text:
|Publication number
|Publication type
|Application number
|Publication date
|Dec 29, 1992
|Filing date
|Mar 20, 1991
|Priority date
|Mar 20, 1991
|Fee status
|Also published as
|Publication number
|Walter G. Rakitsky, Danny D. Richey
|Original Assignee
|Merck & Co., Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (7), Referenced by (24), Classifications (17), Legal Events (9)
|External Links: USPTO, USPTO Assignment, Espacenet
Concrete compositions contain aggregate (e.g., sand and rock), cement and water. When water is added to the cement, a paste forms which hardens over time to a solid structure. Various additives have been used in cement compositions to modify their properties. Long fibers such as asbestos reduce the sagging of these pastes and thus is beneficial when applying tiles to a vertical surface. Freezing point depressants are used when cements are to be poured in subfreezing temperatures.
Bentonite clay has been used for this purpose. Other polymers, such as the polyvinyl alcohols and methyl methacrylates, have been used to reduce friction when pumping these pastes and to otherwise modify their workability. Fumed silica is used as an additive to make stronger concrete with reduced permeability.
U.S. Pat. No. 4,963,668 describes cement compositions comprising 0.01 to 0.9% welan gum by weight of dry cement to improve workability, suspension of aggregates, air entrainment, sag resistance, flow characteristics and resistance to water loss.
Incorporation of fluid-enhancing polymeric material into cement-containing mixtures is difficult when the fluid-enhancing material requires hydration. Such hydration must be achieved by lowering the initial amount of water used to mix the cement and sand, hydrating the polymer with water, and then adding the polymer/water dispersion to the initial cement/sand/water mix to obtain a cement/sand/water/polymer mixture having the desired final weight ratio.
When water is held out of the concrete to hydrate the polymer, the amount of water which can be used to initially disperse cement and sand is insufficient to form a uniform mix. Large golf and bowling ball-size agglomerates form which do not disperse even when the balance of the mixing water is added. Furthermore, pre-hydration of the polymer does not occur quickly enough to stay in synchronization with the typical 60-90 second batch plant mixing cycle. It is also impractical to have a large quantity of hydrated polymer solution available for inclusion into the concrete without significant additional costs for preservation, mixing, and storage.
Addition of water containing hydrated polymer to a dry cement/sand mixture such that the desired cement/sand/water/polymer weight ratio is achieved immediately is undesirable because the polymer can interfere with early stages of cement hydration and may impair mechanical properties of the mixture. Such addition also makes dispersion of the cement particles more difficult.
The present invention is a rapidly hydrating welan gum useful for improving cement workability. The gum is an improvement over the prior art because predispersion/prehydration of the gum prior to mixing with concrete is not required in order to obtain a uniform, workable mix.
The invention is a rapidly hydrating welan gum which is useful for situations where welan gum addition in a pre-hydrated dispersion form is not pratical.
The gum has hydration characteristics sufficient for it to be dry blended with cement and other chemical additives or admixture such as an air entraining agent, corrosion inhibitor, accelerator or retarder, or as a dispersion in a carrier which is typically a superplasticizer (dispersant), and then added to a preformed cement/water pre-mix. The preformed cement/water pre-mix may also contain aggregate (e.g. sand and rock) sufficient for concrete composition formation. The polymer does not swell and generate viscosity in the carrier which makes it a convenient way to add welan gum to cementitious products. Because of its enhanced hydration properties, the polymer is able to achieve full functionality under field make-up conditions. Typical batch plant mixing cycles are from 60-120 seconds at relatively low shear rates.
Welan gum describes an industrial grade of a microbial polysaccharide produced by the growth of the Alcaligenes strain ATCC 31555 in a pure culture fermentation using carbohydrates as a carbon source. The product is recovered from the fermentation broth by precipitation with alcohol. Welan gum is a polysaccharide gum which comprises principally a heteropolysaccharide containing the neutral sugars D-glucose, D-glucuronic acid, L-rhamnose and L-mannose and glycosidically linked acetyl ester groups. The structure of this polysaccharide is described in Jansson P E, Lindberg B, and Widmalm G (1985) Carbohydrate Research 139, 217-223.
The rapidly hydrating welan gum used in the present invention is a novel form of welan gum. Kang et al., U.S. Pat. No. 4,342,866, describes a procedure for making welan gum that does not have hydration characteristics such as those of the rapidly hydrating welan gum of the present invention.
This gum is prepared by a procedure which includes many of the steps used to prepare welan gum described in U.S. Pat. No. 4,342,866 (the welan gum hereinafter referred to as "welan gum S-130"), i.e., S-130 fermentation followed by precipitation, drying and milling. However, the welan gum useful in the present invention is obtained by modification of the S-130 process. The modification involves adjustment of the fermentation broth, prior to precipitation, to a pH of between about 10.5 and 12.5, preferably with KOH or soda ash, more preferably 45% KOH, followed by heating between about 170� F. and 230� F. for approximately 3-20 minutes. Precipitation followed by drying and milling occur in the normal manner. Preferably, the pH is adjusted to between about 11 and 11.5, and the broth is heated for about 5 minutes at 210� F. It is also preferable to add calcium propionate, more preferably 0.2%, to the broth before pH adjustment.
A. Characteristics of Colonial Morphology
On nutrient agar, small yellow colonies appear in one day at 30� C. with the diameter reaching about 1.5 mm after 5 days' incubation. The colonies are round, smooth, convex, mucoid, and opaque. The yellow color becomes more deep and the texture of colonies becomes hard after prolonged incubation.
On YM agar, small mucoid yellow colonies appear in one day and the diameter reaches about 3 mm after 5 days' incubation. The colonies are round, smooth, convex, and opaque, but the top of the colonies are flat. No membraneous hard texture is observed.
B. Characteristics of Cell Morphology
Strain S-130 is a gram-negative rod-shaped bacterium. On nutrient agar the average size of the cell is about 0.5-0.6 by 1.2-1.6 μm; ends of the cells are tapered and curvature was often seen. The size and shape of the cells do not change significantly after prolonged incubation.
On YM agar the average cell size is 0.6-0.8 by 1.6-2.0 μm, but the cell becomes longer (3-4 μm); accumulation of PHB is significant. Motility is positive. Flagella stains (modified silver nitrate method) show that the strain has mixed flagellation, i.e., polar and lateral flagella, as well as peritrichous flagella.
C. Physiological and Biochemical Characteristics
The following are results of tests employed:
Cytochrome oxidase is weak or negative; catalase positive.
Organism is capable of growth at 37� and 41� C., but not at 43� C.
Tolerance to 3.0% NaCl, but not to 6.5% NaCl.
Growth at pH between 5 and 12.
Aerobic acid but not gas was produced from various carbohydrates, such as:
______________________________________ D-xylose lactose L-arabinose maltose D-glucose melibiose fructose sucrose galactose trehalose mannose raffinose______________________________________
Litmus milk was reduced, but not peptonized.
ADH was positive, but not LDC, ODC, and PDA.
MR positive, but negative for VP, indole, and urease.
Esculin gelatin (weak) and Tween 80 (weak) were hydrolyzed, but not casein, starch, cellulose, pectin.
No phosphatase, and haemolysis negative.
0.1% triphenyltetrazolium chloride was not inhibitory.
Survival at 60� C. for 30 minutes.
Organisms grow on EMB agar and Tellurite Blood, but not on SS and MacConkey agar.
D. Antibiotic Susceptibility Test
The strain S-130 is susceptible to the following antibiotics.
______________________________________Kanamycin 30 μgNeomycin 30 μgChlortetracycline 5 μgNovobiocin 30 μgErythromycin 15 μgTetracycline 30 μgGentamicin 10 μgCarbenicillin 50 μg______________________________________
and not susceptible to:
______________________________________Penicillin 10 unitsStreptomycin 10 μgColistin 10 μgPolymyxin B 300 units______________________________________
E. Nutritional Characteristics
Organic growth factors are not required and ammonium salts serve as the sole nitrogen source. A total of 30 organic compounds are utilized as sole source of carbon and energy. Most carbohydrates are utilized.
F. G+C Content of the DNA
No DNA analysis was performed.
G. Identification by API System
The strain could not be identified by this system.
H. Identification
The strain S-130 is a gram-negative aerobic rod-shaped organism. The mode of flagellation of the organism is mixed; polar and peritrichous flagella (possibly degenerate flagella) are seen. According to Bergey's Manual (8th Edition), such organisms belong as a member of the genus Alcaligenes.
