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United States Patent U.S. C]. 252-430 5 Claims ABSTRACT OF THE DISCLOSURE Substantially colorless, highly polymeric condensation polyesters are prepared from a lower dialkyl ester of a bifunctional dicarboxylic acid and a bifunctional glycol by using a catalyst composition comprising a substantially amorphous, partially hydrated titanium dioxide dispersed in a liquid carrier compound.
This application is a continuationin-part of Bell and Strickland U.S. Ser. No. 441,857, filed Mar. 22, 1965, now abandoned which in turn is a continuation-in-part of Bell and Strickland U.S. Ser. No. 170,485, filed Feb. 1, 1962, now abandoned.
This invention relates to an unusually effective catalyst useful in preparing fiberand the film-forming linear condensation type polyesters of bifunctional dicarboxylic acids and bifunctional glycols, e.g., poly(ethylene terephthalate). This catalyst is freshly precipitated titanium hydroxide which is advantageously prepared by the process described below. The catalyst composition may also be defined as an anhydrous slurry of partially hydrated titanium dioxide dispersed in a liquid carrier compound. The catalyst is effective during the ester interchange reaction producing essentially monorneric esters of the acid and glycol and is also unexpectedly highly effective during the subsequent polymerization.
The prior art to which this invention relates contains a great number of disclosures relating to various methods for preparing fiberand film-forming condensation type polyesters. A great number of polyesterification catalysts have been disclosed along with various techniques for conducting the polyesterification using such catalysts. One of the most basic patents relating to this field is US. 2,465,319. A great number of other patents describe various catalysts and various processes which can be employed, for example, US. 2,720,502; US. 2,901,466; etc. The use of a titanium catalyst is not new in the art, but the particular catalyst employed in this application for the process defined herein is novel and quite unobviously highly effective, especially with regard to the eificacious production of polyesters having substantially no color. The state of the art with respect to simple esterification processes using colloidal or other types of dispersions of titanium dioxide, titanium hydroxide, or other forms thereof is set forth in Danish Patent 44,122. The use of such compounds which have not been prepared in the manner described in this application is also set forth in British Patent 849,109 and US. Patent 3,056,817.
The latter patent gives a typical description of hydrated titanium dioxide gels (preferably 60-95 percent hydrated) and discloses their use as esterification catalysts. It is indicated that when the degree of hydration falls much below 24 percent, then utility as a catalyst is seriously impaired.
In contrast to the prior art, the applicants have unexpectedly discovered that ester exchange reactions can be quite advantageously promoted by employing as a catalyst an anhydrous slurry of partially hydrated titanium dioxide dispersed in a certain type of preferred liquid carrier wherein the degree of hydration is from about 2 percent to about 14 percent. This discovery and the advantages associated with it were quite unexpected.
Moreover, the present invention is especially useful in polyesterification reactions and particularly those Where the final polymerization is done under solid phase conditions as illustrated by Examples 4-7 hereinbelow.
One of the most crucial problems in selecting a catalyst for use in preparing polyesters is the avoidance of color and cloudiness in the polyester produced. This is especially crucial in the case of those polyesters to be used to form a support or film base for photographic emulsions (either color or black-and-white) where the optical requirements are such that a substantially colorless and clear polyester is of great importance. Those titanium catalysts which have been disclosed in the prior art are generally characterized by efficacious activity except for the fact that the color of the product is not considered to be adequate for the preparation of polyesters to be used as photographic film base or for other purposes where substantially no color is desired.
It is an object of this invention to provide a novel polyesterification process using freshly precipitated titanium hydroxide (also called hydrated titanium dioxode, 2-14 percent hydration) so as to produce linear polyesters having substantially no color. It is an additional object of this invention to provide a process for producing the freshly precipitated titanium hydroxide catalyst to be used in conjunction with the polyesterification process.
It is a further object of this invention to provide a process for producing substantially colorless linear polyesters. Other objects will become apparent elsewhere herein.
There is no reason in this specification to indulge in an extensive elaboration of the various processes which can be employed in preparing polyesters. Those US. patents mentioned above as well as many other patents and papers in the literature describe such processes in great detail. A common feature of all of the processes with this invention is concerned is that they begin with a lower dialykyl ester of a bifunctional dicarboxylic acid which is condensed with a bifunctional glycol.
Although the polyesterification process can be thought of as taking place in two stages, the: process which is sometimes referred to as the melt polyesterification process does not necessarily need to be conducted with any particular interruption between the two stages. When the polyesterification is being conducted using apparatus designed to provide a continuous process, it is sometimes advantageous to divide the process into a number of separate stages conducted in a number of separate pieces of apparatus. However, the process can still be considered to be essentially an initial ester interchange reaction followed up by a final polyesterification reaction, which can, if desired, be interrupted so as to employ the melt polyesterification technique for part of the polyesterification and a solid phase technique for the remainder of the polyesterification. When the solid phase technique is employed, it can be performed either under a vacuum or under atmospheric pressure using an inert gas. Of course, intermediate reduced pressures can be employed as well as pressures above atmospheric.
A preferred embodiment of this invention provides an improvement in a process for preparing a highly polymeric condensation-type linear polyester by condensing a lower dialkyl ester of a bifunctional dicarboxylic acid with a bifunctional glycol wherein the alkyl radicals contain from 1 to 4 carbon atoms, the dicarboxylic acid is predominantly composed of an aromatic acid containing from 1 to 2 benzene rings and from 8 to 20 carbon atoms and the glycol contains from 2 to 10 carbon atoms, by first preparing at an elevated temperature in the presence of a catalyst a substantially monomeric intermediate polymer (also designated as a prepolymerU under conditions facilitating removal of the lower alkanol formed from said lower dialkyl ester by ester interchange with said glycol and then polymerizing at an elevated temperature said intermediate polymer in the presence of a catalyst under conditions facilitating removal of superfluous quantities of said glycol. This preferred embodiment of the invention consists in having said catalyst present in a concentration of from 0.001 percent to 0.1 percent based on the weight of said lower dialkyl ester, said catalyst being essentially composed of freshly precipitated titanium hydroxide which has been precipitated from an aqueous solution of a titanium halide with arm monium hydroxide, filtered, dispersed in an alkanol of 4 to 8 carbon atoms, and isolated from the residual water by azeotropic distillation whereby said titanium hydroxide remains as a dispersion in said alkanol, said dispersion being used as said catalyst in said process.
The degree of polymerization is proportionate to the inherent viscosity of the polyester. A convenient solvent for measuring the inherent viscosity is a mixture of 60 percent phenol and 40 percent tetrachloroethane, although other solvents such as carbon tetrachloride can be employed. The inherent viscosity for different polyesters does not necessarily represent the same molecular weight. The highly polymeric polyesters contemplated by this invention correspond to an inherent viscosity of at least 0.5 for poly(ethylene terephthalate). Other polyesters having the same molecular weight (12,000-l3,000 or higher) may have higher or lower inherent viscosities (such as 0.4) indicative of said minimum molecular weight. As a broad generalization, it is desired that the polyesters especially useful for preparing fibers and films have an inherent viscosity of about 0.55 or higher.
Whenever the term inherent viscosity (I.V.) is used in this application, it will be understood to refer to viscosity determinations made at 25 C. using 0.25 gram of polymer in 100 ml. of a solvent composed of 60 percent phenol and 40 percent tetrachloroethane.
This invention will be further illustrated by the following examples of preferred embodiments, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.
EXAMPLE 1.-PREPARATION OF FRESHLY PRE- CIPITATED TITANIUM HY DROXIDE FOR USE AS CATALYST Thirty-seven grams of titanium tetrachloride (0.195 mole) was slowly added with vigorous agitation to 400 grams ice water. The temperature was maintained below 20 C. throughout the addition of the titanium tetrachloride. To this clear solution was slowly added 180 grams of percent ammonium hydroxide which had been previously cooled to 0 C. The precipitated titanium hydroxide was collected by filtration and washed free of ammonium chloride by slurrying with distilled water. The excess water was removed from the titanium hydroxide by washing with methanol. The titanium hydroxide Was suspended in 150 grams butanol and any remaining methanol removed from the slurry by distillation. Two hundred cubic centimeters of benzene was added to the butanol slurry and the last traces of excess water removed as the benzene azeotrope. When water was no longer observed in the benzene reflux, the benzene was removed by distillation. The resulting slurry in butanol was passed through a 150-mesh (Tyler) screen in order to remove any large particles. The weight of the resulting effluent was adjusted to 180 grams by the addition of butanol so that the slurry contained 5.2 percent titanium (calculated as metal). This slurry may be used directly as the catalyst for polymerization.
This process can also be employed using other titanium halides such as titanium tetrabromide. Moreover, other azeotropic agents can be used such as toluene. Other variations of the process are obvious to those skilled in the art.
