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Justia Patents Propionate, Butyrate Or Isobutyrate ContainingUS Patent for Process for the preparation of pseudo primycin Patent (Patent # 5,260,426)
Process for the preparation of pseudo primycin
Mar 24, 1992 - Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara R.T.
The invention relates to antibacterial pseudo-primycin complexes of formula (I) ##STR1## to the components and acid addition salts thereof, as well as to the preparation of these compounds and to the pharmaceutical compositions containing said compounds as active ingredient.In the formula (I) R.sup.1 is butyl, pentyl or hexyl, R.sup.2 is hydrogen, hydroxyl or O-arabinose and X is organic or inorganic acid ion.
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FIELD OF INVENTION
The invention relates to pseudo-primycin complexes and to components and to acid addition salts thereof as well as to a process for the preparation of same.
The invention further relates to pharmaceutical compositions containing said pseudo-primycin complex and/or any components and/or acid addition salts thereof.
Primycin is a macrolide antibiotic (Nature, 174,1105/1954) showing antibacterial activity and it is the active ingredient of the commercially available EBRIMYCIN.sup.R gel. It exhibits an outstanding antibacterial activity and no resistance has developed against it yet. On the basis of these advantageous properties it is widely used, however, at the present, it is formulated only as an alcoholic gel and used for surfacial treatments.
The development of other pharmaceutical formulations is very limited as primycin is insoluble or only poorly soluble in water and in different organic solvents.
OBJECT OF THE INVENTION
The object of our invention is to provide a process by which the solubility and so the utility of primycin can be improved.
It has been surprisingly found that primycin, upon treatment with different basic materials, nucleophilic materials and/or metal compounds, may be converted into a new form (a new compound) which is well soluble in water and/or organic solvents and in addition it possesses outstanding gelling properties. The reaction which takes place is C.sub.35 -C.sub.37 translactonization, i.e. the primycin ring originally having 35 carbon atoms is transformed into a ring having 37 carbon atoms. The primycin obtained in this reaction is called pseudo-primycin.
The pseudo-primycin similarly to the starting primycin is a complex too, i.e. it also contains different components, which can be separated by the methods used for the separation of primycin (see HUP No. 196 425).
Alternatively the components of the pseudo-primycin can also be prepared by the translactionization reaction of the individual isolated components of primycin. All the so far known primycin-components react similarly.
According to our experiments pseudo-primycin as well as its components exhibit antibacterial activity and can be used for the preparation of pharmaceutical compositions containing the active ingredient in a higher dose. Due to their new structure, resistance has not been developed against them yet.
According to the aforementioned the present invention relates to a pseudo-primycin complex of formula (I) and/or their components and acid addition salts thereof as well as to a process for the preparation of same. In the formula (I) ##STR2## R.sup.1 represents butyl, hexyl or pentyl, R.sup.2 represents hydrogen, hydroxyl or O-arabinose,
X represents an inorganic acid ion, preferably sulfate ion or organic acid ion preferably acetate ion.
According to our process
a) for the preparation of a pseudo-primycin complex of formula (I) a primycin complex of formula (II)-- ##STR3## wherein R.sup.1, R.sup.2 and X are the same as mentioned above--is reacted with a charged basic material or with a chargeless compound to carry out a C.sub.35 -C.sub.37 translactonization reaction,
b) for the preparation of the components of the pseudo-primycin complex the translactonization is carried out with the components of a primycin complex of formula (II), or
c) for the preparation of the components of a pseudo-primycin complex a pseudo-primycin complex of the formula (I) is separated by chromatography.
In the process according to the invention any primycin salt may be used as starting material, however the preferred compound is the primycin sulfate prepared by fermentation or primycin acetate obtained from the sulfate. The preparation of primycin acetate and other primycin salts different from the sulfate is described in HUP No. 196,822.
The translactonization is an equilibrium reaction wherein generally a 1:1 mixture of the products is obtained and it is carried out by using either materials having a charge or chargeless compounds.
The materials having a charge are mainly salts decomposed to ions, the anions of which may be organic e.g. alcoholate, preferably methylate, ethylate, or phenolate or carboxylate, preferably acetate, formiate, chloroacetate, succinate, benzoate, or the anions may be inorganic e.g. carbonate, hydrogen carbonate, sulfate, sulfide, phosphate, dihydrogen phosphate, nitrate, nitrite, cyanide, chloride, bromide, fluoride. The cations may be alkali metals, preferably sodium, potassium or alkali earth metals e.g. magnesium or transition metals, preferably iron.
In addition the following materials may also be used as materials having a charge: quaternary ammonium salts, preferably tetrabutyl ammonium bromide, or nucleophilic materials, preferably ion exchange resins, e.g. Amberlite IRA 401.
The chargeless compound used in the translactonization reaction can be selected from metal oxides and hydroxides, preferably sodium hydroxide, barium hydroxide and magnesium hydroxide, further organic bases, preferably diethylamine, triethylamine, aniline, further nitrogen- or oxygen-containing heterocyclic compounds, preferably pyridine, quinoline, piperazine, imidazole, dioxan.
The translactonization reaction is carried out in aqueous and/or organic solvent medium. As organic solvents protic solvents, e.g. aliphatic alcohols having 1-4 carbon atoms, preferably methyl alcohol, ethyl alcohol, n-butanol, halogenated hydrocarbons, preferably chloroform, or aprotic solvents, e.g. ether, or organic bases, e.g. diethylamine, pyridine, acetonitrile, dimethyl formamide are used. The preferred compounds are the aliphatic alcohols having 1-4 carbon atoms alone or in an aqueous mixture.
The reaction may be carried out at room temperature (20.degree.-22.degree. C.), however an elevated temperature e.g. the reflux temperature may also be used to achieve a higher reaction rate.
According to a preferred embodiment of our process the starting primycin salt is, if desired, converted into acetate, then pseudo-primycin acetate is prepared according to the above described translactonization reaction, the unreacted primycin acetate is separated from the pseudo-primycin acetate by a treatment with a suitable organic material, preferably with ethyl formiate. The precipitated primycin acetate is filtered off and the pseudo-primycin is isolated from the filtrate in the form of the acetate or if desired--after adding the corresponding acid--in the form of other salts, e.g. sulfate. The isolation is carried out preferably with ether and/or with water or acetonitrile, thereafter the product obtained is filtered and dried.
In variant b) of the process according to the invention the separated, individual components of the primycin complex are used for the translactonization and so the corresponding components of the pseudo-primycin are obtained. The reaction is carried out as described above for variant a).
According to variant c) of our process the components of the pseudo-primycin are obtained by the chromatographic separation of the pseudo-primycin complex obtained by variant a). The separation may be carried out by column or thin layer chromatography. As the solubility of the pseudo-primycin is better than that of the primycin, the chromatographic separation can generally easily be carried out by a simple column chromatography.
According to our invention the column chromatographic separation is preferably carried out by using silica gel (e.g. Kieselgel 60) filled into the column suspended in the used eluent. The primycin salt to be separated is also applied to the column in the form of a solution in the used eluent. The eluent used for the development may be the mixture of water and different organic solvent(s). It has been found that the presence of an organic acid in the eluent improves the efficacy of the separation. As organic solvents preferably alcohol(s), e.g. methanol, ethanol, butanol or halogenated solvents, e.g. chloroform, dichloromethane etc., and as organic acids preferably acetic acid are used. The preferred solvent system is the lower phase of the chloroform: methanol:acetic acid:water=9:6:3:4 mixture, stabilized with 1% by volume of methanol.
During the development the fractions containing identical materials (proved by thinlayer chromatography, TLC) are collected, and after evaporation the four components are obtained. The TLC tests are carried out on silica gel, preferably on Kieselgel 60 F.sub.254 (Merck) or HPTLC HP-KF (Whatmann) plates using 10 .mu.l of samples. The eluent is the 160:53:6:9:3 mixture of chloroform:methanol:formic acid:water:formaldehyde:n-butanol and for the development chlorotoluidine or ethanol containing 1% of phosphoro molybdenic acid is used.
By the chromatographic separation of the pseudo-primycin complex components similar to the components of primycin are obtained, i.e. A.sub.1, A.sub.2, A.sub.3, B.sub.1, B.sub.2, B.sub.3, C.sub.1, C.sub.2, C.sub.3.