TABLE I______________________________________Biochemical and Other Miscellaneous Tests Employedfor the Strain S-130______________________________________Oxidase: Kovac's + (weak)Pathotech + (weak)Catalase +OF medium:Oxidative +Fermentative -Gas from glucose -H2 S production -TS1 from cystine �Ammonium from NTpeptoneβ-Galactosidase (ONPG) +Argnine dihydrolase +Lysine -decarboxylaseOrnithine decarboxylaseTryptophan deaminase NTPhenylalanine deaminase -Urease -Indole -MR test +VP test -Nitrate reduction -Nitrite reduction -Denitrification NTN2 -fixation:Growth in Burk's medium +Nitrogenase activity NTMelonate (oxidation) -Phosphatase -Haemolysis (sheep blood) -Litmus milk: acid, -reduction only3-ketolactose productionSurvival at 60� C. +for 30 min.TSI: Slant AcidButt No growthGas -Egg Yolk Reaction -Hydrolysis of:Gelatin + (weak)Casein -Starch -Tween 80 + (weak)Pectin -Alginate NTCellulose -Chitin -DNA NTEsculin +Growth onvarious media:EMB agar +MacConkey agar -SS agar -Mannitol salt agar -TCBS agar -Tinsdale tellurite +blood agarPseudosel agar NTPigment production:King A medium -King B medium -Dye reaction:Congo red -______________________________________ + = positive - = negative NT = not tested
Heteropolysaccharide is produced during the aerobic fermentation of suitable aqueous nutrient media under controlled conditions via inoculation with the organism of the unnamed Alcaligenes species. The media contain sources of carbon, nitrogen and inorganic salts.
In general, carbohydrates (for example, glucose, fructose, maltose, sucrose, xylose, mannitol and the like) can be used either alone or in combination as sources of assimilable carbon in the nutrient medium. The exact quantity of the carbohydrate source of sources utilized in the medium depends in part upon the other ingredients of the medium but, in general, the amount of carbohydrate usually varies between about 2% and 5% by weight of the medium. Preferably 3% glucose is used. These carbon sources can be used individually, or several such carbon sources may be combined in the medium. In general, many proteinaceous materials may be used as nitrogen sources in the fermentation process. Suitable nitrogen sources include, for example, yeast hydrolysates, primary yeast, soybean meal, cottonseed flour, hydrolysates of casein, corn steep liquor, distiller's solubles and the like. The sources of nitrogen, either alone or in combination, are used in amounts ranging from about 0.05% to 0.5% by weight of the aqueous medium.
Among the nutrient inorganic salts which can be incorporated in the culture media are the customary salts capable of yielding sodium, potassium, ammonium, calcium, phosphate, sulfate, chloride, carbonate, and the like ions. Also included are trace metals such as cobalt, manganese, iron and magnesium.
It should be noted that the media described in the examples are merely illustrative of the wide variety of media which may be employed, and are not intended to be limitative.
As an alternative medium, S-130 may be grown under low Ca++ conditions, i.e., in deionized water, or some other aqueous system substantially free of Ca++ (i.e., less than about 4 ppm Ca++ per 1% gum in the final fermentor broth).
The fermentation is carried out at temperatures ranging from about 25� C. to 35� C.; however, for optimum results it is preferable to conduct the fermentation at temperatures of from about 28� C. to 35� C. The pH of the nutrient media for growing the Alcaligenese culture and producing the polysaccharide S-130 can vary from about 6 to 8, preferably 6.5 to 7.5.
A small scale fermentation is conveniently carried out by inoculating a suitable nutrient medium with the culture, and after transfer to a production medium permitting the fermentation to proceed at a constant temperature of about 30� C. on a shaker for several days.
The fermentation is initiated in a sterilized flask of medium via one or more stages of seed development. The nutrient medium for the seed stage may be any suitable combination of carbon and nitrogen sources. The seed flask is shaken in a constant temperature chamber at about 30� C. for 1-2 days, or until growth is satisfactory, and some of the resulting growth is used to inoculate either a second stage seed or the production medium. Intermediate stage seed flasks, when used, are developed in essentially the same manner; that is, part of the contents of the flask from the last seed stage are used to inoculate the production medium. The inoculated flasks are shaken at a constant temperature for several days, and at the end of the incubation period the contents of the flasks are recovered by precipitation with a suitable alcohol such as isopropanol.
For large scale work, it is preferably to conduct the fermentation in suitable tanks provided with an agitator and a means of aerating the fermentation medium. According to this method, the nutrient medium is made upin the tank and sterilized by heating at temperatures of up to about 121� C. Upon cooling, the sterilized medium is inoculated with a previously grown seed of the producing culture, and the fermentation is permitted to proceed for a period of time as, for example, from 2 to 4 days while agitating and/or aerating the nutrient medium and maintaining the temperature at about 30� C. This method of producing the heteropolysaccharide is particularly suited for the preparation of large quantities.
After fermentation, calcium propionate is preferably added to the fermentation broth, and the fermentation broth is adjusted to a pH of between about 10.5 and 12.5 with KOH or soda ash, preferably 45% KOH. pH adjustment is followed by heating between about 170� F. and 230� F. for approximately 3-20 minutes. Preferably, the pH is adjusted to between about 11 and 11.5, and the broth is heated for about 5 minutes at 210� F., and amount of calcium propionate added is about 0.2%.
After the adjustment period, the gum is precipitated using a suitable alcohol such as isopropanol. The precipitate is dried in typical fashion.
After drying, the product is milled according to standard milling procedures. Target mesh size varies according to desired product characteristics. For example, larger mesh size material, e.g. 80 mesh, is preferred for transport of the material using conventional dry material handling systems. Smaller mesh size material, e.g. 140 mesh, is preferred for enhanced rapid hydration performance. In all cases, however, the gum produced according to the described procedure, using described fermentation broth pH adjustment and subsequent heating steps, possesses rapid hydration characteristics as compared to conventionally prepared welan gum produced according to the procedure described in U.S. Pat. No. 4,342,866.
Glucuronic acid was identified by using the method of Bhatti et al., Biochim. Biophys. Acta 22 (1970) 339-347. Absolute configurations of the sugars were determined by the methods devised by Gerwig et al., Carbohydrate Research 77 (1979) 1-7, and by Leontein et al., Carbohydrate Research 62 (1978) 359-362.
Methylation analyses were performed essentially as described in Jansson et al., Chem. Common. Univ. Stockholm, 8 (1976) 1-75. Methylated polymers were recovered by dialysis against water, followed by freeze-drying. Low-molecular-weight products were recovered by reversed phase chromatography on Sep-Pak C18 cartridges, Waeghe et al., Carbohydrate Research 123 (1983) 281-304. The sample was diluted with an equal volume of water and applied to the column. This was washed with water and acetonitrile-water (15:85), and the sample was eluted with acetonitrile.
The methylated polysaccharide (1.5 mg) was dissolved in freshly distilled tetrahydrofuran (2 mL). Lithium borohydride (10 mg) was added and the solution boiled under reflux for 2 hours. Excess of lithium borohydride was decomposed with M acetic acid, chloroform (5 mL) was added, and the solution was washed several times with water, dried, and concentrated.
To a solution of the methylated polysaccharide (1.5 mg) in dimethyl sulfoxide (1.5 mL) were added a trace of toluene-p-sulfonic acid and 2,2-dimethoxypropane (0.1 mL) in order to eliminate any water present. Sodium methylsulfinylmethanide in dimethyl sulfoxide (2M, 1 mL) was added, and the mixture was agitated in an ultrasonic bath for 30 minutes and kept at room temperature for 15 hours. Trideuteriomethyl iodide (0.5 mL) was added with external cooling and the mixture agitated in the ultrasonic bath for 30 minutes. The excess of methyl iodide was removed by flushing with nitrogen, and the solution was diluted with water and added to a Sep-Pak C18 cartridge. The material was recovered as described above. The product was hydrolyzed with 2M trifluoroacetic acid for 15 hours at 100� C. and the mixture of methylated products was analyzed (Table II, column C).
Approximately 50% of the rapidly hydrating welan gum polysaccharide units contain an O-acetyl group. An acid hydrolysate of the fermented polysaccharide contained glucose, rhamnose and mannose in the relative proportions 43:46:11. It further contained glucuronic acid, identified by g.l.c. of a sample that had been methanolyzed and trimethylsilylated using the procedure described by Bhatti et al.
Absolute configurations of component sugars were determined by g.l.c. of the glycosides obtained on solvolysis with chiral 2-butanol followed by trimethylation, as devised by Gerwig et al. The glucose and glucuronic acid have the D configuration and the rhamnose has the L configuration. The mannose has the L configuration. This was confirmed by g.l.c. of the glycosides obtained on solvolysis with chiral 2-octanol followed by acetylation, as devised by Leontein et al.
Methylation analysis without and with carboxyl-reduction of the methylated polysaccharide, gave the products listed below, columns A and B respectively.