A batch of the hydrated titanium dioxide slurry prepared as described in Example 1 was analyzed with Karl Fisher reagent to ascertain the amount of water. After dehydrating a portion at C., it was determined that the hydrate had 3.73 percent water of hydration. Since there was a possibility that not all water had been eliminated, another portion was dehydrated at 650 C. until a constant weight was achieved; this procedure showed that the hydrate contained 4.66 percent water of hydration.
The titanium oxide hydrate was examined by X-ray diffractrometry and the diffraction pattern indicated that the material was amorphous, or if a crystalline phase did exist, the particle size was less than 25 angstrom units in mean dimension. Therefore, these titanium compounds may be designated as substantially amorphous. Whenever the term substantially amorphous appears in this application, it will be understood to refer to compounds which, when examined by X-ray diffractrometry (having a lower measurement limitation of 25 angstrom units in mean dimension), appear to be amorphous.
Other catalyst slurries can be similarly prepared using the process of Example 1 but employing other halides, azeotropic agents, and liquid carriers other than butanol.
Thus, this invention provides a catalytic composition for promoting ester exchange between a relatively high boiling alcohol and an ester of a relatively low boiling alcohol and an organic carboxylic acid, said catalytic composition consisting of an anhydrous slurry of substantially amorphous, partially hydrated titanium dioxide having from 2 to 14 percent by weight of water of hydration and dispersed in a liquid carrier compound which is a saturated alcohol having 1 to 3 hydroxyl groups.
The preferred catalyst composition contains from about 2 to about 20 percent titanium (calculated as the' metal).
The relatively high boiling alcohol involved in the ester exchange is advantageously monohydric or dihydric. This alcohol is a glycol when the process is intended to produce a polyester. In such a case, the organic carboxylic acid is a bifunctional carboxylic acid, e.g., a dicarboxylic acid. Of course, other ester exchange reactions can be conducted as is well known in the art as illustrated by the above-mentioned US. Patent 3,056,817, especially in columns 3 and 4, where the term alcoholysis or transesterification is used.
Preferably the carrier compounds for the catalyst slurries of this invention contain from 1 to 10 carbon atoms and, besides butanol, can be illustrated by ethanol; hexanol; decanol; ethylene glycol; tetramethylene glycol; decamethylene glycol; 1,4-cyclohexanedimethanol; glycerol; and various isomers and homologs of these illustrative compounds. Especially preferred carrier compounds are the saturated monohydric and dihydric alcohols. Such compounds are most advantageous when they function in the preparative process to facilitate the elimination of water, avoid subsequent absorption of water, and do not :deleteri-ously affect any ester exchange reaction into which they are ultimately introduced.
Butanol has been found to be especially advantageous with respect to the preparation of a catalyst slurry for use in preparing polyesters. This catalyst composition is preferably an anhydrous slurry of freshly precipitated amorphous titanium dioxide hydrate dispersed in butanol, said slurry having from about 2 to about 20 percent titanium calculated as metal, said hydrate containing from about 3 to about 5 percent water of hydration. In such a composition, the carrier is anhydrous, but the titanium dioxide contains water of hydration.
The amount of partially hydrated titanium dioxide which is present in the catalytic composition is not critical in the process of this invention.
1n the above-described preferred method of preparing the' slurry, the freshly precipitated titanium hydroxide (hydrated titanium dioxide) was washed with distilled water until free from ammonium and halogen ions or salts, then with methanol. The methanol wash may be considered the first step of the dehydration. The methanol-washed titanium hydroxide was dispersed in butanol and the methanol removed by distillation. The methanol was removed at this time to eliminate ditliculty during the subsequent benzene treatment. Benzene was then added to the butanoltitanium hydroxide system, and the mixture further dehydrated, water being removed as the benzene azetrope (benzene-water azetrope, B.P. 69.25 C.). When the mixture was dry, as evidenced by the absence of water in the benzene distillate, the excess benzene Was removed by distillation (benzene, B.P. 80.09 C.). The resulting dispersion of titanium hydroxide in butanol was filtered through a l50-mesh (Tyler) screen to remove large particles, diluted to the desired concentration with additional butanol, and used as such.
As may be noted in J. W. Mellors A Comprehensive Treatise on Inorganic and Theoretical Chemistry, titanium hydroxide (orthotitanic acid) dried at room temperature is reported to contain 29.8331.1l percent water which corresponds to TiO -2H O. When dried at 60-70 C., orthotitanic acid corresponds to 4TiO -3H O (calcd. 14.25 percent water) and at 100 C., corresponds to 2TiO -H O (calcd. 10.12 percent water). In view of these dehydration data, the catalyst employed in the present invention can be characterized as a dispersion of colloidal titanium hydroxide in butanol wherein the titanium hydroxide contains less than 14 percent water of hydration. Mellors book was published by Longrman & Co., 1930, vol. VII, pp. 39-41.
EXAMPLE 2.PREPARATION OF POLY(ETHYL- ENE TEREPHTHALATE) Fifty-eight and two-tenths grams of dimethyl tereph thalate (0.3 mole), 37.2 grams of ethylene glycol (0.6 mole), and 0.1 ml. of a fresh slurry prepared as in Example l were placed in a flask and heated under nitrogen with stirring at 185 to 190 C. Methanol evolved rapidly, and the alcoholysis was complete in approximately thirty minutes.
The temperature of the colorless residue was raised to 280 to 285 C. over a period of forty to fifty minutes. The reaction mixture (intermediate polymer) was placed under reduced pressure (about 1 mm. of mercury) and the temperature held at 280 to 285 C. for approximately thirty minutes. The melt viscosity increased rapidly, and at the end of the thirty minutes, the vacuum was released with nitrogen.
The inherent viscosity of the colorless polymer was found to be 0.67. It had a Gardner color value of about one.
EXAMPLE 3.-PREPARATION OF POLY( 1,4-CYCLO- HEXYLENEDIMETHYLENE TEREPHTHALATE Thirty-eight and eight-tenths grams dimethyl terephthalate (0.2 mole), 40.3 grams 1,4-cyclohexanedimethanol (0.28 mole), and 0.1 ml. of a fresh slurry prepared as in Example 1 were placed in a flask and heated under nitrogen with stirring at 190 to 200 C. Methanol evolved rapidly, and the alcoholysis was complete in thirty to forty minutes.
The temperature was raised to 300 C. during a period of forty to fifty minutes. The reaction mixture was then placed under reduced pressure (about 1 mm. mercury), and the temperature held at 300 C. for one hour. The melt viscosity increased rapidly, and at the end of one hour, the vacuum was released with nitrogen.
The inherent viscosity was found to be 0.63, and the polymer remained colorless.
6 EXAMPLE 4 Three and eighty-eight one-hundredths grams dimethyl terephthalate (0.02 mole), 3.8 grams cyclohexane-l,4-dimethanol (0.0264 mole), 1.256 grams dibutyl sebacate (0.004 mole), and one drop of a fresh slurry prepared as in Example 1 were placed in a test tube and heated under nitrogen. The temperature was raised from 180 C. to 287 C. over a period of minutes. Methanol and butanol evolved, and the alcoholysis was complete at the end of this time.
The reaction mixture was then placed under reduced pressure (about 1 mm. of mercury) and the temperature held at 290 C. for approximately ten minutes. The vacuum was released with nitrogen.
After cooling to room temperature, the resulting prepolymer was colorless, and the inherent viscosity was found to be 0.23. The intermediate polymer (can also be referred to as prepolymer) was ground to pass 60-mesh (Tyler) screen. The prepolymer was heated at 220 C. under reduced pressure (about 0.1 mm. of mercury) for three hours to build-up the molecular "weight.
The resulting polymer was colorless, and the inherent viscosity was found to be 1.00.
EXAMPLE 5 The procedure described in Example 4 was repeated except that the dibutyl sebacate was replaced with 0.816 gram isosebacic acid (0.004 mole). The resulting polyester was found to have an inherent viscosity of 0.82.
EXAMPLE 6 The procedure described in Example 4 was repeated except that the dibutyl sebacate was replaced with 0.004 mole of dimethyl isophthalate. A colorless bui1tup polymer was obtained.
EXAMPLE 7 The procedure described in Example 4 was repeated except that the dibutyl sebacate was replaced with 0.67 gram succinic anhydride (0.0067 mole). The resulting polymer was colorless and had an inherent viscosity of 1.31.
EXAMPLE 8 Six and twenty-seven one-hundredths grams of the dibutyl ester of p,p-sulfonyldibenzoic acid (0.015 mole), 0.3 gram succinic anhydride (0.003 mole), 3.1 grams 1,5- pentanediol (0.029 mole), and one drop of a fresh slurry prepared as in Example 1 were placed in a test tube and heated under nitrogen. The temperature was raised from C. to 260 C. over a period of two hours. Butanol evolved, and the alcoholysis was complete at the end of this time.
The reaction mixture was placed under reduced pressure (about 1 mm. mercury) and the temperature held at 260 C. for approximately ten minutes. The vacuum Was released with nitrogen.