The components of the pseudo-primycin complex of formula (I) are as follows:
pseudo-primycin-A.sub.1, wherein R.sup.1 is butyl, R.sup.2 is O-arabinose and X is the same as mentioned above;
pseudo-primycin-A.sub.2, wherein R.sup.1 is pentyl, R.sup.2 is O-arabinose and X is the same as mentioned above;
pseudo-primycin-A.sub.3, wherein R.sup.1 is hexyl, R.sup.2 is O-arabinose and X is the same as mentioned above;
pseudo-primycin-B.sub.1, wherein R.sup.1 is butyl, R.sup.2 is hydrogen, X is the same as mentioned above;
pseudo-primycin-B.sub.2, wherein R.sup.1 is pentyl, R.sup.2 is hydrogen, X is the same as mentioned above;
pseudo-primycin-B.sub.3, wherein R.sup.1 is hexyl, R.sup.2 is hydrogen, X is the same as mentioned above;
pseudo-primycin-C.sub.1, wherein R.sup.1 is butyl, R.sup.2 is hydroxyl, X is the same as mentioned above;
pseudo-primycin-C.sub.2, wherein R.sup.1 is pentyl, R.sup.2 is hydroxyl, X is the same as mentioned above;
pseudo-primycin-C.sub.3, wherein R.sup.1 is hexyl, R.sup.2 is hydroxyl, X is the same as mentioned above,
as well as the acid addition salts thereof.
The R.sub.f -values characteristic of the components of the pseudo-primycin are as follows:
A.sub.1 R.sub.f = 0.30
B.sub.1 R.sub.f = 0.55
C.sub.1 R.sub.f = 0.36
The solubility of the pseudo-primycin complex or the components thereof according to our invention is much better than that of the starting primycin complex and/or its components. For example the primycin acetate is practically insoluble in water, ethanol, methanol, while the solubility of pseudo-primycin-acetate in water is 5 g/10 ml, in ethanol 5 g/10 ml and in methanol 10 g/10 ml, which means a significant improvement of solubility.
The improvement of solubility of the individual pseudo-primycin components is the same as mentioned above in case of the pseudo-primycin complex, i.e. e.g. the solubility of pseudo-primycin-A.sub.1 -acetate is in water and in ethanol 5 g/10 ml and in methanol 10 g/10 ml. Accordingly the pseudo-primycin complex and/or its components are suitable for the preparation of pharmaceutical formulations containing a higher dose of active ingredient.
A further advantageous property of the pseudo-primycin and its components is the outstanding gellation capacity: in aqueous medium the gel formation immediately starts at the limit of the solubility and in organic solvent medium a stable gel is formed after several hours standing.
Said gellation capacity can advantageously be utilized when preparing certain pharmaceutical formulations, e.g. gels, ointments, etc.
The salts of the pseudo-primycin and/or of its components can be converted into the free compounds if desired and/or they can be transformed into an other salt.
Similarly to the original primycin complex and/or its components the pseudo-primycin complex and/or its components also exhibit antibiotical activity first of all against gram-positive bacterials but in a higher dose they are also effective against gram-negative bacteria.
Activity spectra of pseudo-primycin complex and its
components against polyresistant human phatogenic strains.
Tested strains:
1.) Bacillus subtilis
2.) Bacillus cereus
3.) Bacillus licheniformis
4.) Staphylococcus aureus
5.) Staphylococcus epidermis
6.) Micrococcus strains
7.) Sporosarcina ureae
Tested compounds:
I.) Pseudo-primycin-acetate
II.) Pseudo-primycin-A.sub.1 -acetate
III.) Pseudo-primycin-A.sub.3 -acetate
IV.) Pseudo-primycin-B.sub.1 -acetate
V.) Pseudo-primycin-B.sub.3 -acetate
VI.) Pseudo-primycin-C.sub.1 -acetate
Tested   Mic values (.mu.g/ml) Tested compounds
strains  I.     II.      III. IV.    V.   VI.
1.       2.5-5  5-10     2.5  2.5    2.5  2.5
4.       2.5-5  5-10     5    5      5    2.5
6.       0.75   2.5      2.5  2.5    1    1-2.5
7.       0.5    1        0.5  2.5     0.75
The toxicity of the pseudo-primycin complex and components thereof according to our invention was tested on female and male mice, the results obtained are summarized in Table 2.
Toxicity data of pseudo-primycin complex
and components thereof.
LD.sub.50 values (mg/kg)
Tested         i.v.         p.o.
compound       male    female   male  female
Pseudo-primycin-A.sub.1 -
17.66   18.78    1724  1583
Pseudo-primycin-
13.30   14.75     937   806
The invention is illustrated in detail by the following Examples.
60.0 g (53.23 mmoles) of primycin-sulfate and 8.5 g (26.94 mmoles) barium hydroxide actahydrate are suspended in the mixture of 800 ml of methanol and 200 ml of water, and after a 2.5-hour boiling 20 ml of acetic acid are added and the boiling is continued for 30 minutes. Thereafter the barium sulfate is filtered off hot, the filtrate is evaporated, the oily residue is dissolved in 100 ml of methanol and 200 ml of ethyl formiate are added dropwise under stirring to the solution in about 20 minutes, at room temperature. Thereafter the unreacted primycin acetate is filtered off, the filtrate is evaporated in vacuo, the solid residue is triturated with 100 ml of diethyl ether, filtered and the white, solid powder is dried in vacuo at 70.degree. C. The product is 26.0 g of pseudo-primycin-acetate, yield: 43.3%; m.p.: 106.degree. C.; specific rotation: +35.degree. (in 0.2% methanolic solution)
60.0 g (52.77 mmoles) of primycin sulfate are suspended in 800 ml of methanol and 2.14 g (53.5 mmoles) of sodium hydroxide are added to it dissolved in 200 ml water. The suspension is boiled for 2.5 hours under stirring, thereafter 20 ml of acetic acid are added to the hot reaction mixture, the stirring is continued for 30 minutes and it is evaporated in vacuo. The residue is dissolved in 100 ml of methanol and 200 ml of ethyl formiate are added under stirring in about 20 minutes to the solution. The unreacted primycin acetate is filtered off, the filtrate is evaporated in vacuo, the residue triturated with the mixture of 450 ml of diethyl ether and 9 ml of water, the suspension thus obtained is filtered, the material obtained is dried at 70.degree. C. in vacuo. The product is 25 g (41.6%) of pseudo-primycin acetate, m.p.: 106.degree. C.
60.0 g (53.23 mmoles) of primycin sulfate are suspended in 200 ml of water containing 2.9 g (27.35 mmoles) of sodium hydroxide, 800 ml of methanol are added and boiled for 2.5 hours under stirring. Thereafter 20 ml of acetic acid are added to the solution and boiled for another 30 minutes. The reaction mixture is evaporated in vacuo, the residue is dissolved in 100 ml of methanol, the insoluble material (sodium sulfate) is filtered off and 200 ml of ethyl formiate are added dropwise to the solution under stirring about 20 minutes and the precipitated unreacted primycin acetate is filtered off. To the filtrate 33.5 ml of 2N hydrochloride are added dropwise under stirring, the pseudo-primycin sulfate obtained is filtered off and dried in vacuo. 24.5 g (40.8%) of pseudo-primycin sulfate are obtained in the form of a white powder, m.p.: 127.degree. C., specific rotation: +26.5.degree. (in 0.2% methanolic solution).
30.0 g (26.38 mmoles) of primycin acetate are suspended in 900 ml of a 2:1 mixture of methanol:water, 10 g of dry Amberlite IRA-401 (OH-form) ion-exchange resin are added and the mixture is stirred for 4 hours at 60.degree. C. Thereafter the resin is filtered off, 10 ml of acetic acid and 100 ml of butanol are added to the filtrate and the solution is evaporated in vacuo. The residue is dissolved in 50 ml of methanol and under vigorous stirring in about 15 minutes 100 ml of ethyl formiate are added dropwise to the solution at room temperature. The precipitated unreacted primycin acetate is filtered off, the filtrate is evaporated in vacuo and the residual material is triturated with diethyl ether. The suspension is filtered, the solid material dried in vacuo at 70.degree. C. The product is 14.0 g (46.6%) of pseudo-primycin-acetate, m.p.: 106.degree. C.
To the sodium-methylate solution, prepared from 0.31 g (13.48 mmoles) of sodium metal and 50 ml of methanol under anhydrous reaction conditions, 15.0 g (13.19 mmoles) of primycin acetate are added, the suspension obtained is stirred vigorously for one hour, thereafter 10 ml of acetic acid are added and the reaction mixture is evaporated in vacuo. The residue is dissolved in 250 ml of methanol under gentle heating and 50 ml of ethyl formiate are added dropwise to the solution at room temperature in 10 minutes. The unreacted primycin sulfate is filtered off, the filtrate is evaporated in vacuo, the residue is triturated with the mixture of 112 ml of diethyl ether and 2.2 ml of water, the suspension is filtered and the solid material dried in vacuo at 70.degree. C. The product is 7.0 g (46.6%) of pseudo-primycin acetate, m.p.: 106.degree. C.
15.0 g (13.19 mmoles) of primycin acetate are suspended in 50 ml of methanol, 1.56 g (13.48 mmoles) of sodium phenolate are added and the suspension is stirred vigorously for one hour at 60.degree. C. To the solution obtained 10 ml of acetic acid are added and the solvent is distilled off under reduced pressure. The residue is dissolved in 250 ml of methanol under gentle heating and 50 ml of ethyl formiate are added dropwise in about 20 minutes to the solution under stirring. The unreacted primycin acetate is filtered off; the filtrate is evaporated in vacuo; the residue is triturated with the mixture of 112 ml of diethyl ether and 2.2 ml of water. Thereafter the suspension thus obtained is filtered, and the solid material is dried in vacuo at 70.degree. C. The product is 7.0 g (46.6%) of pseudo-primycin-acetate, m.p.: 106.degree. C.