TABLE II______________________________________METHYLATION ANALYSIS OF THEPOLYSACCHARIDE AND SOMEDEGRADATION PRODUCTSa Mole %Sugarb Tc A B C D E______________________________________1,2,3,5-Rhamnitol 0.38 13 222,3,4-Rha 0.59 12 7 162,3-Rha 0.94 26 21 182,3,4,6-Glc 1.00 54 362,3,4,6-Man 1.00 10 7 19 52,4,6-Glc 1.67 26 23 .sup. 43d2,3,6-Glc 1.92 33 342,6-Glc 2.79 26 23 4 32,3-Glc 3.56 19______________________________________ a Key: A, methylated polysaccharide; B, methylated and carboxylreduced polysaccharide; C, uronic aciddegraded polysaccharide; D, acidic tetrasaccharide; E, acidic penta and tetrasaccharide. b 2,3,4Rha═2,3,4tri-O-methyl-L-rhamnose, etc. c Retention time of the corresponding alditol acetate, relative to 1,5di-O-acetyl-2,3,4,6tetra-O-methylD-glucitol on an SP1000 glasscapillar column at 200� C. d >90% Trideuteriomethyl at 0-4.
In order to determine the sequence of the sugar residues, the rapidly hydrating welan gum polysaccharide was subjected to a uronic acid-degradation (Lindberg et al. Carbohydrate Research 28 (1973) 351-357 and Aspinall et al. Carbohydrate Research 57 (1977) c23-c26). The fully methylated polysaccharide was treated with sodium methylsulfinylmethanide in dimethyl sulfoxide, methylated (using trideuteriomethyl iodide), and hydrolyzed, and the mixture of methylated sugars was analyzed (Table II, column C). 2,6-di-O-methyl-4-O-trideuteriomethyl-D-glucose was derived from the branching D-glucopyranosyl residue, the 4-position of which was liberated on degradation of the uronic acid. The 3-substituted D-glucopyranosyl residue linked to 0-4 of the uronic acid was released by β-elimination and further degraded by β-elimination, with release of the 4-substituted L-rhamnopyranosyl residue. A considerable part of this residue was also degraded.
The polysaccharide imparts viscosity to an aqueous medium when dissolved in water in low concentrations. Because of this, its sensitivity to shear and overall rheology, it is useful as a thickening, suspending, emulsifying, stabilizing, lubricating, film-forming, or binding agent, especially in aqueous systems. In particular, it has uses in the following applications or products: adhesives, wall-joint cements, grouts and mortars, spackling compounds, can sealing, boiler compounds, latex creaming, welding-rod fluxes, brazing pastes, ceramic glazes and extrusions, cleaners and polishes, toys, emulsions (latex, asphalt, silicone), silver recovery, seed coatings, spray control for pesticides or herbicides, emulsifiable concentrated and flowable pesticides and herbicides, tobacco binders, water-based inks, lithographic fountain solutions, leather finishes, hydro-mulching and hydro-seeding, textile printing and finishing, wet-end paper additives, wet-end paper retention and formation aid, anti-stick compounds, mold-release agents, liquid resins, slurry and packaged explosives, petroleum and water-well drilling muds, petroleum workover and completion fluids, petroleum stimulating fluids, fracturing, spacer fluids, gravel packing cosmetics, pharmaceutical suspensions and emulsions.
A. Culture Maintenance
The unnamed Alcaligenes organism, ATCC 31555, grows quite well on NA agar, with good colonial morphology. The incubation temperature is 30� C. The organism produces a yellow pigment.
B. Seed Preparation
Flask seeds are prepared in YM broth incubated at 30� C. for 24 hours, then used to inoculate seed medium which is the same as final fermentor medium. A 5% inoculum is used for a 14 L fermentor.
C. Final Fermentor Medium
The following medium gives acceptable results in the 14 L fermentor and can be used for larger scale 20 L and 70 L fermentors:
______________________________________ Glucose 3.0% K2 HPO4 0.05% Promosoy 0.05% NH4 NO3 0.09% MgSO4 7H2 O 0.01% Fe++ 1 ppm HoLe salts 1 ml/L______________________________________
The pH is controlled between 6.5 and 7.5. At 0 hours, pH is 7.3 and residual carbon source was measured to be 3.07%. After 25.5 hours, pH was 7.0 and beer viscosity measured 2350. After 63.5 hours, pH was 6.3 and beer viscosity 3950, and the reaction is terminated by adding 4% isopropanol.
HoLe salts are a trace element solution containing tartrate, magnesium molybdate, CoCl3, ZnCl2, CuCl2, boric acid, manganese chloride and ferrous sulfate.
The initial agitation and aeration rates were 400 rpm and 3 L/M, respectively. The aeration remained constant throughout the fermentation. The agitation was increased as necessary during the fermentation to ensure good mixing. Maximum agitation was 1600 rpm.
When a low calcium product is desired, the medium above is used with deionized water.
D. Broth Adjustment
During this stage, 0.2% calcium propionate is added to the broth. The fermentation broth is adjusted to a pH of 11-11.5 with 45% KOH, followed by heating at 210� F. for 5 minutes.
E. Recovery
Good fibers are produced under precipitation conditions giving 58-62% spent IPA.
F. Drying
Product is recovered after drying with rotary air dryers.
After drying, the product is milled according to standard milling procedures. Target mesh size varies according to desired product characteristics. For example, larger mesh size material, e.g. 80 mesh, is preferred for transport of the material using conventional dry material handling systems. Smaller mesh size material, e.g. 140 mesh, is preferred for enhanced rapid hydration performance. In all cases, however, the gum produced according to the described procedure, using described fermentation broth pH adjustment and subsequent heating steps, possesses rapid hydration characteristics as compared to conventionally prepared welan gum produced according to the procedure described in U.S. Pat. No. 4,342,866.
Measurements of the gum of the present invention in 2% KCl show excellent viscosity development, with excellent NaCl stability and maintenance of viscosity up to at least 300� F.; slight gelation of gum is observed in 2% KCl.
Cement compositions which can be made with the subject rapidly hydrating welan gum comprise cement, fine and/or coarse aggregate, and other optional additives used for various purposes by those skilled in the art. Various types of cements, as well as additives, are described below.
A typical composition for forming a cubic yard of concrete includes about 400-800 lbs. cement; about 120-480 lbs. of water, preferably 0.3-0.6 weight fraction based on weight of cement used; about 1200-4000 lbs. of fine and/or coarse aggregate, preferably 1:3-5 weight ratio of cement: fine and/or coarse aggregate; 0.1-2 lbs. rapidly hydrating welan gum of the present invention, and other optional desirable additives.
Cement compositions of the present invention are prepared using a procedure whereby a portion of the cement powder, optionally with other dry ingredients, is dry-blended with rapidly hydrating welan gum prior to addition to a mixture of cement, water, and fine and/or coarse aggregate. The dry-blend comprises the total amount of rapidly hydrating welan gum to be added and an amount of cement approximately equal to 5 to 20 times by weight the amount of rapidly hydrating welan gum to be added.
In one example, 1 lb. of rapidly hydrating welan gum is combined with 10 lbs. of cement to form a dry-blend. 560 lbs. of dry cement is mixed together with 275 lbs. of water, 1970 lbs. coarse aggregate and 1145 lbs. of fine aggregate, for a period of time, to distribute the cement and aggregate and begin hydration. Thereafter, the gum and cement dry blend is added.
Cement compositions include hydraulic cements, i.e., finely ground and calcined calcium silicates and calcium aluminates which when mixed with water react to form a hard, rock-like mass. Cement is e.g. portland cement, portland pozzolan cement (containing about 15-40% pozzolan) blast furnace slag cement, slag cement (containing blast furnace slag and hydrated lime), masonry cement (e.g., adhesive mortars), construction concrete (containing sand and aggregate), oilfield cement (i.e., cements with retarders to prevent rapid setting so that they may be used at high temperatures and pressure environments of deep wells), aluminous cement (containing high amounts of calcium aluminates), expansive cements (containing high sulfate and alumina concentrations and which expand on hardening), air entrained cement (containing compounds which retain air bubbles and thus yield frost- and chemical-resistant concretes), lightweight concrete (containing low density materials such as furnace clinker, pumice, foamed slag, fly ash, gas, wood, etc.) heavy concrete (containing dense material such as barite, iron ore (i.e., illmenite or hematite), steel, etc.), and low heat concrete (with modified compositions that minimize heat generation during the setting process).
Oilfield cements are basically the same as those used in construction (i.e., portland cement). The American Petroleum Institute has set specifications for oilfield cements. These as classified as "A" through "H", and "N", all of which are useful in compositions of this invention.
Cement additives in oilfield cements are materials mixed in the slurry for reducing or increasing density, increasing volume at reduced unit cost, accelerating or retarding slurry thickening time, increasing strength, preventing loss of whole cement slurry, increasing or improving the durability, decreasing water loss from the slurry, and increasing or decreasing the viscosity of the cement slurry.
It is a purpose of the invention to use rapidly hydrating welan gum for controlling water loss from cement slurries and as a suspending agent. The gum increases workability of cement compositions. The increased workability is conveniently achieved by dry blending rapidly hydrating welan gum with a portion of cement and then adding the gum/cement blend to a cement/water pre-mix. Incorporation of rapidly hydrating welan gum in this fashion eliminates the need for prehydrating the gum prior to a cement/sand/water mix and avoids interference with the hydration reaction of cement and water.
It improves the ability of cement slurries to be easily placed in crowded area such as around re-inforcing bars without aggregate settling.
