon sugar
(serves 16)
Fudgy Pecan Brownies
(1 dozen)
Banana Walnut Loaf
A classic banana bread with walnuts
(9"x5")
Poppyseed Bundt Cake
Deliciously light poppyseed bundt cake with lemon cream cheese frosting
Cranberry-Orange Walnut Loaf
Two Eggs Any Style
Two eggs any style: poached, over easy, over hard, sunny side up, etc.
Add choice of bacon, ham, or link sausage
Add choice of Italian Sausage or Canadian Bacon
Add English Muffin
+.75
Egg Whites, Scrambled
Egg whites scrambled with green onions, mushrooms, and spinach and served with sliced tomatoes
Two poached eggs covered with spinach, mushrooms, and Hollandaise sauce and served on an English muffin w/home fries
Nelson's Rancheros
Two poached eggs nestled on black beans, topped with our homemade salsa, and served with home fries and tortillas
Scrambled eggs, smoked salmon, and green onions served with a bagel and cream cheese
Lox Bagel Platter
Smoked salmon, cream cheese, red onions, and capers served on a bagel with sliced tomatoes and cucumber


text:
HomeActionEverest VR: Journey to the Top of the World
Everest VR: Journey to the Top of the World
April 29, 2020 davidhague178181403 Action, Case Studies, Interviews, Press Release, Today, Virtual Reality 0
Blackmagic Design today announced that the stunning new 8K 3D documentary "Everest VR: Journey to the Top of the World," produced by Facebook's Oculus, was edited, graded and stitched with DaVinci Resolve Studio and Fusion Studio.
In April of 2017, world famous climber Ueli Steck died while preparing for climbing both Mount Everest and Mount Lhotse without the use of bottled oxygen. Ueli's close friends Jonathan Griffith and Sherpa Tenji attempted to finish off this project while award winning VR director and alpine photographer Griffith captured the entire story.
Over the course of three years, Griffith shot footage following Tenji and some of the world's most accomplished climbers on some of the world's most extreme locations. The series also includes footage that lets viewers witness what it is like to be engulfed in a Himalayan avalanche, cross a crevasse and staring deep in its depths, take a huge rock climbing fall, camp under the stars and soak in the view from the top of the world.
Griffith worked with a veteran VR post production expert Matthew DeJohn for editing and color correction, VR stitching expert Keith Kolod and Brendan Hogan for sound design.
"It really was amazing how a small crew was able to get all of this done. The collaboration between myself as the cameraman and Matt and Keith was a huge part of being able to get this series done and done at such as a high quality," said Griffith.
"Matt and Keith would give suggestions on how to capture for VR, how camera wobbling impacted stitching, how to be aware of the nadir and zenith in each frame and to think about proximity issues. The efficient post production process helped in letting us focus on what was needed, and I am incredibly happy with the end result. Everyone on the project worked above and beyond, and the results show."
DeJohn was tasked with bringing together a huge amount of footage from a number of different high end camera systems.
"A VR project usually has different teams of multiple people for editing, grading and stitching, but with DaVinci Resolve, Keith and I handled everything," DeJohn said. "DaVinci Resolve is ideal for VR post. The fact that every tool I needed was in a single app made the entire process efficient and cost effective. So much time was saved simply by just having to switch apps with a few mouse clicks instead of shutting down the process by moving files from one system to another."
For editing, DeJohn used DaVinci Resolve Studio to cut the series at 2Kx2K, relinked to 8Kx8K source and then change the timeline resolution to 8kx8K for final color and rendering. He used the Fairlight audio editing tab for its expanded toolset which allowed him to make fine adjustments, manage different narration takes with audio layers, and manage varied source files such as mono narration, stereo music, and 4-channel ambisonic spatial audio.
"With color correction, I used Resolve to ensure we kept and honest look throughout and to make that look consistent across various camera systems and shooting conditions.