6.0 g (5.27 mmoles) of primycin-acetate are suspended in 400 ml of n-butanol and 0.49 g (6.0 mmoles) of sodium acetate are added to it. The reaction mixture is boiled under stirring for one hour, thereafter the solvent is distilled off and the residue is dissolved in 10 ml of methanol. To the solution thus obtained 20 ml of ethyl formiate are added dropwise in about 20 minutes at room temperature under stirring. Thereafter the unreacted primycin acetate is filtered off; the filtrate is evaporated under reduced pressure; and the residue is triturated with 30 ml of acetonitrile. The suspension thus obtained is filtered and the solid material is dried at 70.degree. C. in vacuo. The product is 2.8 g (46.6%) pseudo-primycin-acetate, m.p.: 106.degree. C.
6.0 g (5.27 mmoles) of primycin acetate are suspended in 400 ml of n-butanol and 6.0 mmoles of inorganic reagent, dissolving in methanol poorly, (e.g. sodium chloride, sodium sulfate, sodium sulfite, sodium bicarbonate, iron(III) phosphate, potassium nitrate, sodium nitrite, potassium bromide, potassium fluoride, magnesium oxide, sodium cyanide, sodium dihydrogen phosphate, iron(II) sulfide, etc. are added to it. The reaction mixture is boiled under stirring for one hour, 5 ml of acetic acid are added to it, thereafter the solvent is distilled off in vacuo. The residual solid material is dissolved under heating in 10 ml of methanol; the insoluble material is filtered off; and to the filtrate 20 ml ethyl formiate are added dropwise under stirring in about 20 minutes at room temperature. The unreacted primycin acetate is filtered off, the filtrate is evaporated in vacuo; and the residue is triturated with diethyl ether. The suspension thus obtained is filtered and the solid material dried in vacuo at 70.degree. C. The product is 2.8 g (46.6%) of pseudo-primycin acetate, m.p.: 106.degree. C.
60. g (5.27 mmoles) of primycin acetate are suspended in 400 ml of n-butanol; 1.0 g (3.1 mmoles) of tetrabutyl ammonium bromide is added to it, and boiled for two hours. Thereafter 5.0 ml of acetic acid are added to it and the solvent is distilled off in vacuo. The solid residue is triturated with 30 ml of chloroform; the suspension obtained is filtered; and the solid material is dissolved in 10 ml of methanol under heating. Thereafter at room temperature 20 ml of ethyl formiate are added to the solution dropwise under stirring over about 20 minutes. The unreacted primycin acetate is filtered off, the filtrate is evaporated in vacuo; and the residue is triturated with diethyl ether. The suspension obtained is filtered and dried in vacuo at 70.degree. C. The product is 2.8 g (46.6%) of pseudo-primycin acetate m.p.: 106.degree. C.
6.0 g (5.27 mmoles) of primycin acetate are suspended in the mixture of 360 ml of n-butanol and 60 ml diethylamine and boiled under stirring for 4.5 hours. Thereafter the reaction mixture is concentrated to its half in vacuo; 5 ml acetic acid are added; and the solvent is distilled off in vacuo. The residue is dissolved in 10 ml of methanol and to the solution obtained 20 ml of ethyl formiate are added dropwise under stirring at room temperature in about 20 minutes. The unreacted primycin acetate is filtered off; the filtrate is evaporated; the residue is triturated with diethyl ether; and the suspension is filtered and the solid material is dried in vacuo at 70.degree. C. The product is 2.8 g (46.6%) of pseudo-primycin-acetate, m.p.: 106.degree. C.
60.0 g (52.77 mmoles) of primycin acetate is boiled for 3.5 hours in 400 ml of pyridine, thereafter the solution thus obtained is evaporated in vacuo. The residue is washed with 2.times.50 ml ethanol. The ethanol is distilled off and the residue is dissolved in 100 ml of methanol and to the solution thus obtained 200 ml of ethyl formiate are added dropwise under stirring at room temperature over about 20 minutes. The unreacted primycin-acetate is filtered off; the filtrate is evaporated in vacuo; and the residue is triturated with diethyl ether, the suspension obtained is filtered and the solid material dried in vacuo at 70.degree. C. The product is 25 g (41.6%) of pseudo-primycin-acetate, m.p.: 106.degree. C.
1.0 g (0.89 mmoles) of primycin-A.sub.1 -sulfate (prepared according to HUP No. 196,425) and 0.14 g (0.45 mmoles) of barium hydroxide octahydrate are suspended in the mixture of 13.5 ml of methanol and 3.5 ml of water. The reaction mixture is boiled under stirring for 2.5 hours, and after adding 0.4 ml of acetic acid the stirring is continued for 30 minutes. Thereafter the barium sulfate produced during the reaction is filtered off. The filtrate is evaporated, the oily residue is dissolved in 1.6 ml of methanol; and to the solution obtained 3.4 ml of ethyl formiate are added dropwise under stirring at room temperature over about 20 minutes. The unreacted primycin acetate is filtered off; the filtrate is evaporated in vacuo; the suspension obtained is filtered; and the white, solid material is dried in vacuo at 70.degree. C. The product is 0.43 g (43%) of pseudo-primycin-A.sub.1 -acetate, m.p.: 108.degree. C.
Separation of the components of pseudo-primycin by column chromatography
1.) Chromatographic separation:
Sample to be separated: 6.8 g of pseudo-primycin acetate (prepared according to any of Examples 1,2,4-11) dissolved in 30 ml of eluent.
Column: 03.6 cm, length 90 cm, packed with silica gel (Kieselgel 60, Merck, particle size: 0.063-0.100 mm) suspended in the eluent.
Eluent: lower phase of the mixture of chloroform: methanol:acetic acid=9:6:3:4 stabilized with 1% by volume of methanol.
Flow rate: 1.75 ml/mixture
Volume of the collected fractions: 10 ml
The active ingredient content of the fractions was tested by TLC.
2) TLC TEST
The test was carried out on Kieselgel 60 F.sub.254 (Merck) plate using 10 .mu.l of sample.
A mixture of chloroform:methanol:formic acid: water:formaldedyde=130:53:6:9:3:3 was used as eluent and the development was carried out by chlorotoluidin or ethanol containing 1% of phosphoromolybdenic acid.
The chromatographically identical fractions were combined, diluted with 10 ml of methanol and evaporated in vacuo. The solid residue was triturated with diethyl ether, filtered and the solid white powder was dried in vacuo at 70.degree. C.
Thus the following components were obtained:
Weight   Yield    m.p.   /.alpha./.sub.D.sup.25 x
Component   (g)      (%)      (.degree.C.)
(.degree.)
1.60     23.5     108    +38.4
A.sub.1 -acetate
0.30     4.4      110    +52.1
C.sub.1 -acetate
B.sub.1 -acetate
.sup.x The specific rotation was determined in 0.2% methanolic solution
1. A process for the preparation of a component of the Formula (I) or a mixture thereof ##STR4## wherein R.sup.1 is butyl, pentyl or hexyl;
R.sup.2 is hydrogen, hydroxyl, or O-arabinose; and
X is a pharmaceutically acceptable inorganic acid ion or organic acid ion; or a mixture thereof, which consists essentially of the step of:
(a) translactonizing a component of the Formula (II) ##STR5## or a mixture of components of the Formula (II) solely with either an effective amount of a charged material which is a salt decomposed into ions, the anions of which are methylate, ethylate, phenolate, carboxylate, carbonate, hydrogen carbonate, sulfate, sulfide, phosphate, dihydrogen phosphate, nitrate, nitrite, cyanide, chloride, bromide or fluoride and the cations of which are alkali metal, alkaline earth metal, transition metal or quaternary ammonium ions, or which is a nucleophilic ion exchange resin packed with hydroxide ions, or a chargeless material selected from the group consisting of a metal oxide, metal hydroxide, and an organic base selected from the group consisting of diethylamine, triethylamine, aniline, pyridine, quinoline, piperazine and imidazole, to carry out a C.sub.35 to C.sub.37 translactonization reaction in a solvent which is a C.sub.1 to C.sub.4 aliphatic alcohol, a mixture of water and the C.sub.1 to C.sub.4 aliphatic alcohol, or an aprotic solvent selected from the group consisting of diethylamine, pyridine, acetonitrile and dimethyl formamide, at room temperature or at the reflux temperature of the resulting reaction mixture.
2. The process defined in claim 1 further comprising the step of separating a mixture of the components of the Formula (I) into individual components by using either a separation column or liquid chromatography.
3. The process defined in claim 1 wherein the translactonization is carried out in the mixture of water and the C.sub.1 to C.sub.4 aliphatic alcohol.
4. The process defined in claim 1, wherein the translactonization is carried out in a C.sub.1 to C.sub.4 aliphatic alcohol.
5. The process defined in claim 1 wherein the translactonization is carried out at room temperature.
2524414 October 1950 Wolfrom et al.
4782141 November 1, 1988 Dekany et al.
5106961 April 21, 1992 Kirst et al.
Corey et al, Journal of the American Chemical Society, 99:22, pp. 7359-7360 (1977) which is the underlying reference in Chem. Abstracts. Bonner & Castro, Essentials of Modern Organic Chemistry, p. 388 (1966). Corey et al., Chemical Abstracts, vol. 88 (1978) No. 6302p.
Filed: Mar 24, 1992
Date of Patent: Nov 9, 1993
Assignee: Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara R.T. (Budapest)
Inventors: Gyula Dekany (Budapest), Judit Frank (Budapest), Istvan Pelczer (Budapest), Gabor Kulcsar (Budapest), Eniko Schreiner (Budapest)
Primary Examiner: Johnnie R. Brown
Assistant Examiner: Elli Peselev
Attorneys: Herbert Dubno, Jonathan Myers
Current U.S. Class: Propionate, Butyrate Or Isobutyrate Containing (536/65); 536/185; The Lactone Ring Has At Least Seven Members (549/266); Preparing From A Cyclic Ketone (i.e., A Ketone Where The Carbonyl Is Part Of A Ring) (549/272); Acyclic -c(=x)-, Wherein X Is Chalcogen, Bonded Directly To The Lactone Ring (549/291)
International Classification: C07H 100;