After cooling to room temperature, the resulting prepolymer was colorless, and the inherent viscosity was found to be 0.19. The prepolymer was ground to pass 60- mesh (Tyler) screen. The prepolymer was heated at 203 C. under reduced pressure (about 0.1 mm. of mercury) for two hours.
The resulting polymer was colorless, and the inherent viscosity was found to be 1.32.
EXAMPLE 9 A vessel equipped with a stirrer, distilling head, and nitrogen inlet was charged with 9.7 grams (0.05 mole) of dimethyl terephthalate, 11.5 grams (0.08 mole) of cyclohexane-1,4-dimethanol (70 percent trans), 22.5 grams (0.008 mole) of poly(tetramethylene glycol) having a molecular weight of 2,800, and one drop of a fresh slurry as prepared in Example 1. The reaction vessel was swept with nitrogen, stirred, and heated to 200 C. When about 65 percent of the theoretical amount of methanol had been evolved, the temperature of the reaction mass was raised over a period of 30 minutes to 280 C. A vacuum was then applied so that the pressure was rapidly reduced to 0.3 mm. of mercury over a period of less than ten minutes. The molten mass was sttirred at less than 0.3 mm. of mercury at 275 C. to 280 C. for 60 minutes. At the end of the polyesterification, the polymer was cooled under vacuum and removed from the flask. It was a hard rubbery mass with an inherent viscosity of 1.15 and contained about 65 percent by weight of poly(tetramethylene glycol). This colorless polymer was extruded to form a highly flexible, elastic, and colorless film.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
We claim:
1. A catalytic composition for promoting ester exchange between a relatively high boiling alcohol and an ester of a relatively low boiling alcohol and an organic 2. A catalytic composition as defined by claim 1 wherein said liquid carrier compound contains from 1 to 10 carbon atoms.
3. A catalytic composition as defined by claim 1 wherein said liquid carrier compound is butanol, and said titanium dioxide has from about 3 percent to about 5 percent water of hydration.
4. A catalytic composition as defined by claim 1 wherein said liquid carrier compound is ethylene glycol.
5. A catalytic composition as defined by claim 1 wherein said liquid carrier compound is 1,4-cyclohexanedimethanol.
References Cited UNITED STATES PATENTS 2,749,248 6/1956 Benson.
2,843,556 7/1958 Moorman 260863 XR 2,901,466 8/1959 Kibler 6161 260-75 2,906,737 9/1959 York 260-75 3,056,817 10/1962 Werber et al 26075 XR WILLIAM H. SHORT, Primary Examiner carboxylic acid, said catalytic composition consisting of 25 L. QUAST Assistant Examiner slurry consisting of substantially amorphous, partially hydrated titanium dioxides having from 2 to 14 percent by weight of water of hydration and dispersed in a liquid carrier compound which is a saturated alcohol having 1 to 3 hydroxyl groups.
US. Cl. X.R.
Patent Citations
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Alcohol History of Use oldest and most widely used drugs natural process, predates human history referenced in bible, Egyptian pictograms oldest known recipe is for beer always been part of American culture Prohibition 1920-1933 alcohol consumption did not decrease permanently crime related to alcohol increased drastically Facts Types of alcohol methyl alcohol (methanol) Wiper fluids, paint thinners, etc. - extremely poisonous isopropyl alcohol (isopropanol) Rubbing alcohol - poisonous ethyl alcohol (ethanol). Facts Ethanol C(2)H(5)OH clear, relatively odorless liquid that is infinitely mixable in water. Facts usually produced by fermenting cereals/fruit yeast, water, and sugar → yeast recombines carbon, hydrogen, oxygen, and water to form alcohol and carbon dioxide different sources of sugar for different alcohols wines use fruit, fermentation goes naturally to 10-20% alcohol concentration beers uses cereals, fermentation is stopped at 3-6 % spirits can have between 50- nearly 100% Facts Percent of alcohol by volume is ½ the listed proof e.g. 80 proof = 40% v/v (volume of alcohol per volume of solution) 5-ounce glass of wine (12% v/v), a 12-ounce beer (4.9% v/v) and 1½ ounces (shot or mixed drink) of 80 proof spirits each contain the same amount of absolute (100%) ethanol Drug Classification Alcohol is not controlled by the Drug Enforcement Administration, therefore not classified, however ... Extent of Use 54.9% of adults reported drinking alcohol in the past month Americans spend over 90 billion dollars on alcohol each year overall per capita consumption has increased between 2000 and 2004 Extent of Use Abuse Binge drinking: 5+ drinks on one occasion 3 adult drinkers in the United States report past- month binge drinking 2001: approximately 1.5 billion episodes of binge drinking Extent of Use Abuse Heavy drinking: 2+ drinks per day 5.9% of adults reported heavy drinking in past 30 days 15 mil. Americans are dependent on alcohol; 500,000 are between the age of 9 and 12 43% of Americans have been exposed to alcoholism in their families total cost of alcohol problems is $175.9 billion a year (compared to $114.2 billion for other drug problems and $137 billion for smoking) Extent of Use Underage Drinking In 2003, 44.9% of 9th through 12th graders reported drinking alcohol in the past month 28.3% of 9th through 12th graders reported binge drinking during the past months Extent of Use Drunk Driving 159 mil. adults reported driving under the influence of alcohol in 2004 In 2000, there were 85,000 deaths attributable to excessive/risky drinking 16,694 people where killed in alcohol related traffic accidents in 2004 Alcohol-related motor vehicle crashes kill someone every 31 minutes and injure someone every two minutes Alcohol related crashes cost around $114 billion/year Effects of Alcohol Physiological 1. Mouth: alcohol enters body 2. Stomach: some alcohol gets into bloodstream 3. Small Intestine: alcohol enters the bloodstream through the walls of the small intestine 4. Heart: pumps alcohol throughout the body 5. Brain: alcohol reaches brain 6. Liver: alcohol is oxidized by the liver Effects of Alcohol Physiological Liver: alcohol dehydrogenase breaks down alcohol Alcohol dehydrogenase oxidizes alcohol to acetaldehyde Acetaldehyde dehydrogenase oxidizes the acetaldehyde to acetyl CoA eventually alcohol is converted to carbon dioxide and water The liver can metabolize about ½ ounce of ethanol per hour (depending on body size, food intake, etc.). Effects of Alcohol Physiological Arthritis Kidney Disease Cancer Liver Disease Fetal Alcohol Malnutrition Syndrome Nervous Heart Disease Disorders Hyperglycermia Obesity Hypoglycemia Psychological Disorders Effects of Alcohol Neurochemical The GABA-benzodiazepine receptor complex Very important inhibitory receptor type for mammals Gamma aminobutyric acid (GABA) opens up ion channels, lets in Cl ions Hyperpolarization occurs (less chance for action potential) Effects of Alcohol Neurochemical Alcohol's impact on GABA processing Alcohol binds to GABA-benzodiazepine receptor following consumption Then, once GABA also binds to the receptor, more Cl ions are admitted through than without the alcohol. Effects of Alcohol Neurochemical Consequences and dependency Certain cognitive functions are sedated The brain will become dependent on alcohol for neural inhibition Effects of Alcohol Neurochemical glutamate and the N-methyl-D-aspartic acid (NMDA) receptor glutamate action on NMDA receptors is excitatory; it increases the activity of brain neurons alcohol inhibits the NMDA receptors decrease in excitatory actions of glutamate Effects of Alcohol Neurochemical Triggers apoptosis Very dangerous during synaptogenesis, and explains the brain damage associated with FAS Connected to alcohol's NMDA antagonist and GABAmimetic properties Effects of Alcohol Neurochemical also affects the synthesis and receptors of opioid peptides, which are responsible for euphoria and anesthesia Increased turnover of norepinephrine and dopamine Decreased transmission in acetylcholine systems Increased production of beta-endorphin in the hypothalamus Effects of Alcohol Psychological Alcohol dependency Tolerance and Withdrawal Alcohol use for longer periods than intended. Desire and/or unsuccessful efforts to cut down or control alcohol use Considerable time spent obtaining or using alcohol, or recovering from its effects Important social, work, or recreational activities given up because of use Continued use of alcohol despite knowledge of problems caused by or aggravated by use Effects of Alcohol Psychological Short term effects: anxiety, restlessness, slowed heart and respiratory rates, blurred vision and poor motor coordination Long term effects: cirrhosis, cancers, cardiac diseases, skin diseases, gastritis and sexual dysfunction, irreversible neurological and psychological health conditions Effects of Alcohol Psychological Other effects: sleep disturbance, academic disruption, and verbal, physical or sexual violence, interpersonal and environmental problems, such as traffic accidents, physical and sexual violence, property damage, family problems and divorces Nearly 40% of admissions to mental hospitals and 50% of arrests are alcohol-related Treatments Active Ingredients of Effective Alcohol Treatment Early detection, including screening and brief interventions Comprehensive assessment and individualized treatment plan Care management Individually delivered, proven professional interventions Contracting with patients Social skills training Medications Specialized services for medical, psychiatric, employment or family