Cement slurries containing rapidly hydrating welan gum show more uniform density as the curing process proceeds. The suspension properties of the gum keep the slurry more uniform, yielding less aggregate settling and less free water on the surface of the slurry.
Cement additives which are useful in compositions of this invention include mineral admixtures, accelerators, retarders, fluid loss reducers, dispersants, extenders and loss circulation materials, antifoam agents, and weighting materials.
Mineral admixtures include silica fume, fly ash, blast furnace slag or fibers.
Accelerators include calcium chloride, sodium silicate (Diacel A), sodium chloride (salt), ammonium chloride (NH4 Cl), or combinations or solutions of these salts.
Retarders include calcium or sodium lignosulfonates or other lignin derivatives, borax compounds, CM HEC (carboxymethylhydroxethylcellulose), sodium or calcium gluconates, and sugars.
Fluid loss reducers include bentonite, high, medium and low viscosity HEC, polyethylene imines and amines, long chain alcohols, CM HEC, polyvinyl pyrrolidones, and fine inorganic solids (such as talc).
Dispersants include sodium citrates, sodium napthalene sulfonates, lignin and lignin derivatives to reduce viscosities of cement slurries and to aid in fluid loss control by dispersing the particles in the slurry.
Extenders and loss circulation materials include pozzalons, asphalts, gilsonites, bentonite, diatomaecous earth, and various materials to plug passages where loss of whole cement occurs.
Antifoam agents include long chain alcohols such as octanols, stearates and their salts.
Weighting materials include barite, hematite, and illmenite to increase the density of cement slurries.
The cement compositions of this invention can be conveniently prepared by adding rapidly hydrating welan gum in dry form to the rest of the compositions. The invention is further defined by reference to the following preparations and examples, which are intended to be illustrative and not limiting.
A cubic yard of concrete was prepared according to the procedure of the present invention. To prepare a suitable cement slurry, 6 lbs. of API type G cement was dry blended with 0.3 lbs. 140 mesh rapidly hydrating welan gum prepared according to the procedure described in Example 1. The dry blend was added to a cement/water aggregate pre-mix, containing 560 lbs. cement, 1800 lbs. aggregate, and 283 lbs. water, to produce a homogeneous, smooth soft cement slurry, the viscosity of which increased with increasing gum concentration and with time.
A cement slurry was prepared according to the procedure of Example 2, except that Portland type A cement was used instead of API type G cement, and 0.5 to 0.8% Lomar PW dispersant was added to the gum/cement dry blend. The resulting slurry produced a homogeneous, smooth soft cement slurry.
Following the procedure of Example 3, but substituting welan gum prepared according to the procedure described in U.S. Pat. No. 4,342,866 for rapidly hydrating welan gum, cement, water, dispersant and gum were mixed. Because the gum did not hydrate properly, a low-viscosity, non-homogeneous material containing visually distinguishable gel balls was obtained.
A slurry containing H cement, 0.7% dispersant, 46% water and 0.3% rapidly hydrating welan gum (all based on dry weight), according to the procedure described in Example 2, was prepared. A smooth, soft, homogeneous cement slurry was obtained.
A. Culture Maintenance
The unnamed Alcaligenes organism, ATCC 31555 grows quite well on nutrient agar. The incubation temperature is 30� C. The organism produces a yellow pigment.
B. Seed Preparation
Flask seeds are prepared in YM broth incubated at 30� C. for 24 hours with shaking. Fresh YM broth seeds are then started using a 1% inoculum. After 24 hours incubation at 30� C. with shaking these YM seeds are used to inoculate a one-gallon fermentor containing a seed medium which is the same as the final fermentor medium except that it contains 0.5% K2 HPO4. The inoculum size is 6.7% and the fermentation temperature is 30� C. The air flow rate is one L/M and the agitation is set at 400 RPM. At 25 hours this seed was used to start a 30 L fermentor with an inoculum size of 5%.
C. Final Fermentor Medium
The following medium gives acceptable results in the 30 L fermentor and can be used for larger scale fermentors such as 70 L.
______________________________________Glucose 3.0%K2 HPO4 0.13%Promosoy 0.25%NH4 NO3 0.03%MgSO4.7H2 O 0.05%Fe4.7H2 O 10 ppmAntifoam (Hodag K-21)Tap Water______________________________________
The pH is controlled between 6.5 and 7.5. At 0 hours, the residual carbon source was measured to be 3.08%. At 69 hours, the pH was 6.55 and the beer viscosity was 42,500 cP.
The initial agitation and aeration rates were 300 rpm and 5 L/M, respectively. The eaction rate was increased to 10 L/M at 20 hours and then remained constant through the fermentation. The agitation was increased to 700 RPM (maximum) at 20 hours.
When a low calcium product is desired, the medium above is used with deionized water.
D. Broth Adjustment
During this stage, 0.2% calcium propionate is added to the broth. The fermentation broth is adjusted to a pH of 11-11.5 with 45% KOH, followed by heating at 210� F. for 5 minutes.
E. Recovery
Good fibers are produced under precipitation conditions giving 58-62% spent IPA.
F. Drying
Product is recovered after drying with rotary air dryers.
After drying, the product is milled according to standard milling procedures. Target mesh size varies according to desired product characteristics. For example, larger mesh size material, e.g. 80 mesh, is preferred for transport of the material using conventional dry material handling systems. Smaller mesh size material, e.g. 140 mesh, is preferred for enhanced rapid hydration performance. In all cases, however, the gum produced according to the described procedure, using described fermentation broth pH adjustment and subsequent heating steps, possesses rapid hydration characteristics as compared to conventionally prepared welan gum produced according to the procedure described in U.S. Pat. No. 4,342,866.
This product was demonstrated to have hydration and solution properties similar to the sample described in the Example 1.
A rapidly hydrating welan gum is prepared according to the procedure of Example 1 wherein during recovery the pH is controlled at 11 and the temperature is maintained at 170� F. for 5 minutes. The dried gum is milled to 140 mesh size.
A rapidly hydrating welan gum is prepared according to the procedure of Example 1 wherein during recovery the pH is controlled at 11 and the temperature is maintained at 210� F. for 5 minutes. The dried gum is milled to 80 mesh size.
A rapidly hydrating welan gum is prepared according to the procedure of Example 1 wherein during recovery the pH is controlled at 11, the temperature is maintained at 210� F. for 5 minutes, and the broth is sheared through a high shear mixer. The dried gum is milled to 80 mesh size.
a rapidly hydrating welan gum is prepared according to the procedure of Example 1 wherein during recovery the pH is controlled at 11.5 and the temperature is maintained at 170� F. The dried gum is milled to 80 mesh size.
A rapidly hydrating welan gum is prepared according to the procedure of Example 1 wherein during recovery the pH is controlled at pH 11.5, the temperature is maintained at 170� F. and the broth is sheared through a high shear mixer. The dried gum is milled to 80 mesh size.
A rapidly hydrating welan gum is prepared according to the procedure of Example 1 wherein during recovery the pH is controlled at 11 and the temperature is maintained at 211�-215� F. The dried gum is milled to 80 mesh size.
Control welan gum is prepared according to the procedure described in Example 1 with the exception that Step D ("Adjustment") is not performed. The procedure includes step C, followed by heating of the broth to 170� F. for 5 minutes, followed by Step E. Three different batches were prepared (13a, 13b and 13c) and each was milled to 40 mesh size and 150 mesh size.
In order to determine hydration characteristics for rapidly hydrating welan gums produced in accordance with the procedure of the invention, the gums were combined with polyethylene glycol and viscosity measurements were made using a Solution Rate Tester.
The tester can measure the hydration rate of polymer solutions by monitoring the torque on a beaker as it is being stirred at a constant speed. As the gum dissolves and the viscosity increases, beaker torque increases. While factors such as turbulence, non-laminar flow, pseudoplasticity, etc. prevent a direct correlation of torque reading and viscosity, plotting torque against time provides a good indication of viscosity development.
Material is tested at 0.5 wt. % in synthetic tap water for 15 minutes at 600 rpm in a Solution Rate Tester. Samples are added in a polyethylene glycol slurry at a ratio of 3 parts glycol to 1 part gum.
Viscosities are measured after 15 minutes of mixing plus 1 hour rest and after shearing for 1 minute in a blender and 18 hours rest. Ideally, the blended solution should be de-aerated before the viscosity is measured, or a defoamer added to the gum solution before blending. 3 grams of glycol and 1 gram of dry gum are weighed into a 10 ml beaker. The slurry is mixed with a small spatula by hand for about 30 seconds. 2.6 grams of the slurry are then placed into a 5 cc syringe, and the syringe tip cut off to prevent shearing. 127.4 grams of synthetic tap water is weighed into the stainless steel beaker used with the Solution Rate Tester.