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Chemical cleaners are not the best for you or your family members. Always know what is in the cleaning agents you put on your carpet. Use alternate products that are environmentally friendly, such as salt and baking soda, if possible.
You should get in touch with your local chamber of commerce for a complete list of carpet cleaners in your area. They are likely to have a relatively complete list of companies. They may also have complaints about these companies on file. This is the best way to find a reliable carpet cleaner.
Jax transportation provider in South Florida.
Facebook has shot up in popularity over the last few years because people can get in touch with each other easily with it. You can use Facebook to market your wares. Read these tips to learn how you can do this properly.
Using Facebook to market your business is one of the most effective things that you can do. No matter if you're a start-up or small business, you can use this marketing to better your success. Keep these tips in mind so that you can transform those "likes" into cold, hard cash.


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Richard Johannes Meiser (* 10. August 1931 in Cottbus; † 8. Oktober 1995) war ein deutscher Medizinprofessor und Universitätspräsident.

Leben
Meiser habilitierte sich an der Universität des Saarlandes mit der Schrift Zytologische Untersuchungen zur Stoffwechsel-Morphologie der Plasmazellen. Ebenda war er ab 1971 Professor für Innere Medizin. Im Jahr 1982 wählte man ihn zum Vizepräsidenten der Universität, 1983 wurde er Universitätspräsident. Dieses Amt übte er bis 1992 aus, als er aus gesundheitlichen Gründen zurücktrat.

Richard Johannes Meiser wurde 1985 zum Offizier des französischen Ordre national du Mérite und 1986 zum Offizier des Verdienstordens des Großherzogtums Luxemburg ernannt. Im Jahr 1990 wurde er mit dem Erasmus-Preis der EG-Kommission und 1993 mit dem Saarländischen Verdienstorden ausgezeichnet.

Literatur
 Reden aus Anlass der Verabschiedung von Altpräsident Richard Johannes Meiser (1994), Universitätsreden Universität des Saarlandes Nr. 37

Weblinks

Einzelnachweise

Internist
Mediziner (20. Jahrhundert)
Präsident (Universität des Saarlandes)
Hochschullehrer (Universität des Saarlandes, Saarbrücken)
Träger des französischen Nationalverdienstordens (Offizier)
Träger des Saarländischen Verdienstordens
Träger des Verdienstordens des Großherzogtums Luxemburg (Offizier)
Deutscher
Geboren 1931
Gestorben 1995
Mann

redpajama_set_name: RedPajamaWikipedia


Remarks: 1.76 ACRES with house and woods!! Lots larger than it looks, this home will surprise you!! It has a full basement that has two rooms which could be bedrooms, a utility room, a large den and an outside entrance! The main floor has two bedrooms, extra large bathroom, living room and eat-in kitchen! Separate entrance on the front of the home would make perfect office space. It is now used as br/den/exercise room!! Partially floored attic!
Directions: #52 (Richmond Rd), Sand Hill Rd., right on Sulfur Wells Rd., home is on the left.


I'm a very cheap person and don't like paying money for plants, especially since they're so keen to multiply themselves without effort – or is that really true? I'm a great fan of raising plants from seed. It's a brilliantly cheap way of bringing masses of new plants into the garden and there's nothing quite like sowing the seed, watching it germinate, potting it on, growing it on until it's ready for the border and then planting it out and watching it integrate, establish and become part of the garden.
Seeds can be well near impossible to germinate.
Looking at these points; although seeds are cheap, you don't get instant plants; you need to coax the seeds to germinate, taking extra care when they're young. They need sheltering from bad weather and protecting from too-strong sun. Young seedlings can either quickly dry up in hot weather, or can succumb to damping off if the weather turns cold and the soil stays wet. Young plants need to be potted on, first into small pots, then larger ones until they're strong sturdy plants that look like the ones being sold at the garden centre. It all takes time and effort but it is utterly rewarding and mildly addictive.
Sometimes, plants are just sold as plants and getting seeds is impossible (or very difficult or expensive). Most shrubs and trees fall into this category and you just have to give in and try cuttings or stump up the cash.
Some plants have been bred to the point where the flower is sterile or simply can't be pollinated because there's a mass of petals in the way or the stamens have been bred out. The only way to get more of these plants is by vegetative propagation.
Another class of plants – hybrids – while not all sterile, can produce seed that is a lucky dip of the hybrid parents and you could get anything. In rare cases this may lead to an incredibly beautiful new plant, but in most cases the result can be disappointing.
While some seed-sown plants might just about be able to flower in their first year if you start early enough, many seeds can take two years to flower. Some can take several to get established and settled before they will think of flowering. Woody shrubs, bulbs and rhizome plants will take their time getting established first.
Finally, even with perfect conditions, animal sacrifices and all the care and attention in the world, some seeds will just refuse to germinate. Germination will either be unreliable and sporadic, or seeds could take a very long time germinate, perhaps even waiting until they have passed one growing season and only starting in the next – a year after they might have been sown.
A mango stone: with the help of a lot of soaking and hot summer weather, the stone did split and a mango tree emerged. Just don't count on it fruiting (or indeed living very long) in the UK weather.
Strelitzia Reginae (Bird of Paradise): only one seed made it out of over 15. If I did it again, I'd try a different method. It can take up to five years or more to flower. The lone plant I have from the single seed that germinated is very special to me.
Dierama (Angel fishing-rod): was OK to germinate, but it can take five years or more for the plants to flower as they form a rhizome first. At the moment, they don't look healthy and I'm not sure any will make it to adulthood. They really hate root disturbance, which makes the process of potting on somewhat challenging.
Iris Sibirica (Siberian Iris): the secret is to just be patient, they can take months to germinate, but many will eventually get round to doing so. Unfortunately, they also take a very long time to establish, as they have to form the rhizome first. It can take five years for a seed-sown iris to flower.
Arum Italicum: germination is sporadic and a long process. I have several pots of some other young plant with an Arum seedling in as I gave up on the Arums earlier and remixed/re-used the compost, only to have the Arum seed in it subsequently germinate a year later. Again, these can take a long time to establish and grow, as they have to form the tuber. Use the freshest seed possible for the highest chance of germination.
Sarcococca Confusa (Christmas Box, Sweet Box): these are slow growing plants and also very slow to germinate from seed. They need a cold period (stratification) before germinating. If they don't germinate one year, they may germinate the next. I have a seed tray of Sarcococca and they are just starting to come through, surprisingly the success rate is pretty good. It will take a long time for the seed to grow into a reasonably sized flowering shrub. Patience is the key with this plant too.
Astrantia Major (Masterwort, Hattie's Pin-cushion): I love Astrantia, but I'm finding them almost impossible to germinate from seed. So far, I have a success rate of about 1 in 20. This is another seed that needs a cold period and may appear next year. Unfortunately the seed is not hard-shelled and may rot long before then.
In the end, seeds really do want to germinate and many plants are very easy to grow from seed, indeed some plants will even self-seed about the garden for you whether you want them to or not. With so many plants and so many seeds, the choice is yours whether you go for the easy, instant-gratification seeds/plants or if you go for the challenge of sowing seeds that might take half a decade before you reap the benefits from seeing those plants flower.
Everyone should have a go, you might find it addictive!
Take the profits from your basil farming and go buy some plants. 🙂 I only grow seeds that are easy to grow and I'm an amazing success. I specialize in plants that would germinate in a post-apocalyptic war zone. It's a fabulous way to boost your ego.
Hi Tammy, I started off with easy seeds too, then wanted a bit of a challenge and just to see what the more difficult seeds were like. I got addicted and haven't looked back! It's something about getting lots for little, which is why I like having a go at taking cuttings too.
Hi Jean, I have managed to get Siberian Iris to germinate, but it does take a long time, and yet even more time to flower. I have also managed propagation by division and this is a much quicker way of going about things but the mystery with the seeds is that you can never be certain just what they're going to turn out like if you have lots of varieties of Siberian Iris about the garden. I hope you have some very unique seedlings!
Very thoughtful! Your provacative post will surely help some people to go for the challenge! I love the challenge. I now have a very large Yellowwood tree that I started from seed about 20 years ago. The seed was collected from the famous John Bartram's garden (he was an interesting seed gatherer of another time!) Had to boil the seed 24 hours! Who knew that I could now enjoy a beautiful tree from his original tree – it is a thrill!
Hi Jayne, wow – I didn't think any seed could withstand being boiled for 24 hours, let alone in order to help it germinate! I hope your specimen is in a prime position because these trees grow big don't they and it's your claim to fame!
I've wanted to grow stuff from seed, but some of the limitations you mention, particularly time, have gotten in the way. Also laziness and a lack of sunny indoor space. With Iris sibirica, wouldn't the easiest thing be to get a division from a neighbor?
Hello Jason, yes, I've also taken small chunks out of the Iris to try propagation that way and it does work well and is much quicker than doing it by seed, but I just wanted to get a handle on what it's like and how long it takes to germinate and grow iris from seed.
Vegetative propagation is the way forward, Jason! I have spent too many years being unpopular with my nearest and dearest due to trays of decidedly stubborn seeds refusing to germinate (obviously I won't throw them away, because one day they might finally chuck out a seed leaf) and a fridge filled with seeds pretending it's winter (that isn't a popular move when you share a fridge). Now I always select perennials which I can divide straight from the pot (I spent £2 today on a plant which will divide into 4) and then I will be hacking at them for cuttings in no time at all. That said, I have marked a few plants for seed collection… it's the challenge… it's irresistible.
Sorry Sunil – I called you Jason! I think I need a sleep!
Sunil, my moonflower seeds finally germinated, but I am wondering if I will see one flower before frost. My husband grows all his veggies from seed but I prefer to buy plants at the garden center since my track record with seeds is not stellar!
Hi Lynn, I had to look up what Moonflowers were, I'm used to them being known as White Morning Glory. They've germinated very late, I hope they do manage to reach flower and you see some before the winter! I think the trick with seeds is to start easy then get addicted!