problems Continuing care Strong bond with therapist or counselor Longer duration (for alcohol dependent persons) Participation in support groups Strong patient motivation Treatments Antabuse blocks the oxidation of alcohol at the acetaldehyde stage resulting in increased concentration of acetaldehyde Accumulation of acetaldehyde produces unpleasant symptoms: flushing, throbbing in head and neck, throbbing headache, respiratory difficulty, nausea, copious vomiting, sweating, thirst, chest pain, hyperventilation, tachycardia, hypotension, marked uneasiness, weakness, vertigo, blurred vision, and confusion psychological effectiveness through conditioning Treatments Naltrexone blocks effects of alcohol by competing for opioid receptors in the brain reduces craving, helps patients remain abstinent, interferes with the tendency to want to drink more if a recovering patient slips and has a drink Significant reduction in drinking, well tolerated Treatments Alcoholics Anonymous Patient must first "hit bottom" before anything can be done Functions as a hub for wisdom and support Spiritual and social as opposed to biochemical techniques Drank too much? Formal name for hangover: veisalgia Norwegian word for "uneasiness following debauchery" (kveis) and Greek word for "pain" (algia) 75% of alcohol consumers have experienced a hangover at least once 15% have one every month 25% of college students feel symptoms weekly Symptoms of hangover Headache Nausea Poor sense of overall Fatigue well-being Difficulty sleeping and Sensitivity to light, sound concentrating Diarrhea Dehydration Loss of appetite Anxiety weakness Trembling Increased heart rate and blood pressure What causes a hangover? Dehydration Causes pituitary gland in brain to block creation of vasopressin Vasopressin increases water reabsorption in the kidneys Without vasopressin, kidneys send water straight to bladder, increasing urination Study: 250 mL of alcoholic beverage causes body to expel 800-1000 mL of water. Aftereffects help create hangover Dehydration Headaches: result of dehydration. Organs need more water and take it from brain (blood vessels dilate) Frequent urination secretes salts and potassium which are necessary for nerve and muscle function Low levels can result in fatigue, nausea, headaches. Alcohol breaks down glycogen in the liver. Turns it into glucose and secretes it via urine (causes weakness) Congeners Definition: toxic chemicals created during alcohol fermentation process Give flavor, smell and appearance to alcohol Greatest amounts found in red wine and dark liquors White wine, and clear liquors: less congeners, less frequent and less severe hangovers Combining alcohols mixes the various congeners causing very severe hangover Acetaldehyde When alcohol dehydrogenase breaks down alcohol in the liver, ACETALDEHYDE is formed Acetaldehyde attacked by acetaldehyde dehydrogenase and GLUTATHIONE is formed Acetaldeyhyde dehydrogenase and glutathione form nontoxic acetate. Process works well if only few drinks consumed BUT… …What happens when you drink alot? Liver runs out of glutathione quickly Toxic acetaldehyde builds up in body as liver rushes to produce more glutathione Men have more acetaldehyde dehydrogenase and glutathione than women Glutamine Rebound Alcohol inhibits glutamine (natural body stimulant) When drinking stops, body tries to make up for lost time by producing more glutamine than it needs Increase in glutamine stimulates brain while person tries to sleep (prevents deep sleep, contributes to fatigue) Can also be responsible for tremors, restlessness, increased blood pressure and anxiety And… Alcohol absorbed directly through stomach, stomach cells become irritated. Promotes secretion of HCl which can send the signal to the brain to vomit (can reduce hangover symptoms) HCl levels can lead to diarrhea and loss of appetite How to prevent/remedy hangovers? Fried or fatty foods before drinking (stick to stomach longer and slow down absorption of alcohol) Eggs the morning after (energy, contain lots of cysteine that breaks down hangover-causing toxin acetaldehyde) Bananas the morning after (lost electrolytes, replenishes potassium) How else? Water: fights dehydration, and dilute byproducts of stomach (adding salt and sugar to water helps too) Drinking glass a water for each alcoholic beverage slows down drinking, giving body more time to break down alcohol Fruit juice the morning after (replenishes vitamins, increases energy, increases rate that body expels toxins) Painkillers? Tylenol contains acetaminophen which your liver metabolizes and in combo with alcohol can cause release of a toxic metabolite Can cause liver damage over time Non-caffeinated, acetaminophen free painkillers are better to use (aspirin)
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Release Date:
December 4, 2001
Fresh off of the international success of La Dolce Vita, master director Federico Fellini moved into the realm of self-reflexive autobiography with what is widely believed to be his finest and most personal work. Marcello Mastroianni delivers a brilliant performance as Fellini's alter ego Guido Anselmi, a film director overwhelmed by the large-scale production he has undertaken. He finds himself harangued by producers, his wife, and his mistress while he struggles to find the inspiration to finish his film. The stress plunges Guido into an interior world where fantasy and memory impinge on reality. Fellini jumbles narrative logic by freely cutting from flashbacks to dream sequences to the present until it becomes impossible to pry them apart, creating both a psychological portrait of Guido's interior world and the surrealistic, circus-like exterior world that came to be known as "Felliniesque." 8 1/2 won an Academy Award for Best Foreign-Language Film, as well as the grand prize at the Moscow Film Festival, and was one of the most influential and commercially successful European art movies of the 1960s, inspiring such later films as Bob Fosse's All That Jazz (1979), Woody Allen's Stardust Memories (1980), and even Lucio Fulci's Italian splatter film Un Gatto nel Cervello (1990). Jonathan Crow, Rovi
- Genre: Drama
- Category Ensemble Film, Satire, Psychological Drama, Showbiz Comedy
- Theme: Filmmaking, Creative Block
- Run Time: 02 hr 18 min
- Language: Italian
- Subtitle Language: English
- Picture Format: widescreen
- Lead Actor: Rossella Falk , Sandra Milo , Claudia Cardinale , Marcello Mastroianni , Anouk Aimée
- Supporting Actor: Polidor , Georgia Simmons , Giuditta Rissone , Annibale Ninchi , Edy Vessel , Eddra Gale , Matilda Calnan , Rosellin Como , Mark Herron , John Stacy , Cesarino Miceli Picardi , Mario Conocchia , Guido Alberti , Ian Dallas , Annie Gorassini , Gilda Dahlberg , Eugene Walter , Mino Doro , Madeleine Le Beau , Neil Robinson , Mario Pisu , Barbara Steele , Olimpia Cavalli , Caterina Boratto , Tito Massini , Jean Rougeul , Dina de Santis , Maria Antonietta Beluzzi
- Director: Federico Fellini
- Academy Awards (2)
- Academy Awards , Best Foreign Language Film , 1963 , Federico Fellini
- Academy Awards , Best Black and White Costume Design , 1963 , Piero Gherardi
- Academy Awards (3)
- Academy Awards , Best Director , 1963 , Federico Fellini
- Academy Awards , Best Black and White Art Direction , 1963 , Piero Gherardi
- Academy Awards , Best Original Screenplay , 1963 , Federico Fellini, Ennio Flaiano, Tullio Pinelli, Brunello Rondi
other Info.
- Online Item #: 11328858
- Store Item Number (DPCI): 246-00-2917
- Made in the USA or Imported


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Do dress to impress
Fine print: Not to impress others, but to impress
yourself. Studies show that taking care
of your appearance in the a.m. boosts your performance and confidence
throughout the day.
Don't procrastinate
Forget bullies, procrastination is seriously your largest
enemy from now on. My best tips to avoid the delay? Create a homework schedule
and stick to it, write down all of your assignments in a planner and finish
things sooner than later.
Do make an older
Befriend an upperclassman who can give ya the low-down on
teachers, classes and the ins and outs of freshman year at your school.
Don't skip class
Unless you're really sick or have a family emergency, it's
best to sit your bum in that seat, no matter how much ya don't wanna be there.
It can be really hard to catch up on even just one class in high school, so if
you can be there, then, well, be there.
Do be on time
The earlier you are for classes, the more teachers will
respect you and take you seriously. That'll be huge when, say, you want to
change project partners when you're buddied up with a slacker, or you really
need an extension on that Hemingway essay.
Don't bust your
When your parents give ya the freedom to hang with your buds
solo at the mall on the weekend, they're also giving ya free rein over your
bank account. Remember, you don't have an endless supply of money, so getting a
part-time job and handling your money responsibly is essential.
Do find a study buddy
Instead of heading to your desk to fight through your
textbook solo, join a study group that can make the most of manpower—and
explain concepts you're not getting. But remember: This is a study group, not a
gossip sesh!
Don't let a
relationship consume your life
Although relationships are wonderful things to have, your
education always comes first. Talk to your significant other about this—perhaps
create some sort of "work, then play" schedule for texting/skyping during
weeknights, and on the eve of huge tests.