______________________________________ BrookfieldSample LVT, cP, 3 rpm % Final Minutes to reach(Example #) 1 hour blended Viscosity 90% torque______________________________________ 7 14,600 15,800 92.4 1.83 8 6,900 6,650 100 2.16 9 7,200 6,900 100 2.3010 7,800 8,000 97.5 9.0511 9,300 9,700 95.9 7.8312 7,250 6,100 100 2.3313a (40 mesh) 10,000 12,000 83.3 33.28(150 mesh) 9,200 9,600 95.8 11.7913b (40 mesh) 10,000 13,400 74.6 18.64(150 mesh) 8,400 100 10.5813c (40 mesh) 8,550 14,000 62.9 23.48(150 mesh) 8,400 13,000 64.6 10.76______________________________________
In addition to the uses described above, uses for the rapidly hydrating gum of the present invention include use as an antiwashout admixture for the construction and repair of structures underwater, production of a fluid, non-bleeding grout for post-tensioned structures, improvement of bond between reinforcing steel and concrete, shotcrete, lightweight concrete, air entranced concrete, oilfield cements, fiber containing concrete, extruded concrete products, precast products as well as general use in grouts. Concentrations of the gum required for adequate functionality vary with the application.
|Cited Patent
|Filing date
|Publication date
|Jul 5, 1943
|Oct 24, 1950
|Nat Lead Co
|Well cementing composition
|Jan 25, 1967
|Mar 11, 1969
|Martin Marietta Corp
|Hydraulic cement mix containing saccharide polymers
|Jan 26, 1977
|Feb 14, 1978
|Kao Soap Co., Ltd.
|Hydraulic cement composition
|Dec 29, 1976
|Jun 20, 1978
|Texaco Inc.
|Method of and composition for cementing oil wells
|Apr 23, 1981
|Aug 3, 1982
|Merck & Co., Inc.
|Heteropolysaccharide S-130
|Jun 14, 1989
|Oct 16, 1990
|Merck & Co., Inc.
|Welan gum in cement compositions
|Title not available
|Citing Patent
|Filing date
|Publication date
|Apr 7, 1994
|Oct 3, 1995
|Piljac; Goran
|Pharmaceutical preparation based on rhamnolipid
|Apr 3, 1995
|Aug 6, 1996
|Breslauer; Charles S.
|Ultra-light high moisture retention tile mortar
|Aug 21, 1995
|Feb 17, 1998
|Breslauer; Charles S.
|Ultra-light high moisture retention title mortar
|Jan 31, 1996
|May 12, 1998
|Cortec Corporation
|Corrosion inhibitor for reducing corrosion in metallic concrete reinforcements
|Apr 16, 1998
|Aug 22, 2000
|Pharmacia Corporation
|Stable suspension of hydrocolloids and superplasticizer
|Sep 4, 1997
|Aug 29, 2000
|Pharmacia Corporation
|Methods for improved rheological control in cementitious systems
|May 31, 1996
|Sep 12, 2000
|Pharmacia Corporation
|Stable suspension of hydrocolloids
|Oct 20, 2000
|Nov 26, 2002
|Ashland Inc.
|Asphalt release agent
|Nov 20, 2012
|Philip Morris Usa Inc.
|Oral tobacco product having a hydrated membrane coating and a high surface area
|Dec 18, 2009
|Jan 1, 2013
|Schlumberger Technology Corporation
|Delivery of nanodispersions below ground
|Feb 6, 2009
|Jun 25, 2013
|Philip Morris Usa Inc.
|Pre-portioned moist product and method of making
|May 28, 2010
|Sep 24, 2013
|Philip Morris Usa Inc.
|Oral moist smokeless tobacco products with net-structured gel coating and methods of making
|May 24, 2013
|Jun 10, 2014
|Philip Morris Usa Inc.
|Pre-portioned moist product and method of making
|Oct 31, 2012
|Oct 28, 2014
|Philip Morris Usa Inc.
|Oral tobacco product having a hydrated membrane coating and a high surface area
|Nov 13, 2007
|May 19, 2015
|Philip Morris Usa Inc.
|Moist tobacco product and method of making
|Jun 10, 2014
|Jul 7, 2015
|Philip Morris Usa Inc.
|Pre-portioned moist product and method of making
|Aug 16, 2012
|May 24, 2016
|Halliburton Energy Services, Inc.
|Geopolymer cement compositions and methods of use
|Nov 13, 2007
|Aug 28, 2008
|Philip Morris Usa Inc.
|Moist tobacco product and method of making
|Feb 6, 2009
|Dec 10, 2009
|Philip Morris Usa Inc.
|Pre-portioned moist product and method of making
|Apr 14, 2011
|Philip Morris Usa Inc.
|Moist smokeless tobacco product with textured coating
|May 28, 2010
|May 5, 2011
|Philip Morris Usa Inc.
|Oral moist smokeless tobacco products with net-structured gel coating and methods of making
|Jun 23, 2011
|Schlumberger Technology Corporation
|Delivery of nanodispersions below ground
|Jan 22, 2007
|Jul 26, 2007
|Cognis Ip Management Gmbh
|Compounds and methods for treating fly ash
|Jan 22, 2007
|Feb 12, 2009
|Cognis Ip Man Gmbh
|Compounds and methods for treating fly ash
|U.S. Classification
|536/114, 106/729, 536/119, 536/123, 536/4.1
|International Classification
|Cooperative Classification
|European Classification
|Nov 16, 1992
Owner name: MERCK & CO., INC., NEW JERSEY
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|Mar 20, 1995
Owner name: MONSANTO COMPANY, MISSOURI
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Our pool had been empty for about 30 years when we bought the home. It was an old concrete pool with some cracks and peeling paint. Genie Pool restored the pool and has maintained it for the last 5 years beautifully. I highly recommend them for any pool need!!
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let us complete that job for you in 1 Day, and save a couple gallons of water in the process.
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Updated: 6/11/2015

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Jack Moore FanGraphs Chat – 9/20/11
Print This Post
Jack Moore's work can be seen at VICE Sports and anywhere else you're willing to pay him to write. Buy his e-book.
10 PLAYER keeper league H2H: please tell me who to keep for dynasty league (in a vacuum, position for hitters doesnt matter, just pick best hitters overall):
Hitters: Joe Mauer, Eric Hosmer, Dustin Ackley, Jeter, Brett Lawrie, Jason Heyward, Chris Young (OF), Bryce Harper, Mike Trout, Brandon Belt, Dominic Brown, Jesus Montero, Moustakas….
Pitchers: King Felix, Jared Weaver, Matt Moore, Julio Teheran….


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I've been taking 50mg of Atenolol twice daily for 9 months and it hasn't brought my BP down as much as my doctor wants it too. Now she has added 20mg Lisinopril once a day. Can I take the 2 together without
side effects?
Can I take Atenolol with Lisinopril?
- Posted:
- 1 Mar 2010 by lori91761
- Topics:
- high blood pressure, atenolol, lisinopril
I've been taking 50mg of Atenolol twice daily for 9 months and it hasn't brought my BP down as much as my doctor wants it too. Now she has added 20mg Lisinopril once a day. Can I take the 2 together without
Responses (1)
2 Mar 2010
people responds to high blood pressure medications differently. Since the added med lisinopril comes from your doctor, it is wise to take it. Observe the med for at least 2 to 3 weeks since that's the time where side effects are mostly observe. Buy med in small quantity to avoid waste if the doctor prescribed another one. I'm also on my third med for bp since the 2 have side effects. I'm still waiting for 2 more weeks to see if this med will work best for me. Hope this will help.
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1 answer • 20 May 2011
My mom(84) is on Lisinopril and Atenolol. Why should she be on 2 hypertension meds?
if she has never had a heart attack? She just has high blood pressure.
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U.S., Canada To Face Off For The Gold
The United States and Canada will face a rematch in the men's hockey competition in Vancouver on Sunday.
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We want everyone in our cities to experience respect, justice and care.
We recognize that exclusion, isolation and destructive dependencies are some of the greatest challenges in our communities.
We acknowledge and honor the innate resourcefulness that is found in everyone, and believe in strengthening and empowering these resources.
Everyone are vital to our communities and we wish to include and invite people to participate in them.


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J brand jeans
Kristin Cavallari in J Brand
Kristin Cavallari was seen out running errands with her boyfriend, Jay Cutler. Maybe she was cheering him up after The Bear's loss this past week. I think they're definitely an interesting couple – he's nothing like Justin Bobby. Either way, Kristin seems happy, she recently told People magazine how in love with Jay she was!
Kristin looks slim these days, especially next to Jay! She wore her J Brand skinny jeans again. She's been wearing a lot of J Brand recently. While I'm not typically a fan of lighter washes, I think these fit her laid-back style perfectly. You can buy J Brand jeans at JBrandjeans.com.
Anne Heche in J Brand
Anne Heche wore a pair of J Brand "Major" high-rise Japanese Twill pants in Black while attending the Cedar Rapids premiere at the 2011 Sundance Film Festival. Anne is such a cute little svelte thing isn't she?!
I think I know Anne the best from her role in the movie Volcano, though she started her career with playing the good and evil twins Vicky and Marley on the NBC soap opera Another World. Oh and I totally forgot about her dating Ellen DeGeneres… You can buy these jeans here.