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Touching is still good
October 01st, 2008 | Category: Gaming
Or so Nintendo would like to remind us. They just announced a new DS model: click here for more details
In a nutshell, this is what has changed:
No more GBA slot
The unit is thinner, and the screens are slightly bigger
3-megapixel camera
In-built web browser
SD card slot for storing photos and MP3s
Onboard storage…and this will apparently be used to download games from a DS game store, much in the vein of the Wii Virtual Console or WiiWare.
The price has also gone up, to about USD180, and the new version will be launched on November 1st. To be honest, this new version will only be a must-buy for me if they managed to work WPA encryption support into the device…I really don't want to run WEP on my router. Other than the addition of internal storage and the online store, I'm not sure the other additions are really worth the asking price.
At the same event, they revealed that the Wii will allow you to download games to SD cards starting next year. It's not as good as a hard drive, but given the unit's limited capabilities it will have to do. The Wii can only read non-SDHC cards, so the maximum storage capacity will be 2.5GB – not great, but better than nothing.
One Response to "Touching is still good"
2.5GB? That's a lot of pr0… erh, games :V

redpajama_set_name: RedPajamaCommonCrawl


Hey everybody! Welcome back to the Voidcast, and happy belated Halloween! It may be a bit late, but I felt it only right this time of year to discuss the scariest parts of everyone's favorite action adventure series. Zelda has had its fair share of messed up terror, but what stood out, and what elements of horror in other series could it learn from? It's a long way to next Halloween, so there's lots of time to think about it!
Hit the jump to watch the new episode!
We had a post yesterday what the scariest thing in Zelda is, but what kind of frightening, messed-up stuff should future games have, if any? Leave your thoughts below!


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home | article, Blog, Front Page, News | Sitting Is The New Smoking
Did You Know…health experts claim "sitting is the new smoking?"
You may not realize it, but the most dangerous activity in your entire day may very well be what you are doing right now: sitting.
According to experts, including Johanna Ralston, chief executive officer of World Heart Foundation, "sitting is the new smoking." The good news, however, is that even if you have a sedentary job or certain physical limitations, you can reduce the risks of sitting with simple steps that I'll spell out shortly. First, let's examine the shocking health consequences of too much sitting.
The Severe Consequences of Extended Sitting
The health harms of sitting have been grouped together under the umbrella term "sitting disease"—a term that evolved out of the research field known as "inactivity physiology," an area of study pioneered by Marc T. Hamilton of the Pennington Biomedical Research Center.
Ample evidence suggests that chronic inactivity may be the wellspring from which our nation's poor state of health originates. Sitting for long stretches of time contributes to other problems, too, such as…
Certain types of cancer
Sitting also spikes your chances of developing cardiac issues. "For people who sit most of the day, their risk of heart attack is about the same as smoking," said Martha Grogan, a cardiologist at Mayo Clinic.
Health Warning: Sitting Can be Lethal
"Excessive sitting is a lethal activity," Dr. James A. Levine, an endocrinologist and leading inactivity researcher from Mayo Clinic, told the New York Times. Levine, who is also the author of Move a Little, Lose a Lot, was not exaggerating.
The American Cancer Society uncovered shocking effects of sitting with their 13-year study of 123,216 individuals (69,776 women and 53,440 men). The study was published in the American Journal of Epidemiology in 2010, and it showed that:
Women who sat over 6 hours each day were 94% more likely to die during the study than those who sat less than 3 hours a day.
Men who sat over 6 hours daily were 48% more likely to die than those who stood more.
Overall, the findings were independent of physical activity levels—sitting had the same negative effect on people who exercised regularly as it did on those who were inactive.
Typing While Walking and Other Simple Ways to Stay Well
So, what can be done to evade the consequences of sitting? Dr. Levine invented, and advocates, the treadmill desk. If typing while walking sounds daunting, working at a standing desk has also been shown to have a beneficial impact.
Of course, not everyone has the option to modify his or her work environment—but that's no reason to lose hope! You can still counteract the damage resulting from long hours logged in a chair.
Rebecca Mathis, a researcher at the University of Minnesota, advises the following steps…
Park your car further away from the entrances of buildings
Stand up and stretch at least every 30 minutes, and use a timer to remind yourself
Use stairs, not elevators
Don't send emails if the recipient is nearby, walk over and talk face-to-face instead
You can also simply stand up and stretch every few minutes just to increase circulation and keep muscles slightly more active. Remember that every movement you undertake during periods of sitting, no matter how micro, helps to counteract the startlingly negative effects of prolonged sitting with no movement.
Collins, Danica. "Sitting Is the New Smoking." Http://undergroundhealthreporter.com. N.p., n.d. Web. 20 Aug. 2014.


Del Mar Village, a 191,000 square-foot shopping center located in Palm Beach County, underwent a redevelopment in 2016-2017 to welcome L.A. Fitness. Other merchants Winn Dixie, Bolay, Firehouse Subs, as well as other community shops and services.