Do balance old and
Meeting a diverse group of people will in turn make you more
cultured and open to different ideas, but that doesn't mean ya won't need your
old buds. Hang on to all your hunnies—in HS, it's totally cool to be a social
circle butterfly.
Don't give in to peer
One of the most important lessons learned when growing up is
to listen to the beat of your own drum. People will respect you more and
gravitate towards you if you don't follow the crowd. It takes a lot of courage
to be your own person, and to be comfortable in your own skin, but doing so
will not only boost your confidence, it will make you the "cool" one.
Do challenge yourself
Instead of going for the easy A, pick a class or club that's
out of your comfort zone. Hello, broader horizons!
Don't waste your
When your workload increases during high school, sometimes
you'll need to make smart sacrifices, like skipping a party Friday night to
work on a project, so you can hang with your buds on Saturday. If you're
careful about balancing work with your social life, you'll be able to get it
all done and have a blast.
Do reinvent yourself
If there are things you didn't like about yourself in middle
school—low self-confidence, serious slacker tendencies—you can make a total
transformation before the first day.
Don't forget your fam
Yeah, yeah, you're really busy. But that doesn't mean you
can just ditch your fam. Always reserve some time to talk to and hang out with
them. Parents and siblings can always provide some of the best advice and
reality checks. They will always have your back. Never forget that!
Do take things slow
Here's a bit of guy advice: you don't have to get a
boyfriend as soon as you get into high school. Although it may seem tempting to
leap into a relationship, explore your options, befriend lotsa boys and see who
you mesh with. You'll have a whole lot besides boys to deal with in high
school—more important things like work, your girls and grades. The boys will
never disappear—that I can guarantee—so take your time.
Don't get in trouble
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text:
a woman or girl mainly concerned with material things
from song by Madonna
So tensions were high before the material girl's Tuesday-night show on the Riviera.
And one 53-year-old material girl who is performing the half time show says she would rather date Eli than Tom.
Look at the photos today, and the chemistry between Jesus and the material girl is palpable.


text:
Originally launched 25 years ago this Indian and Bangladeshi restaurant took the Cowley Road by storm, setting the trend for other Indian restaurants to follow. Now Aziz is back – with a re-launch that will set the trend for the next 25 years!read more
The Bear and Ragged Staff in Cumnor is a delightful country Inn set in tranquil countryside just outside Oxford. They are renowned for their excellent seasonal and locally-sourced cuisine and are also a Visit Britain 4 Star Inn offering modern guest accommodation complete with en-suite and Wi-Fi facilities.read more
The Ashmolean Museum of Oxford - Art and Archaeologyread more


text:
I would highly appreciate if someone could critique this approach for me.
I'm building an application where a user can define several attributes & generate a form to share with his users, much like Wufoo.
This is my approach.
User has_many sources & Source embeds_many source_attributes
Here, all of the user defined fields are stored in SourceAttributes. When i need to generate a form, I generate a model on the fly like this.
def initialize_set
model_name = self.set_name.gsub(' ','').classify
# Unique Class name
klass_name = "#{model_name}#{self.user.id}"
object = self
klass = Class.new do
include Mongoid::Document
# Collection names have to be set manually or they don't seem to work
store_in collection: self.collection_name
# Pick up attributes from SourceAttribute & define fields here
object.source_attributes.each do |m|
field m.field_name.gsub(' ','').underscore, type: object.class.mapping[m.field_type]
def self.collection_name
# I get a warning here when the class is re-loaded. Should i worry? I'm considering Object.send :remove_const here
Object.const_set klass_name, klass
With this approach, I'll have a separate collection for every form the User defines. This seems to work but I have a couple of problems.
- Type Safety
The fields I generate above don't seem to be type safe. I am able to save a String in an Integer field.
The type seems to have been set correctly. I double checked this by calling fields on klass & checking the options[:type] attribute.
I'm using simple form & it doesn't recognize type automatically. I have to mention it explicitly using as:
- Scalability
I'm not sure if my approach of generating models on the fly is correct. I've never seen anyone use this before.
Moved to a separate question. Please check comments.
So I was wrong. My model is type safe, but it seems to fail silently. Is there a way I can make it throw an exception?
# age is correctly defined as an Integer
klass.fields.slice "age"
=> {"age"=>#<Mongoid::Fields::Standard:0xb7edf64 @name="age", @options={:type=>Integer, :klass=>Engineer50bc91a481ee9e19ab000006}, @label=nil, @default_val=nil, @type=Integer>}
# silently sets age to 0
klass.create!(age: "ABC")
=> #<Engineer50bc91a481ee9e19ab000006 _id: 50cff12181ee9e16f1000003, _type: nil, employee_code: nil, name: nil, age: 0, years: nil, number: nil>
# returns true when saved
object = klass.new
object.age = "ABC"
=> true
PS: This is my first time using mongoid :)
My problem with Integer validation might be with Ruby & not mongoid.
As mentioned in my previous update,
# silently sets age to 0
klass.create!(age: "ABC")
=> #<Engineer50bc91a481ee9e19ab000006 _id: 50cff12181ee9e16f1000003, _type: nil, employee_code: nil, name: nil, age: 0, years: nil, number: nil>
I believe "ABC" is being typecasted
=> 0
I tried to overcome this problem by using validates_numericality_of like this
object.model_attributes.where(field_type: "Number").map(&:field_name).each do |o|
validates_numericality_of o.gsub(' ','').underscore.to_sym
Unfortunately, this checks for presence as well. I tried this workaround
validates_numericality_of o.gsub(' ','').underscore.to_sym, allow_nil: true
But this completely ignores the numericality validation. Tried allow_blank as well with no luck.


text:
TEMPTU LA hosted Charlotte Salt, up-and-coming british actress, from The Tudors and Beowolf! Not only does Charlotte hail on the big screen, but she has turned her passion for beauty and health into an amazing blog, In the Eye of the Beholder, as a forum for reviews on brands, tips from professional makeup artists, and tips on general health and well being.
We were thrilled she stopped by to check out the TEMPTU AIRbrush Makeup System for herself, and after a quick one on one lesson, you can see how gorgeous she looks!
Check out her blog HERE!
thankyou again ladies! i was a blast and the makeup is insane!!!….ill be blogging very soon xx
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June 24, 2015 9:26 PM
RT @HH_NYC: The Beautiful Emmy Rossum on the cover of Herring & Herring OBJECT! Pre-Order NOW! http://t.co/plEnI5sGRR http://t.co/LQre9kqzRB
June 24, 2015 9:24 PM
Loving everything about @ChiaraFerragni's new Fall Campaign! #NaturalBeauty http://t.co/GGGqDCWy4w
June 22, 2015 2:11 PM
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Your shopping experience has just been elevated to even greater heights at Scotts
Square, a luxury mall in Orchard Road. Immerse in the art of fine shopping here
where all your discerning retail indulgences are met. Experience the elegance of international luxury brands, designer labels and
titillating dining options.
Founded in 1924, the Damiani brand is an ambassador of true Italian style; it is asymbol of distinction that brings out the best in Italian jewelry tradition.Damiani won 18 International Diamonds Awards, most influential and prestigious recognition for jewelry design,honoring the best creations using diamonds.
Creativity, craftsmanship and originality are key elements that have driven the Damianifamily for nearly a century, together with an immense passion for an art formthat was passed down from father to son, and now, into its third generation.
All jewels at Damiani are handcrafted with the highest level of care for details, an absolutedemonstration of the goldsmith's virtuosity. It is an embodiment of longlasting tradition with a strong focus on design that immortally personifiedDamiani's distinguished collections.
Founded in 1837, the House of Hermès began as a maker of harnesses and saddles, with a passion for perfection. Six generations of enterprising artisans have expanded into different crafts, conquering new markets with the house growing by remaining creatively loyal to the values of its founders. Respectful of the past as they were enthusiastic about the future, they passed on the reverence for beautiful materials, the love of craftsmanship made to last, and the verve to keep on making it new. From leather and silk to ready-to-wear, watches and fine jewellery, discover the world of Hermès at Scotts Square.
Inverted Edge, Singapore-based online retailer that features independent contemporary fashion designers, celebrated its 2nd Anniversary by opening a brick and mortar retail presence in Scotts Square.
With that, Inverted Edge is now able to deliver an in-store digital experience to customers, and working with innovative technology application and hardware partners to offer real world access to its roster of new contemporary brands as well as its popular personal styling services.
Brands that will be featured in the Scotts Square store include the collections of the Singapore winners of the Harper's BAZAAR Asia New Generation Designer Award 2015, Silvia Teh and Lionel Low, a selection from the regional winners of the BAZAAR Award, as well as Japanese designers Divka, Atsushi Nakashima and Gilet, plus Juliette Hogan, NOM*D, Zambesi and Kate Sylvester from New Zealand, Stylestalker from Australia and Bless'ed Are the Meek from Hong Kong.