VR forces you to be real, and I used DaVinci Resolve to keep every scene realistic because any hint of oversaturation or an unnatural grade would ruin the VR experience," he continued. "I colored the project from the very first edit so when it came to finalize the color it was just a process of touching things up."
Fusion Studio was used for stereoscopic alignment fixes, motion graphics, rig removal, nadir patches, stabilization, stereo correction of the initial stitch, re-orienting 360 imagery, viewing the 360 scenes in a VR headset and controlling focal areas. More intense stitching work was done by Kolod using Fusion Studio.
Kolod, explained: "Every shot in this type of production is a VFX shot and I relied on Fusion. It is better, faster and more affordable. The render time is much faster and the seamless integration with the rest of post is incredibly efficient."
Footage of such an extreme environment, as well as the closeness of climbers to the cameras, provided unique challenges for Kolod who had to rebuild portions of images from individual cameras. He also had to manually ramping down the stereo on the images north and south poles to ensure easy viewing, fix stereo misalignment and distance issues between the foreground and background and calm excessive movement in images.
"A regular fix I had to make was adjusting incorrect vertical alignments, which create huge problems for viewing. Even if a camera is a little bit off, the viewer can tell," Kolod said. "The project used a lot of locked off tripod cameras, and you would think that the images coming from them would be completely steady. But a little bit of wind or slight movement in what is usually a calm frame makes a scene unwatchable in VR. So I used Fusion for stabilization on a lot of shots."
"High quality VR work should always be done with manual stitching with an artist making sure there are no rough areas. The reason why this series looks so amazing is that there was an artist involved in every part of the process, shooting, editing, grading and stitching," he finished.
Last Day to Win!
Quick Tutorial: Blackmagic Design ATEM Mini Pro and Facebook Live using XSplit Broadcaster
Blackmagic URSA Mini Pro 4.6K Update
May 27, 2020 davidhague178181403 Broadcast, Camcorders, News, Press Release, The Newsroom 0
Blackmagic Design has announced a major new software update for the original Blackmagic URSA Mini Pro 4.6K camera that adds localization for 11 languages, the ability to embed custom 3D LUTs in Blackmagic RAW clips, […]
56% of Sundance Film Festival created in Premiere Pro. Oh and Adobe Announces "Productions"
January 28, 2020 davidhague178181403 News, The Editing Suite, Today 1
Adobe are saying that 56% of films shown at the Sundance Film Festival were "created" with Premiere Pro, thus making it the most used software at the festival. In a similar vein, Blackmagic Design announced […]
Deadline Hollywood Upgrades to Blackmagic Pocket Cinema Camera 4K
January 8, 2020 davidhague178181403 Camcorders, Case Studies, News, People, Press Release, The Newsroom, Today 0
Deadline Hollywood, arguably the preeminent site for the most up to date breaking news stories in the entertainment industry, recently upgraded their video production unit to Blackmagic Pocket Cinema Cameras 4K for all of their […]


For cab exhaust Peterbilt 579 long hood (123″ BBC) and 567 set-back axle long hood (121″ BBC) models. Cab/80″ sleeper and extender skirts measure 3″ wide. X2ACG2 LED (9) lights. Two block heater cutouts.
This kit is designed for cab exhaust Peterbilt 579 long hood (123″ BBC) and 567 set-back axle long hood (121″ BBC) models. Included in this kit – cab skirts, 80″ sleeper skirts and extenders. Measure 3″ wide, lights are X2ACG2-LED (9). The driver side cab skirt has 2 block heater cutouts. Hardware, lights and harness included.


In 2019, communities across the world will be celebrating Lunar New Year on February 5. Although commonly known as "Chinese New Year", the annual celebration marks the beginning of the year according to the lunar calendar, and is celebrated over a number of days in countries such as China, Vietnam, Korean, Malaysia and Singapore.
Lunar New Year involves visiting family and friends, paying respects to ancestors, giving (or if you're lucky, receiving) packets of "lucky money", and dining on banquet-style feasts. Whip up some noodles for long life, fry up some crisp spring rolls, or try Kylie Kwong's twist on the Cantonese classic dish, sweet and sour pork.