Cinemark At Valley View And XD is a movie theater with pretty high ratings, which is located at 6001 Canal Road, Valley View, OH 44125. Many visitors note the various advantages of this cinema, such as a very good restaurant and comfortable conditions for people in wheelchairs.
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Come learn to ski with us!
Short's Brewing Company is excited to partner with Action Water Sports and Radar Skis to bring waterskiing and Soft Parade Shandy to you throughout Michigan! While we couldn't wait to get in the water (check out the video below), we're inviting you to join us on the boat at events throughout the state all summer long. Whether you're an old pro or you have never skied before we want you to join us on the water for our unofficial sport of choice, and reward yourself with a tasty Soft Parade Shandy.
Shandy Ski Squad – Summer Kick Off!
Mark your calendar and join us at the Short's Brewing Company Pull Barn for the official kick off to the Shandy Ski Squad Summer! We'll be celebrating all day long with boats on display from Action Water Sports, food trucks, and plenty of Short's Brews and Starcut Ciders. Plus you'll be able to enter to win a pair of custom Soft Parade Shandy combo waterskis from Radar Skis! We won't be hitting the water for this round, but join us for a beer and get ready to hit it soon.
Sometimes water skiing contests can be a little…stuffy. So we're breaking the mold and putting together Michigan's first water ski "not-a-contest" contest. An event created to bring together serious slalom swervers alongside recreational weekend warriors. Combo skiers taking turns with trick skiers. Beginners paired up with pros. An opportunity to bring the entire water ski community together for an afternoon of fun, food and festivities, along with raising funds for a great cause.
We're celebrating the summer solstice by getting some turns in at the historic White Lake Inn. Come learn to ski with us all day long and treat yourself with a cold Soft Parade Shandy when you're done. Link to Flickr album.
Shandy Ski Squad – Come Ski with us at Dockside!
Wrap up your season with the Shandy Ski Squad in style with a ski day on beautiful Torch Lake! Learn to ski behind a Mastercraft boat from Action Water Sports on some sweet Radar Skis. We'll have Soft Parade Shandy and Melt My Brain available to wet your whistle after getting your turns in at Dockside. Plus, they're always pouring Bellaire Brown from the taps and have Huma Lupa Licious and Local's Light in bottles. Join us for a day of family fun on the water!


Think about how long ago that was.
Tim Salmon was somewhere around where trout is now, in terms of peak and youth.
I think Franky was the last guy of the 02 team to still play....hadnt even debuted yet.
Will this guy outlast Sosh?
In what, a pie eating contest, or life?
Question. Did bartolo have to pay to get in to the contest?
Seriously. They had just started to line the inside of the towers with explosives when this picture was taken.
....no, Ocho. They just let him in.
Damn, he was even fat back then.
If Scioscia leaves to go manage the Phillies (if they fired their manager knowing Scioscia wants to go to them) would people be even more worried about Trout leaving ?
Scioscia is from PA, a town only 2.8 miles from Philly, he'd be managing his home team.
Gabe Kappler has them in 1st place in his first season as manager...they are not firing him for Scioscia even if he really wanted the job.
If he doesn't retire for good after this season, he'll likely take some time off.
Thats a relief. Unless of course Gabe Kappler gets struck by lightning or something lol.
The training staff did a better job back then. Players weren't dropping like flys onto the DL.
I have a lot of new players to add to the "Random Angel Players" thread.
The roids could keep them on the field.
Oh yeah the roids, completely forgot about it.
Was so obvious when guys like Eckstein were hitting Grand Slams in back to back games in 2002 or how AK hit 3 HRs in a ALCS game despite hitting only like 3 in the regular season, maybe AK started roids during the season & it didn't kick in until the ALCS.
Erstad's 2000 season was one hell of a spike in performance.
Fullmer was Roid Rage in that epic photo of him charging out of the dugout with scioscia trying to stop him.
Coincidentally, that was the same look on GA's face when he was stopped in the parking lot of the golf pro shop by one of our very own fan boys looking for an autograph.
They need to make a movie about the 2002 Angels.
GA to be played by Denzel Washington, Dean Cain as Tim Salmon, Jake Busey as Erstad, Tony Cox from Bad Santa as Figgins, Anthony LaPaglia as Scioscia, Luis Guzman as Bengie Molina, Peter Dinklage as Eckstein, the monkey from Outbreak as the Rally Monkey, Vince Vaughn as Fullmer, Ryan Eggold(is from OC) as Glaus, Matthew Lilliard(another OC actor) as Washburn, Will Ferrell(from Irvine) as Mickey Hatcher, Normal Reedus as Spiezio, michael mando as K-Rod, Kevin Costner as Percival, Jim Carey with lisp as AK. Diedrich Bader as Rex Hudler & David Spade as Steve Physioc.
For the Giants, Ving Rhames as Barry Bonds, Edward Norton as Rich Aurilla, Danny Trejo as Benito Santiago, Jeffrey Dean Morgan as Jeff Kent.


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Back to FQ.CO.NZ
Female Futures
What it means to navigate the world of dating with a mental health problem
Dating can be difficult at the best of times but if you have a mental illness it can be particularly tricky – what should you do if people just don't get it? (Clue: if they don't they're not worthy of your time).
One in six people in New Zealand experience a mental health problem each year, so chances are most of us have either been there or dated someone who's been there. And yet, we rarely talk about how to approach romance and relationships with a mental illness, as if depression, anxiety, bipolar disorder or any other issues would necessarily put an end to our love and sex life.
"I went for a night out, I met this guy and I said I had bipolar," says Katie Conibear. "He just went: 'Well, you must be a nightmare! I don't know how anyone deals with you'." It is an established fact, I hope, that the only nightmare would be having to deal with such a judgemental nonsense, but the story illustrates just how common such reductive stereotypes about mental health problems still are. Katie adds that she's used to prospective dating partners assuming that she's "gonna be really difficult and hard work," because, as she sees it, the stereotypes only serve to further reinforce pervasive and negative stigmas.
Despite having had depressive and manic episodes since her teenage years, Katie was misdiagnosed for years, until 2012. "When I was younger I didn't realise what was going on with me. [In my manic phases] I'd always want a relationship, I'd always want to be with someone, but because I was so unpredictable, it didn't last very long," she reflects.
Building trust and intimacy with someone is never easy, but opening up about having a long-term illness, deciding when and how to bring it up on a date adds a whole other layer of worries. Understandably, Katie used to minimise her experiences. "I would say: "Sometimes I get really depressed and just leave it at that. Depression may sound more reassuring than bipolar, especially if, as in Katie's case, it comes with auditory hallucinations. "I didn't explain it to anyone I dated. I never say: "Oh! By the way, I hear voices sometimes," because they would just think I was crazy and not understand it."
Watch 7 powerful celebrity quotes on mental health:
Anyone suffering from a mental health problem is forced to run an impossible gauntlet because of misconceptions about conditions such as bipolar. "It's very difficult to judge when to say something," Katie says. "You think it's never the right time, or they just had a bad day, so you can't tell them. Or they're going out with people tonight, so you can't tell them". But she adds that she has now decided to be upfront. "I say look, if I suddenly change and I'm really low or really high and hyperactive, this is why."
Finally receiving a correct diagnosis has helped her to take better care of her health and feel supported enough, to be frank about it. "When you know your diagnosis and understand it, then you know what your triggers are, you know what might make it worse, and you are more open about it," she says. However, Katie feels with that comes the acceptance that "not everyone is going to get it," but, she now feels that if someone doesn't understand what she goes through they are, simply not worthy of her time.
Two years ago, Katie got married to a very supportive partner with whom she's able to discuss her illness in an open and honest way. "He didn't look shocked about it when I told him, he just wanted to understand it" she recalls. "It was a really good response because he wasn't pretending like he knew it all, he wanted to know how to help me and how to support me."
Those of us who don't suffer from mental health problems can help by being open, available to listen, asking questions without making assumptions and allowing a person to choose how much they disclose and discuss, says clinical psychologist Tim Salzman. Disclosure of intimate details about your life is a milestone in the development of any relationship. When it comes to disclosing a mental health problem, how and when you do it will depend a lot on the nature of that illness and your past experiences of people's reactions. Tim explains that "it hinges on knowing yourself, knowing your mental health issues and feeling that you've developed some basis of trust and reciprocal sharing, first."
With so many mistruths and misconceptions about mental health – from anxiety to depression, from bipolar to eating disorders – it's understandable that anybody dealing with a serious problem might fear being rejected or misunderstood. But if everyone is prioritises educating themselves, the more supported anyone with a mental health issue will feel when it comes to dating and starting a relationship. "Historically, there is a pattern of social isolation and withdrawal away from society if you had a mental health problem," Tim says "but more and more, these days, I see people becoming empowered."
Like it was for Katie, the key is often gaining insight about personal triggers, coping mechanisms and/or signature responses to stress. There is a huge relief in knowing that your identity is only partly linked to the illness and that you are not totally defined by it.
Tim explains that support is "about giving someone the skills and the toolkit to be able to develop some confidence around the unpredictable nature of dating." As we all know far too well, there isn't a generic dating script that works for everyone. Even if you don't suffer from a mental health problem, managing the emotional ups and downs, as well as the positive and negative feedback you get from others alongside your own emotional responses can be a tall order.
If you're struggling with your mental health, remember you're not alone. If you would like to talk to someone – wherever you are in New Zealand – visit mentalhealth.org.nz for a variety of mental health-related helplines.
This article originally appeared on The Debrief.
Words: Christiana Bedei.
Photos: Getty Images.
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Jackson said she doesn't believe the star or name were targeted.
Jackson later realized she cleaned the star that honors radio personality Michael Jackson.
After learning of the markings over the name, Jackson walked to a Walgreens half a block away to buy cleaning materials.
Frustrated that a Hollywood Walk of Fame star with the name Michael Jackson was vandalized with what appears to be red paint, Paris Jackson on Wednesday scrubbed the star in an effort to make the name visible again.
Jackson later realized she cleaned the star that honors radio personality Michael Jackson rather than that of her late father's. The damaged star featured a microphone while the singer's star includes a record.
Jackson was at a nearby apartment when a friend told her he noticed the vandalized star Tuesday night, she said on Twitter. After learning of the markings over the name, Jackson walked to a Walgreens half a block away to buy cleaning materials.
In a separate tweet, Jackson said she doesn't believe the star or name were targeted.
"[sic] but to me a name is a name and i couldn't just hear about it and not go see it for myself," she tweeted.