Michael Kors is a leading American luxury lifestyle brand with an influential global presence, offering women's accessories, footwear, clothing and fragrance collections under the signature Michael Kors Collection, KORS Michael Kors and MICHAEL Michael Kors labels. Each reflects the unique point of view of designer Michael Kors: style that successfully juxtaposes tailored and glam, sexy and sporty, polished and casual, whether for day or night, weekend or work, home or destination.
On Pedder, part of the Hong Kong-based Pedder Group, is Asia's leading retailer of high-end footwear and accessories. The unique retail concept store presents to a fashion forward customer the best international edit of designer and contemporary brands. On Pedder at Scotts Square houses a portfolio of over 100 designer brands and a wider stable of contemporary brands such as: Azzedine Alaïa Alexander McQueen Alexander Wang Castaner Charlotte Olympia Chloé Christian Louboutin K Jacques McQ Melissa Pedro García Proenza SchoulerSergio Rossi Stella McCartney Tory Burch Valentino
Founded in 1977, Paul & Shark was named after the founder, Paolo (in English, 'Paul'), and the fitting connection to one to one of the mightiest creatures of the ocean, the shark, synonymous with freedom and casual elegance. Paul & Shark is a 'Made-in-Italy' luxury brand beloved by people with an appreciation of the high-performance use of technical materials, many of which are patented by the brand.
Trixilini - a boudoir where sophisticated ladies indulge their impeccable taste in all things feminine. Radiating self-confidence and style, Trixilini ladies are used to their independence and success, and are gifted with an amazing eye for originality.
Be smitten by a repertoire of beautiful one-of-a-kind dresses and accessories perfect from day to night. Continually inspired, Trixilini brings highly-coveted looks that are beautiful and chic season after season. Toss aside your inhibitions and leave discretion at the door, and be pampered in a decadent realm of fashion and frivolity.
Resist anything but temptation before emerging totally transformed. At Trixilini it's always about you: Be gorgeous, be dazzling, be the girl that everyone envies.
With heavy emphasis on fresh, organic, nutritious ingredients and a light touch on cooking methods, Crystal Jade Pristine at Scotts Square serves up Cantonese dishes with contemporary flair while preserving the traditions of authentic Chinese cuisine.Ingredients such as Sea Whelk, Cordycep, Kampung Chicken, Wagyu Beef and Kurobuta Pork along with a variety of Chinese mushrooms, organic eggs and vegetables take pride of place in a menu that includes doubled-boiled soups as well as steamed, simmered, sautéed dishes.With single-serve portions, communal dishes, business set lunches and organic sets, CrystalJade Pristine is aimed at the sophisticated diner and foodie who relishes authentic Cantonese food served in new and contemporary ways.
Visit Dôme cafés and appreciate a true Dôme experience.
We search the world for the finest Arabica coffee beans, then roast them to perfection.
But coffee is only part of the story. Dôme cafés are equally famous for its superb, fresh and innovative food, magnificent cakes and pastries baked fresh on the premises and gourmet sandwiches and delicious full meal served throughout the day.
A nostalgic Hong Kong restaurant setting with a modern touch, London Fat Duck, is a Chinese restaurant specialising in roast duck and other Hong Kong delights.
Using only a special breed of ducks from Ireland, their signature roast duck dish is prepared using a multi-generational heritage recipe, together with a modern cooking technique, where humidity, air flow, temperature and drying are controlled meticulously. The result is a tender and juicy poultry delight with flavourful, crispy skin.
Maison Kayser is an artisan bakery that emphasises on producing breads, pastries and brioches using traditional baking methods. The breads are all produced with natural liquid leaven as opposed to quick-action commercial yeast. Maison Kayser is renowned for its Baguette Monge and Croissants. The Baguette Monge, which was voted best in Singapore by The Straits Times, is known for its crackly crust and soft cotton-like interior. The Croissants are renowned for being buttery crisp, light and flurry, earning the praise of leading French newspaper, Le Figaro.
Time & Flow Champagne is a premium organic champagne and wine salon and academy, where you can discover a plethora of distinctive flavours of exclusive wines and champagnes offered.
Workshops on wine and champagne are also available at their academy, in partnership with Sarment Group. Renowned for its team of world-class sommeliers, you can learn about the intricate subtleties of wine and its rich history from Mr. Julien Drevon, Head Sommelier South East Asia of Sarment Group.
Wild Honey - No Place Like Home. Wild Honey is all about beautiful breakfasts. All day. Everyday. With its unique take on All Day Breakfast, Wild Honey features several of its renown signature dishes such as The European, The English and The Tunisian along with exciting dishes inspired by the infinite variety and creativity of dishes inspired by other countries and cultures as far flung as Corsica, Persia, Spain and The Caribbean. Travelling the world has never been more comfortable or tasty. Situated on the third floor; Wild Honey Scott's Square builds on the idea of 'No Place Like Home' by offering comfortable spaces as varied as 'The Kitchen Table' that seats twelve to the beautiful and unique open air 'Verandah' that provides gorgeous views to Scotts and Orchard Roads.
Collectors Contemporary celebrates the 50th anniversary of Singapore's independence with one of the most significant artists of the 20th Century.
The pop-up exhibition and sale of the highly coveted Warhol artworks at Scotts Square brings the artist's work into a direct relationship with two of Warhol's obsessions: consumerism and pop culture.
The show will enable collectors and visitors to access artworks containing Warhol's iconic subject matter as well as rare paintings that seldom appear on the art market.
Floral designer Christopher Teo would have you believe flowers speak louder than words. Step into his atelier and you'd be inclined to agree. From handheld bouquets and lavish centrepieces to arrangements bordering on the sculptural, every creation is unique—speaking volumes about the individuality of the patron as well as the artistry of the designer.
Artists who peddle the extraordinary, things that tickle the imagination, brands that stand out from the bland. Together with select collaborators from the little red dot and beyond, K+ presents an experience that is less mindless consumption, more mindful appreciation.
Curated by Kinetic Singapore, K+ is hosted by Scotts Square from 22 January to 31 August 2015 and will feature a changing line‐up through the months.
To keep in the loop, follow K+ at facebook.com/kplussg.
From a curatorial space showcasing artists, K+ grows to encompass retail and workshops in a new unit at #03-03. Shoppers can look forward to retail brands that stand out from the bland, as well as a chance to go behind the scenes and learn from master craftsmen at K+ workshops.
This new space opened on 2 July 2015 with multi-label boutique, nana & bird. Set up by best friends and shopaholics Georgina Koh and Tan Chiew Ling, nana & bird is an established favourite amongst discerning shoppers. Guided by the principle of only stocking what the duo would buy for themselves, the boutique curates a collection of forward fashion and accessories for women and children, and lifestyle brands for the home.
Poetree debuts in Asia the all-natural skincare, bodycare and fragrance collection skincare from Provence marked by rich heritage, authenticity and craftsmanship - sourced from two long-established producers and distilleries of Provençal lavender and olives. Le Château du Bois® and Une Olive En Provence® are both specialised authorities in capturing the full regenerative powers of fine Provençal lavender and the olive tree, a process perfected over generations.
Poltrona Frau is an Italian tradition that found its roots in the humble, labouring hands of a craftsman, Renzo Frau, almost a hundred years ago. Throughout its history, Poltrona Frau has worked with the greatest designers from the likes of Andree Putman, Frank Gehry to Jean-Marie Massaud, creating timeless icons of design. Today, Poltrona Frau is a status symbol of top quality materials, the skills of true craftsmen, all the style of Italy, and elegant, linear designs that shun the transience of fashion.
With a combined experience of over 60 years in hair dressing, our hair gurus at CINQ have all it takes to give professional expertise and great service. Hairstylists are able to alter the way you look, but good hairstylists have the ability to create fitting styles that compliment personalities and lifestyle habits.
Guardian Health & Beauty is the leading health and beauty chain in Singapore. Since 1972, we are the number 1 in store network with over 140 stores strategically located islandwide. Guardian Health & Beauty is a strong trusted household brand with a rich heritage and a strong foothold in its health & beauty offerings in terms of product range and services. Guardian Health & Beauty is renowned for its excellent pharmacy services and an extensive array of international health and beauty products. Guardian's impressive lineup includes premium advanced skincare as well as all the popular brands, the latest medication, vitamins and health supplements, traditional Chinese medicine, over-the-counter medications, nursing aids, salon hair care range and personal care needs. Guardian at Scotts Square is also one of our flagship stores in Singapore which aims to delight customers with stylish counters and a refreshing store concept to provide our shoppers with a memorable shopping experience. Guardian Health & Beauty is your one-stop destination of all beauty, health and wellness solutions. At Guardian, we believe in delighting our customers always.