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Emma Roberts in J Brand
Emma Roberts wore a pair of J Brand "Maria" high rise denim leggings in Hewson while attending the Homework premiere at the 2011 Sundance Film Festival. I love her black on black look with her sweater to mix it up a bit. Emma really has that pretty next door neighbor appeal, doesn't she?
In other news, Emma will appear on Extreme Makeover Home Edition this coming Sunday (January 30th) be sure to check her out! Emma also will be in Scream 4; no offense to anyone but I stopped watching Scream after the first one, do any of you go to those movies? Tell me what I'm missing… You can buy these jeans here.
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Top Stories
Breakthrough solar cell captures CO2 and sunlight, produces burnable fuel
July 28, 2016 03:01 PM - University of Illinois at Chicago via EurekAlert!
Researchers at the University of Illinois at Chicago have engineered a potentially game-changing solar cell that cheaply and efficiently converts atmospheric carbon dioxide directly into usable hydrocarbon fuel, using only sunlight for energy.
The finding is reported in the July 29 issue ofScience and was funded by the National Science Foundation and the U.S. Department of Energy. A provisional patent application has been filed.
Unlike conventional solar cells, which convert sunlight into electricity that must be stored in heavy batteries, the new device essentially does the work of plants, converting atmospheric carbon dioxide into fuel, solving two crucial problems at once. A solar farm of such "artificial leaves" could remove significant amounts of carbon from the atmosphere and produce energy-dense fuel efficiently.


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Metabolism at a Glance / Edition 3by J. G. Salway
View All Available Formats & Editions
Pub. Date: 01/15/2004
Publisher: Wiley
Metabolism at a Glance is a complete review course of metabolism in health and disease and offers a unique approach to the study of this difficult discipline.
Metabolism is a complicated subject involving complex molecules and interrelated pathways. These metabolic pathways are usually taught separately with the result that the student develops a detailed/i>
Metabolism at a Glance is a complete review course of metabolism in health and disease and offers a unique approach to the study of this difficult discipline.
Metabolism is a complicated subject involving complex molecules and interrelated pathways. These metabolic pathways are usually taught separately with the result that the student develops a detailed but compartmentalised approach to metabolism and frequently fails to see the overall picture and its physiological significance.
Using the at a Glance format, the book takes the student through a complete course in intermediary metabolism in an integrated manner. The same chart is repeated throughout the book with the individual pathway under study highlighted.
The book is an ideal text for introductory biochemistry courses and has established itself as an enormously popular book amongst lecturers and students alike. This third edition is fully updated and includes five new chapters to mirror those topics currently taught at undergraduate level:
1. Metabolic Channelling
2. Glucose homeostasis and Reye's Disease
3. Pentose phosphate pathway and the prodcution of NADPH
4. Tryptophan metabolism in health and disease
5. Tyrosine metabolism in health and disease
Product Details
- 9781405107167
- Publisher:
- Wiley
- Publication date:
- 01/15/2004
- Series:
- At a Glance Series
- Edition description:
- Pages:
- 128
- Sales rank:
- 385,840
- Product dimensions:
- 11.40(w) x 13.60(h) x 0.40(d)
Table of Contents
Foreword 8
Preface 9
1 Introduction to metabolic pathways 10
2 Biosynthesis of ATP I: ATP, the molecule that powers metabolism 12
3 Biosynthesis of ATP II: mitochondrial respiratory cheln 14
4 The oxidation of cytosolic NADH: the malate/aspartate shuttle and the glycerol phosphate shuttle 16
5 Metabolism of glucose to provide energy 18
6 Metabolism of one molecule of glucose yields 31 (or should it be 38?) molecules of ATP 20
7 Metabolism of glucose to glycogen 22
8 Anaerobic metabolism of glucose and glycogen to yield energy as ATP 24
9 2,3-Blsphosphoglycerate (2,3-BPG) and the red blood cell 26
10 Metabolism of glucose to fat (trlacylglycerol) 28
11 Metabolism of glucose to fatty acids and trlacylglycerol 30
12 The pentose phosphate pathway: the production of NADPH and reduced glutathione 32
13 Tha pyruvate/malate cycle and the production of NADPH 34
14 Mammals cannot synthesize glucose from fatty acids 36
15 Metabolism of trlacylglycerol to provide energy as ATP 38
16 Glycogen metabolism I 40
17 Glycogen metabolism II 42
18 Glycogen metabolism III: regulation of glycogen breakdown 44
19 Glycogen metabolism IV: regulation of glycogen synthesis 46
20 Regulation of glycolysis: overview exemplified by glycolysis In cardiac muscle 48
21 Glycolysis and the pentose phosphate pathway collaborate In liver to make fat 50
22 Glycolysis In skeletal muscle: biochemistry of sport and exercise 52
23 Regulation of gluconeogenesis 54
24 Regulation of Krebs cycle 56
25 Regulation of fatty acid oxidation: mobilization of fatty acids from storage In adipose tissue 56
26 Fatty acid oxidation and the carnitine shuttle 60
27 The ketone bodies 62
28 Ketone body utilization 64
28 II-Oxidation of unsaturated fatty acids 66
30 Peroxisomal II-oxidation 66
31 Elongation and desaturation of fatty acids 70
32 Cholesterol, bile acids and the steroid hormones 72
33 The omlthlne cycle for the production of urea: 'the urea cycle' 74
34 Metabolic chennelllng: enzymes are organized to enable chennelling of metabolic Intermediate. 76
35 Biosynthesis of the non-essential amino acids 78
36 Catabolism of amino acids I 80
37 Catabolism of amino acids II 82
38 Metabolism of amino acids to glucose in starvatlon and during the period Immediately after refeeding 84
39 Metabolism of protein to fat 86
40 Disorders of amino acid metabolism 88
41 Phenylalanine and tyresine metabolism 90
42 Tryptophan metabolism: the biosynthesis of NAD+, serotonin and melatonin 92
43 Amino acid metabolism, folate metabolism and the 'i-carbon pool' I: purine biosynthesis 94
44 Amino acid metabolism, folate metabolism and the 'i-carbon pool' II: pyrimidine biosynthesis 96
45 Porphyrin metabolism, haem and the bile pigments 98
46 Metabolism of ethanol 100
47 Sorbitol, galactitol, glucuronate and xylltol 102
48 Fructose metabolism 104
49 Metabolic pathways in fasting liver and their disorder in Reye's syndrome 106
50 Diabetes I: insulin-stimulated glucose uptake into cells and glycogen synthesis - signal transduction 1 08
51 Diabetes II: metabolic changes in Type 1 diabetes 110
52 Diabetes III: Type 1 diabetes, Type 2 diabetes, MODY and pancreatic poeell metabolism 112
53 Diabetes IV: Type 2 diabetes and insulin resistance in muscle 114
54 Diabetes V: Type 2 diabetes and insulin resistance in adipose tissue 116
55 Diabetes VI: Type 2 diabetes and insulin resistance in liver 118
Index 121
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California Interscholastic Federation State Football Bowl Games
Saturday's Games
CIF Open Division Bowl Game
De La Salle (Concord) 28, Crenshaw (Los Angeles) 14: Terron Williams-Ward scored twice in the second half on runs of 26 and 4 yards as the Spartans broke a 14-14 tie at halftime and won their second CIF state bowl game title in three years.
Crenshaw took a 14-0 lead in the first quarter on touchdowns run by super junior DeAnthony Thomas (43, 16 yards), but did not score again as the De La Salle defense adjusted. The Crenshaw offense also was hampered when Thomas was injured while playing defense in the second quarter and did not carry the ball again. W
illiams-Ward ended with 165 yards on 22 carries and set a new school record for rushing yards in a season with 2,037.
De La Salle completed a bounceback from early in the season as well since the team suffered losses to national powers Don Bosco Prep (Ramsey, N.J.) and Lakeland (Fla.). Don Bosco Prep moved to No. 1 in the ESPN RISE FAB 50 last week while the Lakeland loss was by just one point.
CIF Division II Bowl Game
Servite (Anaheim) 33, Rocklin 30: Servite (14-1) had the upper hand with a 30-10 lead in the third quarter, but Rocklin (14-1) rallied for 20 straight points to force a 30-30 tie with 8:51 remaining before the Friars converted a game-winning field goal with no time left.
With the game tied at 30, Servite appeared to be in position to take the lead with 2:35 left following a first down inside the Rocklin 5-yard line. But Rocklin's Sean Moore recovered a fumble. Just 45 seconds later, Servite's Jordan Jones struck back for the Friars by intercepting a pass at the 27-yard line. This put Servite in position to run down the clock for a game-winning field goal attempt. Nicholas Echeverry converted a 23-yard field goal to win the game. It was his fourth field goal of the contest.
Servites's Cody Fajardo completed 12 of 21 passes for 182 yards and one touchdown. He also rushed 19 times for 91 yards and another score. Rocklin's Jackson Cummings had 29 carries for 167 yards and two TDs while quarterback Tiger Sorenson passed for 241 yards and two TDs but had two interceptions.