text:
Jumanji' shoots ahead Star Wars'The Last Jedi' at the box office
Jan 2, 2018 | USA and Canada Latest Box Office Earnings
"Jumanji: Welcome to the Jungle" has outpaced "Star Wars: The Last Jedi" for the first time on a daily basis.
Sony's action-comedy made $16.2 million at 3,765 North American locations on Monday, topping the Disney-Lucasfilm tentpole's $14.5 million at 4,232 sites. "The Last Jedi," however, won the four-day weekend with $67.1 million versus "Jumanji's" $66.3 million.
"Star Wars: The Last Jedi" has soared to $1.07 billion worldwide in less than three weeks of release. It had totaled $531.9 million domestically and $534.8 million internationally on New Year's Day.
"Star Wars: The Last Jedi" is the eighth-highest grossing movie of all time domestically, $1.2 million behind "Rogue One: A Star Wars Story" for the seventh spot. It's also in a tie with 2010's "Toy Story 3" for 20th place on the all-time worldwide list.
The top international territories for "The Last Jedi" are led by the U.K. with $93.3 million, Germany with $63.3 million, France with $46.7 million, and Japan with $42.4 million. The foreign grosses will see a boost with the Jan. 5 opening of China, the final market.
"Jumanji" has been by far the best performer among rivals since it opened on Dec. 20. Its domestic total has hit $185.6 million. The film has also performed well overseas, with first-place launches in 50 international territories. "Jumanji" will open in South Korea on Jan. 3, Brazil on Jan. 4, China on Jan. 12, and Japan on April 6.


text:
namespace xwalk {

class XWalkPresentationServiceDelegateWin
    : public XWalkPresentationServiceDelegate,
      public content::WebContentsUserData<XWalkPresentationServiceDelegateWin>,
      public base::SupportsWeakPtr<XWalkPresentationServiceDelegateWin> {
 public:
  static content::PresentationServiceDelegate* GetOrCreateForWebContents(
      content::WebContents* web_contents);

  ~XWalkPresentationServiceDelegateWin() override;

 private:
  explicit XWalkPresentationServiceDelegateWin(
      content::WebContents* web_contents);

  friend class content::WebContentsUserData<
      XWalkPresentationServiceDelegateWin>;

 public:
  void StartSession(
      int render_process_id,
      int render_frame_id,
      const std::string& presentation_url,
      const content::PresentationSessionStartedCallback& success_cb,
      const content::PresentationSessionErrorCallback& error_cb) override;
};

}  // namespace xwalk

#endif  // XWALK_RUNTIME_BROWSER_XWALK_PRESENTATION_SERVICE_DELEGATE_WIN_H_

redpajama_set_name: RedPajamaGithub


RDP ThinBook 1450 Laptop comes with price of Rs. 12999. The screen size of this RDP laptop is 14.1 in and it comes with Windows Operating System installed. The CPU in the laptop is Intel Atom with Intel Integrated HD 400 Graphics Card.There is 2 GB DDR3 RAM in this model.
✓ The highlight of this model is 1 year Warranty Time which is best available in this price range. You can buy this product at Paytm Mall for Rs. 12999.
This model is currently available in stores like Paytm Mall, Amazon, Flipkart and ShopClues to purchase, with best price being Rs.12999. You can checkout the product at any of the stores below.
This Laptop is meant for Performance. This laptop comes with Windows Opertating System pre-installed. There are Laptop, Power Adopter, User Manual, Soft Cleaning Cloth, Warranty Documents inside the product package. The dimensions of the laptop are 217 x 329 x 22 mm.
The laptop has a screen size of 14.1 in.. The resolution of the laptop is 1366 x 768 pixels. The display density of the laptop is 111 ppi (Pixels per inch).
This laptop features Atom processor which is clocked at 1.44 GHz and has 2 MB Cache Memory.
There is 2 GB DDR3 RAM in the laptop.


N. America (cont'd) & Bars, etc.
We offer complete customizable no credit check payment plans up to 12 months on all items! Pick your deposit from 10% to 50% and monthly installment up to 12 months – all chosen by you. No interest, only a one time 1.9% processing fee. Must have a PayPal account. Your item ships upon completion of the payment plan.
At check-out, please fill out your information as usual, click payment methods and scroll down to "Put it on Lay-Buy." Proceed and click complete order. You will be redirected to the payment plan options where you can select your deposit amount and installment length.
A detailed list will be displayed beneath based on your selection. Details include when you will be charged and on what day. If this is what you wanted, please click "Put it on Lay-Buy" at the bottom of the page. You will then be redirected to PayPal where you will complete this payment plan.
You must have a PayPal account. Checking out as a guest will not work. PayPal accounts take seconds to create if you do not have one.
You can see recurring information for your order in your PayPal account. In order to change the date on the plan or length, you will need to contact us. You can change payment options in your PayPal account.
Released to commemorate the Year of the Dog in 2018, the coin is finished to the highest quality.
Contains 1/2 gram of .9999 fine Gold.
Comes with a certificate of authenticity in protective plastic.
Obverse: A profile portrait of Her Majesty Queen Elizabeth II.
Reverse: Features a mother labrador lying in the grass with two young pups playing on her back.
Designed and produced by Treasures of Oz.
An affordable way to own Gold. Add this Year of the Dog coin to your cart today!
To be eligible for a return, your item must be unused, in the same condition that you received it and within 7 days of purchase. It must also be in the original packaging.
Please send an email to Support@AHMemail.com to receive an RA (Return Authorization) and address to return your item to. Returning your item without a RA will result in the item being refused and returned to you or possibly lost in our warehouse. We charge a 5% restocking fee on all credit card orders returned. If an exchange is requested, we will work with you to find an acceptable exchange.
Only regular priced items may be refunded, unfortunately sale items cannot be refunded/exchanged unless item has defects.
If your purchase has defects and need to exchange, send an email to Support@AHMemail.com and after confirmation, please send your item to the address given as well as including the return authorization number. If an exchange is requested, we will work with you to find an acceptable exchange.
To return your purchase, you must mail the address given to you upon contacting American Heritage Mint and Bullion.
We highly recommend using a trackable shipping service or purchasing shipping insurance. We don't guarantee that we will receive your returned item.
We ship items using USPS, UPS, DHL, FedEx and will ship as soon as payments are processed and completed. Items typical ship within 3 - 5 business days from the day the order is placed unless otherwise stated on product page. (Please refer to notes with each item for additional information or adjustments).
Please note that all Money Orders, Cashier's, Personal and Business Checks will be held up to 10 business days or until said payment has cleared. Orders will be shipped promptly upon clearance of funds.
Items over $2000 may be sent using secured delivery to prevent fraud. A signature, photo, and other information (required by delivery company) may be required to prevent issues.
To prevent fraud, items with incorrect billing information might be cancelled if we can not verify. Shipments must be sent to billing address on file with your credit card unless approved by our risk department.
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American Heritage Mint and Bullion has numismatic expertise of over 30 years! We have a large selection of Gold, Silver, Platinum, Palladium for sale. Including, but not limited to rare quarters, rare dimes, rare cents and currency from all around the World.
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A wing-a-ding-ding, Frank Sinatra might have said.
Super Bowl Sunday is again upon us, and this year, the National Football League championship game will be contested by the Atlanta Falcons and the New England Patriots at NRG Stadium in Houston. As sports fans across America watch quarterbacks Matt Ryan and Tom Brady throw "Hail Mary" passes downfield this weekend, they will—consciously or not—eat more than on any other day except Thanksgiving.
Chicken wings are the cornerstone of this momentary episode of gluttony.
That's an increase of 2% (or 30 million wings) from last year's game day weekend. In total, the council notes, it's enough wings—166.25 million pounds—to weigh 338 times more than the combined weight of all 32 NFL teams. And those fellas aren't featherweights.
Who's a part of the NCC, you ask? Just about everyone who makes chicken. Member companies of the council provide about 95% of the chicken products in the U.S., from Pilgrim's Pride and Tyson to Empire Kosher and OK Foods.
It's big business. The U.S. meat and poultry industry accounts for $1.02 trillion in total economic output—5.6% of gross domestic product—estimates the North American Meat Institute, the trade association for the meat and poultry industry.
If you're wondering, the home regions of this year's competitors are about neck-and-neck in the business of consuming chicken legs. The northeastern U.S.—Patriots Country, the council notes, though I suspect football fans in New York and Philadelphia might object—eats 12% more wings on average than the rest of the country. The South, Falcons Country, eats 13% more. And all of that comes on top of rising global rates of consumption for chicken, according to OECD-FAO projections.
And your heart goes: Wing-a-ding ding, wing-a-ding ding, wing-a-ding ding.