MUSEE PLATINUM TOKYO is the Japan's No.1 premier hair removal salon that specialises in S.S.C. hair removal(Smooth Skin Control), the state-of-the-art pain free technology. The service is provided exclusively for women and promises safe and long-lasting results.
Welcome to the finer side of life. From scrumptious delis to vintage wines, the wide gourmet selections at Fairprice Finest will delight shoppers. The supermarket offers hand-picked exquisite seafood and seasonal produce from all over the world. Live the fine life you've always dreamed of. Only here, at FairPrice Finest.
Established in Spain in 1994, Pressto is the world's largest chain of quality express dry cleaning with more than 700 outlets in over 22 countries.
Pressot redefines dry cleaning by assuring the best in garment handling and delivering excellent service using the latest dry cleaning and laundering technologies for finest results. It caters to individuals and professionals who value their garments and wish to see them treated and cared for in the way they deserve.
The development and/or the building plans and/or above technical descriptions are subject to changes. The above summary may not be relied upon as a statement or representation of fact. While every
reasonable care has been taken in preparing this website, the developer and its agents shall not be held responsible or liable for any inaccuracy in its content.
All statements are believed to be correct but are not relied on as statement of representation of fact. All illustrations and perspective of the building and retail floorare artists impressions only and are not
to be relied on as statements or representation of fact.
Technical descriptions are subject to changes.
the Agreement to Lease and Lease Agreement shall form the entire agreement between us as the Landloard and the Tenant and shall supersede all statements, representations or promises made prior to the
signing of the Agreement to Lease and Lease Agreement.


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Today's Paper, also known as the e-Edition, is an online replica of the
printed newspaper. You can view today's paper or previous issues.
A 41-year-old man has been arrested in connection with the crash that happened in the 6300 block of W. Appleton Ave. , police said
A bill that would that would regulate kickboxing and other combat sports in Wisconsin will receive a hearing, according to the Assembly committee chairman, state Rep. Rob Swearingen.
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Original Article
Microbial mat controls on infaunal abundance and diversity in modern marine microbialites
Article first published online: 26 JUL 2013
DOI: 10.1111/gbi.12049
© 2013 John Wiley & Sons Ltd
Volume 11, Issue 5, pages 485–497, September 2013
Additional Information
How to Cite
Tarhan, L. G., Planavsky, N. J., Laumer, C. E., Stolz, J. F. and Reid, R. P. (2013), Microbial mat controls on infaunal abundance and diversity in modern marine microbialites. Geobiology, 11: 485–497. doi: 10.1111/gbi.12049
Publication History
- Issue published online: 14 AUG 2013
- Article first published online: 26 JUL 2013
- Manuscript Accepted: 23 JUN 2013
- Manuscript Received: 2 NOV 2012
Microbialites are the most abundant macrofossils of the Precambrian. Decline in microbialite abundance and diversity during the terminal Proterozoic and early Phanerozoic has historically been attributed to the concurrent radiation of complex metazoans. Similarly, the apparent resurgence of microbialites in the wake of Paleozoic and Mesozoic mass extinctions is frequently linked to drastic declines in metazoan diversity and abundance. However, it has become increasing clear that microbialites are relatively common in certain modern shallow, normal marine carbonate environments—foremost the Bahamas. For the first time, we present data, collected from the Exuma Cays, the Bahamas, systematically characterizing the relationship between framework-building cyanobacteria, microbialite fabrics, and microbialite-associated metazoan abundance and diversity. We document the coexistence of diverse microbialite and infaunal metazoan communities and demonstrate that the predominant control upon both microbialite fabric and metazoan community structure is microbial mat type. These findings necessitate that we rethink prevalent interpretations of microbialite–metazoan interactions and imply that microbialites are not passive recipients of metazoan-mediated alteration. Additionally, this work provides support for the theory that certain Precambrian microbialites may have been havens of early complex metazoan life, rather than bereft of metazoans, as has been traditionally envisaged.


text:
Narrow your search
Critics say Ellen Pao is fostering censorship that will destroy the community-curated news site. Reddit issues mea culpa, saying it's "screwed up" for years.
The company claims the summer sale will have more deals than Black Friday, though the discounts will only be available to its Prime members.
Need a geeky gingerbread treat? Make it so with this tasty "Star Trek" tribute to the U.S.S. Enterprise made by Trekkie bakers.
This Sony leak is the gift that keeps on giving. We'll discuss the latest round of revealing leaks, a new upsetting U.S. obesity report and a cafe in London that only serves breakfast cereal.
Technically Incorrect: Despite a government safety YouTube video that warns people about keeping their heads away from fireworks, a Maine man deliberately places a fireworks mortar tube on his head.
Can a stack of iPhones protect a Samsung Galaxy S6 from a blast fired from a Russian assault rifle? You'll just have to watch and see.
The streaming-music wars are on, with Apple Music and Spotify now locked in a battle on price, features and artist selection. But how do they compare on sound quality? We put them head-to-head to find out.
The big news for iOS 8.4 is Apple Music, but there's a long list of tweaks and fixes to iBooks and more in the latest iOS update.
There's a major shift of production from China to the U.S., which includes some truly affordable electronics and speakers.
The Audiophiliac listens to one of the most affordable, fully featured American-made tube amplifiers you can buy.


text:
I have a low testosterone level and have been prescribed a cream to use for it to be applied to my vagina area. Is this normal and do you recommend it? I kinda got a red flag when my doctor told me that a very few pharmacies in our area would have it. thanks
I am a woman and have been prescribed testosterone cream for low levels. do you recommend this?
- Posted:
- 3 Mar 2012 by dolphin girl
- Topics:
- hypogonadism - male, testosterone, doctor, cream
Answers (8)
I saw my family doctor, which done the hormone test because of my anxiety and thought it might be menopause and it showed my testosterone level was very low. She then referred me to a gynecologist and she prescribed the cream. Did you have any side effects?
As I recall, I used it a short time. A few months. Hormones take time when added to the body. I think you should give it a try because libido loss can really mess up a relationship, if you are in one. Then go back to doc and redo the tests. The GYN will have the best idea what you need. By the way, I had fibroids, big ones, and cysts. Hormones did shrink them down. So will menopause. Don't worry about little ones. Most people have them and they are normally benign. I had the large ones removed, left the little ones, and finally had my miracle baby just before I turned forty. You'd be surprised what can happen. And all that was 25 years ago!
Mostly you should have a GYN who you trust and have a good relationship. He/She will get you what you need. Wishing you wellness.
4 Mar 2012
I received two testosterone injections, a month apart, which were supposed to give me my sex drive back. No sex drive and had horrible, awful, scarring acne for close to two years after. I would research and ask a lot of questions. Make sure your levels are checked and interpreted correctly. I had a lot of hormone-related lab work done which could only be evaluated if the doctor knew where I was in my cycle. She signed off on it all as being ok - when I applied where I was in my cycle to the test results it showed I was extremely low for several hormones. What was the use of doing all that testing if she wasn't going to evaluate it correctly? Anyway - be your own advocate. Get a copy of your lab results and keep them. Google things if you don't understand them - a little time on the Internet can be a valuable teacher. And seek out the specialists - don't leave your health to a general practitioner, especially in a situation like this. Best wishes - ElizaJane
My wife is on HRT and a few years ago she tried T injections... all that accompished was bloating and weight gain. It did little to help her libido.
I am wondering about the testosterone shot... I am 38 years of age and I was told that getting this shot will add weight to me. I am 5'7 121 in pounds. I have never even happy with my size and have tried all types of pills and weight gain protein drinks. I'm at my end. I get married in July of this year and im desperately trying to gain at least 20-25 pounds.. Will this be the right move to make?
Hormones are very strong and can cause a lot of problems if taken incorrectly. Using Testosterone to gain weight, for what is a normal weight for your body - ? Have you found a doctor that will do this for you? I would hate to see you interfere with your endocrine system or your Gyn system and possibly interfere with your possibilities to get pregnant in the future. I'm not saying one shot would do this, but repeated shots may, or you might be someone whose system is very sensitive and where if one hormone shoots up high, then so goes another, then another, etc. This may occur in only a small percentage of the population, but I know 3 people who are this sensitive, and they've had a horrendous time trying to get their bodies on track after medical science sought to make things "better" with just a shot of this here, a medication for this there.
What I am saying is, if this is your normal weight and you are healthy - accept yourself, love how you look and your fiancé loves you like this right? Don't try to improve on how God made you. Please don't take anything that is not naturally made for your body, lightly. It can have huge consequences. ElizaJane23
I suffered most of the ill effects of menopause for over 8 years prior to getting my hormones tested by a professional who showed me the results and went over them with me-making me totally involved with my care. Put me on estrogen and progesterone first and titrated the levels monthly until it seemed to work well for me except for lack of sex drive and bloating did not go away. Put me on compounded testosterone cream (1 mg/ml) daily and it started to work almost immediately.