Servite, which was No. 29 in this week's ESPN RISE FAB 50, completed a run in which it defeated teams that were 12-0, 13-0 and 14-0.
CIF Division III Bowl Game
Serra (Gardena) 24, Marin Catholic (Kentfield) 20: One week after the Cavaliers (15-0) upset FAB 50-ranked Oaks Christian (Westlake Village, Calif.) to win a CIF Southern Section title, they had to fight hard to turn back an upset bid to win a state bowl title. Serra, which moved up to No. 30 in this week's FAB 50, were led by All-American candidate Robert Woods, who scored on touchdown catches of 67 and 30 yards. Marin Catholic (13-2), which was considered at least a three-TD underdog by most prep prognosticators, received a performance from 5-foot-8 junior backup quarterback Chris Tewhill that was almost the stuff of legend. Tewhill had to enter the game due to an injury to regular starter Nate Kristoff. He set one CIF bowl game record (regardless of division) by throwing an 82-yard touchdown pass to Tyler Scott in the second quarter. Playing defense, he later set another CIF bowl game record by picking up a bouncing fumble and scoring on a 52-yard fumble return.
Friday's Games
CIF Division I Bowl Game
Oceanside 24, Bellarmine (San Jose) 19: The Pirates became the second California team to win two CIF bowl games by overcoming a 10-point first-half deficit and putting together a 99-yard drive on the go-ahead touchdown. Oceanside's Rene Siluano scored the game-winner by taking a screen pass 55 yards for a fourth-quarter touchdown. From his safety position, Siluano led a stingy Pirates defense that held Bellarmine (11-2-1) to a net 100 yards rushing as Oceanside became the first team ever to win CIF bowl games in two different divisions, winning in Div. II in 2007. The No. 14 ranked team in the latest FAB 50, Oceanside (14-0) will enter the 2010 season riding a 39-game unbeaten streak (38-0-1), the longest current streak of its kind in the Golden State.
Did you know? That Oceanside is the alma mater of New England Patriots linebacker and likely Hall of Famer Junior Seau.
Small Schools
Modesto Christian 44, Francis Parker (San Diego) 40: In a crazy scorefest in which the two teams combined for 982 yards, a fourth-down stop at the 2-yard line with 1:36 left gave the Crusaders their first CIF state football title. Modesto Christian also became the first team in Northern California history to finish 15-0. Three Crusader running backs topped 100 yards of rushing, led by senior Keaton Engel with 11 carries for
163 yards. The other two were Kevin Roya (13-154) and quarterback Isaiah Burse (16-139). Burse also threw for three scores. Engel's 2-yard run with 5:38 left pulled Modesto Christian in front. But Francis Parker had its chance to go in front before being stopped inside the Modesto Christian 2-yard line.
Yale-bound student-athlete Deon Randall capped a record-breaking career for the Lancers with 36 carries for 280 yards and three TDs. He also threw a pair of TD passes.


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Français : Livre:Huysmans - Le Drageoir aux épices
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President and COO, Champion, Inc.
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LSSU Business, Economics, and Legal Studies Distinguished Alumni '07
Former LSSU Board Trustee
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DEFINITION of 'Muhammad Yunus'
A professor of economics that won a Nobel Peace Prize in 2006 for his efforts in developing social and economic improvements through microcredit operations. Most notably, Yunus founded the Grameen Bank, which is known for loaning billions of dollars to the less fortunate all over the world.
BREAKING DOWN 'Muhammad Yunus'
Born in June 28, 1940, in Bangladesh, Yunus completed his BA and MA at Bangladesh's Dhaka University. He would later complete his PhD in economics at the United States' Vanderbilt University in 1969. Yunus would return to Bangladesh to become the head of Chittagong University's Economics department in the early 1970s. But it wouldn't be until 1976, when his academic work in microcredit would lead him towards the beginnings of forming the Grameen bank and his future Nobel Prize.
Nobel Memorial Prize In Economic ...A prestigious award acknowledging outstanding contributions to ...
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Ronald H. CoaseA British economist who won the 1991 Nobel Memorial Prize in ...
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Hard work, determination and a promise to grandma helps Hardy win national title
Brock Hardy and Sam Sasso scramble against each other in the national freestyle final match. Hardy won, 10-9.
Sean Hales
Managing editor
Wrestler Brock Hardy has a deep understanding of a person being present "in spirit" following a run to capture his first national title int eh 138 weight class at the USAW Cadet Freestyle Nationals tournament—perhaps the toughest tournament in the country—in Fargo, N.D., last week.
In both his semifinal and final matches at the tournament, Hardy (141-5) had to dig deep, and when he did, he found the influence of his grandmother, Edna Hardy, who has been a constant fixture at Hardy's tournaments over the years, but who now has to watch matches in her iPad from home after being diagnosed with ALS last year. Hardy promised his grandmother—who can now only communicate with nods and by typing with a single finger—he would come home with a "stop sign," the name wrestlers have given the plaque awarded to national champions.
Hardy said he had trained particularly hard prior to the tournament, focusing more intently than he ever had before on the things he knew he needed to reach the top of the podium; lessons he had learned during his run to take two second-place finishes at the same tournament last year.
"I was going not to take second," Hardy said. "I was going to get a national title."
While Hardy's training took him so far, he said it was his grandmother's influence, and the promise he made to her, that pushed him over the top when the summit seemed so far.
In the semifinals of the freestyle tournament, Hardy faced Will Lewan (91-11) from Chicago, the same wrestler who had beat Hardy in the in Greco finals, 6-3, earlier in the tournament.
It might have been easy for Hardy to get wound up heading into the match, to think he had to push himself harder to beat an opponent who had already bested him once. However, Hardy said he was able to call on his promise to his grandmother to settle himself and allow him to "do my thing."
And Hardy's "thing" was absolute domination of Lewan. With just 30 seconds expired in the second period, Hardy had accumulated a 10-2 lead. A strong defensive posture helped Hardy cruise to a 12-5 win.
Hardy's win set a finals match-up against Sam Sasso (96-12) from Nazareth, Penn. It was Sasso who sent Hardy home as the runner-up in last year's freestyle tournament, and who was expected to take home a second national title this year.
Despite dealing with an injured hand, Sasso jumped out to a 6-2 lead early in the match. With just two minutes left Sasso held an 8-6 advantage. Hardy said he again found the influence of his grandmother, and earned two takedowns to take his first lead, 10-8, with just 30 seconds remaining. In a complete defensive posture, Hardy got called for avoiding Sasso in the final seconds, a one-point infraction resulting in a 10-9 score.
"That kid was expected to win," Hardy said. "thinking of my grandma was a calibrating moment and allowed me to be able to get to it."
In addition to that, Hardy was focused on getting a measure of revenge against Sasso, and changed his mindset, he said. Last year, he went in a little timid, and wrestled not to lose, but this year, Hardy said, we wrestled to win.
Hardy is a multiple national championship winner, having won previously at nationals in the Kids division. This is his first Cadet-division national title, and with that, and the second-place finish in Greco, Hardy was named a double All-American.
Perry boy wins national championship with U17 Rampage 99 Black team
On July 17, the Rampage 99 Black U17 boys soccer team based out of Roy, but featuring players from several different areas, competed in and won the National President's Cup tournament in Tulsa, Okla.
Local soccer standout, Hunter Satterthwaite of Perry, has played as the Rampage's left defender for the last three seasons. Satterthwaite will play for the Box Elder High School soccer team in the spring.
Rampage has been striving to qualify for a national tournament for several years and finally made their breakthrough this last spring by qualifying for the West Regional President's Cup, although the qualification wasn't without hurdles.
To qualify for the regional tournament, teams must make it through their individual state tournaments. The champion from each state, plus a few wild card teams, qualify for regionals.
The Rampage thought their dream of making a national tournament was dashed when they came up short in the final of the Utah President's Cup and finished in second place.
But the stars aligned for the team as they got their shot in the regional tournament as one of the wild card teams.
They made the most of it and earned a meaningful 1-0 win in the semifinal game against the same team that had beat them in the Utah championship match.
After a 0-0 first half, Satterthwaite was pushed up from his defensive position for a corner kick and was able to connect on a back-heel shot that gave his team a 1-0 lead and proved to be the only goal of the game.
Following the emotional semifinal win, Rampage went on to win the West Regional championship over a team from California to qualify for the National President's Cup tournament.
The national tournament takes only the champion from each region. In the opening round of group play, all teams play against each other.
During the group stage, Rampage built on their momentum from winning the regional and won all three games to set up a matchup against a team from Florida for the national title.
In the championship match, the Soccer Pit Cobras gave Rampage all they could handle, battling to a 1-1 tie at the end of regulation.
But in the overtime period, Rampage proved to have too much firepower, scoring twice in overtime to seal the win 3-1.