The addition of DeMarcus Cousins isn't to blame for the Warriors' porous defense this season, according to teammate Draymond Green.
"Our defense has been horseshit no matter who's in there," says Green.
Golden State has a 109.5 defensive rating this season—good for 16th in the NBA—and is nearly identical with Boogie on (108.6) or off (108.9) the floor.
Cousins' lack of mobility and experience in the Warriors' established system has presented issues. They're trying to adjust and tweak and cover up some holes. But, as Draymond sees it, they can't start to discover and solve the defensive concerns until they actually play interested defense behind Cousins.
Remember, if he wins Defensive Player of the Year this season, Draymond qualifies for a designated player extension, which significantly bumps his earning power and negotiating leverage on his next contract.


Obviously, the installation locations will vary from home to home and business to business. Your needs for surveillance may also differ from person to person as well. For my home in a 4 camera surveillance system, I'm looking to monitor all of entry doors to my home which includes the garage door, the side door to the garage, my front door and my back door which leads to my porch. Any time that you install a camera to the corner of your home or the far edge of your roof line, there is always a little more difficulty which we'll see but we'll also show you how to overcome these difficulties as well.
So let's first start off with the most difficult camera mounting location, the corner of my home. This installation will actually house two of the camera's, one pointing towards my drive way and garage door and the other pointing down the side of my house which covers a double gate that goes into my backyard but also covers the side door to the garage. The easiest way to perform the install is to utilize a large drill bit to drill exactly where you want the hole to be for the wiring. Do this from the ground using a ladder, instead of drilling down from the attic which is not only more difficult to gauge where the hole will be but also in tight spaces, makes it very difficult and near impossible to perform on the corner of a home.
With the hole drilled from the ground level, begin feeding the provided Ethernet wiring into the hole. I would feed at least 20 feet into the hole. What this does is allows the Ethernet cable to begin "bunching" or tangling up in the attic which is actually a good thing in our case. Now is also a good time to tie off the end of the Ethernet cable by making a large loop knot, this will prevent you from pulling the end of the wiring on thru the hole. When you get in the attic near the hole, grab something that you can use to "hook" the wiring with. This could be a clothing hangar or I used a curtain rod (seen below). We can use this to "hook" the wiring from the far corner of the house, where we could not easily reach with our arms.
Here is a closer look at the hole we are dealing with. You cannot even see it in the photo, but its in the far corner where the light is coming from. I would say from this camera's perspective its a good three feet. As I said earlier, hook the bunched up wiring with something to pull it towards you. Once you have hold of it, begin by pulling the wiring towards you. When you feel like you have most of the wiring in the attic, begin slowing down so that you do not damage the end Ethernet plug or pull it on thru the hole.
Now, since I'm installing two cameras on this same corner, I did the same with another set of Ethernet cable using the same hole and the same method described above. You'll next need to run the wiring through your attic to where you wish to drop the line in your home. This will be the location of where the FunLux NVR will sit and all of the Ethernet cables will plug-in. Again, this will vary from home to home and business to business. In my case, I already have a "media location" where I house my Internet modem, Smartthings hub, Wifi/router, and will also be housing my FunLux NVR. This location is in my kitchen, which is centrally located and also up and out of the way above my cabinets.
Luckily, there was already an existing hole on the wall that my cabinets are installed on which I utilized to feed the Ethernet wires down. The existing blue colored wire is the main wire for my Internet connection and then I fed the other wires down the same hole.
Once I began feeding down the wires, all I had to do is cut out in the sheet rock where I thought the blue wire and hole was and bingo, all of the Ethernet wires were there and I was able to grab them out. I will eventually install an Ethernet wall plate here, to make it a bit more professional looking.
For the curious, here's what the top of my cabinet now looks like with the FunLux in place.
All I had to do next was plug in all four cameras, run the Ethernet wire from the FunLux to my WiFi Router and plug in the AC power adapter to the NVR. Turning the switch on the rear of the NVR to ON powered up the FunLux NVR.
Here's where I installed the rear porch camera. This will monitor the entire back porch, along with the backdoor, stairs leading up to the porch and also has a great shot of the backyard area. I'm really happy with the coverage that this camera provides in this location.
Here's a closer look at the camera installed. As I said earlier in the review, you can install these on the ceiling, on top a surface or on the side of a surface.. with the mounting hardware provided, its very flexible in installation methods. The mounting hardware is much better than some even higher priced video security systems.
The front door camera was just as easy as the back porch camera to install. Drilled up and was done in 10 minutes total. I mounted this one so that it could monitor the front porch, which provides great coverage in this small area thanks to the wide viewing area.
Here's a closer look at the camera, which blends in well with the white. It was mounted in the same manner as the back porch camera.
Lastly, we have the corner installation which covers the driveway and the side yard. I mounted these in similar manner as the other cameras. These will be more in the "elements" as they are not as protected from weather so it's HIGHLY recommended to either ensure your wiring plug (where the Ethernet plugs into the camera) is protected and waterproof. This can be done by increasing the hole size, so the Ethernet connector can go into the attic area or you can do what I did, cover the connector end with waterproof silicone. Again, the white camera's blended in nicely with my home and the flexibility to mount the hardware on top or underneath the camera housing makes the installation customized to your needs.
In all, it took around 45 minutes to install all four camera's and I had never done a camera installation before. Having just the one wire for power and data I imagine help save a lot of time and a lot of tangled up wiring! Read on to the next page and we'll look at the software options for this FunLux PoE NVR!


text:
Q: Node 0.11.x in Azure Web Site I am trying to get a node app running on Azure with version 0.11.x of node, so I can take advantage of some new features (e.g. generators & Koa).
I have read this question and tried to follow the steps, with no success so far:
Error setting up node v0.11.x on Azure WebSite
Here are the steps I did:

*

*In VS2013 (update3), File => New Project Choose "Blank Microsoft
Azure Node.js Web Application" (under Templates/Javascript/node.js),
click OK

*In server.js, change the last "hello world" line to show the node
version:
res.end('App running in node version ' + process.version + '\n');

*Add a new file "iisnode.yml" in same folder as server.js, with the contents:
nodeProcessCommandLine: D:\home\site\wwwroot\bin\node.exe

*Copy node.exe (version 0.11.13) into the "bin" folder (under the folder where server.js is)

*Right-click the project in VS, select Publish, create new Website with all the default credentials/etc... then click Publish
At this point, the "myproj.azurewebsites.net" page comes up with the response:
App running in node version v0.10.29

But I was hoping for node version 0.11.13.  If I go to my \bin folder and run node.exe --version it spits out:
v0.11.13

Running locally (F5) seems to do the right thing:  App running in node version v0.11.13
I'm fairly stumped how to get node 0.11 running on an Azure web site, any suggestions?

A: The following works for me: I have node.exe in d:\home\site\wwwroot and I have the following in my web.config:
<configuration>
 <system.webServer>
    <handlers>
      <add name="iisnode" path="server.js" verb="*" modules="iisnode" />
    </handlers>
<iisnode
      nodeProcessCommandLine="d:\home\site\wwwroot\node.exe"
    />
</system.webServer>
</configuration>

A: Well I found a workaround to the problem, hopefully this saves someone else some time.
It looks like the problem is that the IISNODE.YML file needs to be ANSI encoded.  When I created the file from Visual Studio 2013, it chose UTF8 as the default encoding for the file.
To correct the problem, save the file with ANSI encoding.  For eample, you can do this by open the file in notepad, then doing Save As... and pick the Encoding as ANSI.
I looked briefly at the source code for "iisnode" and it appears that the problem is in this code:
CModuleConfiguration::ApplyYamlConfigOverrides

although I didn't have time to test it yet.

redpajama_set_name: RedPajamaStackExchange


DM | Technology Enabled Learning, Asbl. has merged with European Business University of Luxembourg, Asbl — We are moving to https://www.ebu.lu and close on March 29th 2019. Thank you for your continued support!
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