Except for still always being overheated as if my temp level were always high-had temp inside house at 63 during winter and AC down to 67 in summer! My doc who injects me for 8 years for the pain of degen disc, degen joint and fulminant osteoporosis and osteoarthritis noticed one day that I sweated profusely every time when the other in his office were all fine or chilled. He offered to inject me in the neck (right side ganglionic nerve injection) -this actually resets the hypothalamus and it worked as well! Never hot anymore except if I do not use my estrogen and progesterone-still needed these.Told my hormone GYN about this and she keeps his name and number on file to give other women who suffer same problem I did with still overheating even after hormones.
Hope all this info helps! Must BE your own health advocate and RESEARCH EVERYTHING BEFORE DOING_i KNOW i ALWAYS HAVE EVEN PRIOR TO BECOMING an RN at age 53!
4 Mar 2012
Did they prescribe any estrogen along with it?I assume you are female & our testoseone levels are not suppose to be high as a mans, & this drug is most usually given to males. They make estrogen pills that you can take or creams that help with low estrogen & they have a pack that also includes some progesterone the female, male hormore. Just my thoughts...
No she did not. All of my other hormone levels were normal. She only prescribed the testosterone cream to apply.
She did however offer to put me on birth control for ovarian cysts that I occasionally get. I do have a uterine fibroid but she said it was very small and if it started bothering me, she would give me injections to shrink it.
I chose not to do the birth control at the moment and wait and see if I continue to get them.
I'm just concerned over the testosterone cream and its side effects. There is not much information on it for women. And everything I've read says to apply it on your inner thigh or inner arm. She has prescribed rubbing it on the outside of the vagina and I haven't seen any info on that at all.
I do have fatigue and no drive at all. I'm taking a B12 shot one a week for a month and then monthly or I can chose to take the over the counter vitamin.
I'm also being treated for anxiety taking wellbutrin and buspur. I'm not one to take medicine at all and all of this happening to me at once is scary.
Don't forget that the doc is prescribing this as a way to rule out certain other possible conditions. Progesterone does not always work for low testosterone levels. Hence the fact that I was treated for that for a while with the testosterone. Been there, done that. Lots of woman have received this. Try and see what happens. I had a friend who started building some muscle strength for a while. But that was her goal. I had no noticeable change except that somehow my hormones became regulated. Oh, and hot flashes which was actually peri menopause which I did not know I was entering.
I do know that feeling of having drugs suddenly entering my Iife. Hang in there. Use common sense and be honest with the doctors and let them know how worrisome this may be. They should be giving you enough info so you can make a good decision. This would not be long term so you can see and then move on. Or else call the doc and let her know you changed your mind and see what other options are for you. Be your own advocate and things will change for the better. You can do this!
5 Mar 2012
Hi Dolphin Girl,
I am on bio-identical hormones that come in cream or pill form. I too was prescribed testosterone and had no problems with it. The reason that not very many pharmacies carry it is because they usually have to be a compounding pharmacy. The pharmacy that makes mine looks at my hormone levels and then produces a cream specifically for the amount and kind of hormone I need. Does that make sense? If not, let me know and I will try to explain it better.
Your friend -Terri-
Any chance you can say more? It's been a couple of years, and you're perhaps able to help others with a war story of how it has been :)
5 Mar 2012
Just like tlcandmore, I take bio-identical hormones. I get my blood or urine tested and my testosterone, estrogen, etc. is adjusted. I had testosterone cream once and was told to rub it in different spots everyday. Those included my stomach, inner thigh, an inside of my arm. I would NOT put it anywhere near your vagina unless it's supposed to treat that area specifically. I get these hormones from a compounding pharmacy through my gyno. Please see a gyno before you use that stuff around your vagina. If I was told to rub it in different areas each day, I'm assuming it may irritate the skin if applied to the exact same area.
It was my gynecologist that prescribed the cream and told me to rub it on the outside of my vagina three times a week for 8 weeks and then come back. I haven't seen much info on the internet about rubbing it in that area, so it confuses me.
My testosterone level was the only hormone that was low, so I don't take any other hormones.
Hmmm, I don't know what to say. I don't want to say your gyno is wrong so you should ask more questions or at least ask one of your other doctors what their opinion is. Again, why rub it on/around your vagina, unless there is something wrong with that area? You need to know why.
The reason for applying it to your vaginal area is because the tissue is more absorbent than anywhere else in the body. You will absorb a more correct level of your dose by applying it to or around the vagina. This is a very very common practice for hormone therapy. It does not have anything to do with treating a specific area, it has everything to do with absorbtion. The reason for some doctors telling you to "switch it up" in reference to where to apply it is because it stimulates hair growth, thus switching up the areas reduces your chance of hair folical stimulation as the same area is not receiving the dose everytime. Hope this helps.
The reason for rubbing it into your vaginal area is because it is easily absorbed into the body there because of the mucose membrane, very thin tissue in that area.
29 Nov 2014
My brother has been compounding my hormones since 2000. I just saw a doctor who ordered blood tests to check my hormone levels, primarily because my hair won't stop falling out. The doctor's office faxed the results to my brother and she had prescribed testosterone cream on the labia. I didn't like that answer and now the doctor is in Australia until mid January. The way my brother explained it is that the testosterone will increase the libido, it will build up muscle tissue and do several other positive things. It is not dangerous to apply to the labia. I am going to call the office and ask that another physician explain the results to me. Compounding HRT is the way to go. The pharmacist can closely duplicate the hormones naturally produced in your body when menopause causes them to produce less.
It eliminated the migraines I had after my hysterectomy when the gyny only wanted to prescribe synthetic hormones that are no where near as accurate to the hormones my body was producing. I hope this made sense. My brother suggests I try applying the testosterone this way to see how it compares to the troches I was taking. I don't like it but I totally trust my pharmacist.
Am new to this site and have just read dolphin girl and Sbrenner because today I was prescribed the compound to help build up my walls inside in order with a prolapsed bladder so they can then in a few weeks time after renewing the tissue, insert a pessary. Supposed to help with libido too hopefully. I am trying to avoid surgery. This post is 2 years old, I'd be so grateful if you two women or anyone else who used this with a past history, could tell me NOW how you made out and if you had any long term side effects and if hindsight is 20/20 WOULD you do this again? Did it help? Thanks so much!
19 days ago
I've been using a compounded testosterone cream 2%, for about 4 years. I apply it to my vaginal area during the week and to inner thighs on weekends. I am post menopausal and was losing muscle tone and the libido Was totally gone! I will take this forever because I've had nothing but good from it. Libido is through the roof!
How long did it take for you to notice a difference? I just started the testosterone cream today and am really anxious for it to start working. I know it may take a while. I have low libido, muscle tone, and some abdominal fat that I am hoping will go away!
Give it a couple of weeks. Also if you put it on your vulva your clitoris will enlarge and become pleasantly sensitive. If you work out in about 6 months you will notice beautiful muscle definition and you will be stronger. I love everything about it !
Further Information
- Testosterone Information for Consumers
- Testosterone Information for Healthcare Professionals (includes dosage details)
- Side Effects of Testosterone (detailed)
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Suspect killed; 2 La. officers shot
DENHAM SPRINGS, La- A 47-year-old man was fatally shot Monday afternoon by two police officers, both of whom were shot in the confrontation, police said.
The man, Daniel Annison Jr., was shot in his front yard at about 4:15 p.m., police said.
The officers shot in the incident were Cpl. Matthew Martello and David Hooter. WAFB-TV reported that Martello was shot in the face and that Hooter was released from the hospital later Monday.
Police Chief Jeff Wesley said the shooting happened when the officers showed up at the home after Annison's family reported a domestic disturbance. When Annison's mother opened the door, Annison pushed her aside and shot the officers, Wesley said.
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According to NASA, the temperature on Uranus is 60.92 degrees Kelvin. The planet does not have a solid surface. Most of Uranus' mass is made up of icy materials, including water, methane and ammonia.Know More
Uranus is the seventh planet from the sun at a distance of approximately 1.8 billion miles. A day on Uranus is 17 Earth hours, which is equal to the time it takes for Uranus to complete one spin. A year on Uranus is 84 Earth years, which is the amount of time it takes to orbit around the sun. Unlike the other planets, Uranus rotates on its side, which means it spins horizontally.Learn more about Planets
Uranus is the smallest of the gas planets, but its diameter of 51,118 kilometers is still four times longer than the Earth's, according to Universe Today. The volume of Uranus is massive, as it could hold 63 Earths inside its perimeter.Full Answer >
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Originally written on Subway Domer | Last updated 6/18/13
Notre Dame football kicks off in 74 days and it can't come soon enough. It's a tricky situation because you should never "wish your summer away," but then you have days where your emotion, anger, and proclivity towards drinking early in the morning are much more acceptable during the college football season. Exhibit (A) The Subway Domer Garage Sale. I never meant to live tweet this occasion, but reasons happened. [View the story "The Subway Domer Garage Sale" on Storify]
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