In addition to playing quality soccer, the Rampage team was also awarded the Fair Play Award during the national tournament, an award given to the team which demonstrated the best sportsmanship throughout the tournament and is voted on by both the coaches and referees at the tournament.
Utah was also represented at the national tournament by a younger boys team as the U14 Boys Fire FC, based out of Southern Utah, also qualified to compete. Fire FC finished in fourth place at the national tournament.


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Author has written 30 stories for Prototype, Halo, Feed, Left 4 Dead, Misc. Games, Pokémon, Assassin's Creed, Fallout, Mass Effect, Mythology, Transformers, Misc. Books, and Destiny.
Hallo everybody!!
I'm a HUUUUUUGE fanfiction addict as well as a hardcore gamer. Those two colliding just begs for fanfiction to pop out! Most of my fanfic will be from games but I'll upload non-game stuff as well.
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text: Trick Room has always been thought of as not viable for OU, and I guess in a way that's true but I don't think it's completely obsolete. The main problem I find is not the setting up and the short 5-turn timer, but rather the fact that most users of trick room are psychic-typed. Being weak to pursuit and u-turn especially with a trick room team absolutely sucks. But then again, you can work around most things. The team: Victini @ Flame Plate Trait: Victory Star EVs: 252 Atk / 248 HP / 8 Def Brave Nature IVs: 0 Spd - V-create - Bolt Strike - U-turn - Trick Room As the title suggests, Victini is the MVP of this team. V-create just damages everything, and the speed drop makes Victini even faster in trick room. The fact that I don't have to invest in speed means that I can invest in bulk, which means Victini can actually take a hit. Many times Victini can even come in when trick room isn't set up, force a switch (whether the opponent thinks I'm the revenge killer or simply because of the match-up) and then set up trick room itself. Bolt strike is great for water types that love to switch in. U-turn is used over brick break because both Conkeldurr and Reuniclus have fighting moves, and u-turn is great on the last turn of trick room to safely switch out. Porygon2 @ Eviolite Trait: Trace EVs: 252 HP / 184 Def / 72 SDef Bold Nature IVs: 0 Spd - Trick Room - Thunderbolt - Ice Beam - Recover This thing is a great multipurpose wall and can switch in on a variety of threats. It effectively walls jellicent, heatran, chandelure, and many others, and is also useful for switching into dragonite's outrage thanks to a traced multiscale. Boltbeam with recover as usual, and of course trick room. The fact that this thing walls heatran and chandelure also means that I can safely spam V-create with victini. It also has decent synergy with jellicent, being immune to the ghost type attacks while jellicent deals with the fighting. Jirachi @ Leftovers Trait: Serene Grace EVs: 252 HP / 156 Def / 100 SDef Relaxed Nature IVs: 0 Spd - Trick Room - Ice Punch/Stealth Rock - U-turn - Healing Wish Jirachi can also take outrages, and kill back with ice punch. Trick room and u-turn allow a safer switch-in to one of my sweepers. Healing wish is the main purpose though. That move by itself completely changes the game. After using trick room, I can use healing wish to bring back one of my sweepers and effectively finish the game. That's the main reason I'm using jirachi over bronzong. I'm also using jirachi over cresselia because jirachi's steel typing really helps, and trick room teams really don't need the bug, ghost, and dark weaknesses. Sometimes I feel I should run stealth rock because it definitely helps my sweepers get the OHKO's and 2HKO's that they need, but ice punch is still nice. I'm also considering Wish... but I'm not sure if it's necessary. Jellicent @ Leftovers Trait: Water Absorb EVs: 252 HP / 216 Def / 40 SDef Relaxed Nature IVs: 0 Spd - Scald - Recover - Will-O-Wisp - Trick Room Jellicent is cool. Although its weak to ghost and dark, just like psychic types, it's great that it's not weak the bug. Will-o-wisp is great and lets me more comfortably send out my sweepers. Scald is the main STAB move and of course it can set up trick room as well as recover. Very often this absorbs the water attacks aimed at victini (which of course u-turns into jellicent). Conkeldurr @ Life Orb Trait: Sheer Force EVs: 120 HP / 252 Atk / 136 SDef Brave Nature IVs: 0 Spd - Drain Punch - Ice Punch - ThunderPunch - Mach Punch Conkeldurr is great. Hits crazy hard with life orb and sheer force, while drain punch lets it last quite long. Conkeldurr is also the only form of priority on this team, but the funny thing is I never use it that much. I've never actually had a time when I felt screwed because trick room wasn't set up, probably because my sweepers are just bulky enough to take a hit or two. Conkeldurr also has great coverage which is extremely important for sweepers in trick room because of the 5-turn timer. Reuniclus @ Life Orb Trait: Magic Guard EVs: 192 HP / 64 Def / 252 SAtk Quiet Nature IVs: 0 Spd - Trick Room - Psychic - Shadow Ball - Focus Blast I absolutely love reuniclus' ability. It just feels so satisfying when it takes no damage from toxic and burn, entry hazards, sandstorm and hail, and especially ferrothorn's leech seed. Psychic/Ghost/Fighting gives great neutral coverage, and I can afford to use focus blast because I got conkeldurr to back me up. And of course it has trick room to set up for itself since it also has enough bulk to do so. And that's it for the team, comments are greatly appreciated (:


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. . . And Through Rural Towns; Antiques and Art Add Sparkle to a Bed and Breakfast Excursion
By BESS LIEBENSON
Published: October 10, 1999
TRAVELERS in search of fall foliage in full glory are on the road these days. And so my husband and I decided to take a weekend excursion in the northeast corner of the state. Our two-and-a-half-day exploration took us from Canterbury to Brooklyn to Pomfret and Putnam. No malls, no billboards; along the way we were lulled into another age by old barns, houses and churches as well as vistas of pastures, orchards and graveyards by farmers' old stone walls. Some of the houses have been converted into bed and breakfasts, restaurants and galleries. ''With technology,'' said Sandy Spackman, the owner of Chickadee Cottage, the bed and breakfast we chose in Pomfret, ''people can live in a rural environment, in a bucolic historic setting, work out of their homes and maintain their professions.''
Chickadee Cottage offered sophisticated warmth, its living room a haven of cabbage roses on upholstery, furniture floating in the middle of the room. Beyond, french doors led to a gray weathered deck blazing with pots of flowers. On a gentle hill, an old railroad path offered miles of walking trails. Our antique- and plant-laden upstairs bedroom featured a dhurrie rug with squares of herbs and birds.
First stop for sustenance was the Calabash Coffee Company and Cafe on Route 169 in Brooklyn. The circa-1762 house has been a boys' school, a button factory and a candy store. ''On a rainy day, buttons come up from the ground,'' said Dave Helmin, owner and chief coffee roaster, who opened the cafe last year after receiving a $35,000 small business loan. Inside, rooms with assorted tables and chairs house a small artisans' market, gallery and a room with a huge blue enameled coffee roaster as its focal point. (Outdoors is a flagstone patio.) Soup and salad, sandwiches and pastries are on the menu.
We like comparing bed and breakfasts, and were on our way north to visit one of two others, then on to an herbary.
Cobbscroft Bed and Breakfast in Pomfret is home to husband and wife artists who work in a white two-story barn-studio-gift shop where the couple formerly kept horses. Jan McCobb paints furniture, decorative objects and frames in a faux style. Tom McCobb, who teaches in Maine during the summer, is nationally known for his watercolor sea and landscapes.
The 200-year-old adjacent house, with a welcoming odd-shaped porch, has rooms with antiques and wide-planked floors. Our favorite bedroom, one of four, was the stenciled room with hand-painted king-size headboard and garlands of stenciled flowers framing the walls and mirrors.
A little farther north on Route 169 in Pomfret is Martha's Herbary. Behind a fence of birdhouses we found a cemetery for cats and dogs dating to the 1800's, and a bevy of demonstration gardens -- raised cedar beds of culinary herbs, a sunken garden with ponds and statuary, and a garden centered around an ornate birdbath. ''We're harvesting and making teas for the winter,'' said Martha Paul, who conducts cooking and craft classes in an updated theater-like kitchen in her circa-1780 house.
Dinner was taken next door at the Vanilla Bean Cafe, a family enterprise. The cafe has a casual, friendly air with dining inside and out under umbrella tables or picnic tables under the trees. Food is ordered inside from a wide blackboard selection, fresh-caught fish their specialty with moderate prices.
Our next day began over breakfast on the porch of Friendship Valley Bed and Breakfast in Brooklyn, where our hosts were Beverly and Rusty Yates. The buttercup-yellow house, on the National Register of Historic Places, offers five stylishly decorated bedrooms. The 12-acre property -- surrounded by picket fences and stone walls -- include a cow path, now a tree-lined lane in Wallace Nutting's book, ''Connecticut Beautiful.'' Prudence Crandall, who stayed there when the town turned against her for opening a school for young black women in 1833, gave the inn its name.
In Canterbury, at the Prudence Crandall Museum, we learned more about the educator. In the 19th century, when a young black woman enrolled at the school, white parents withdrew their children and so the school became one solely for young black women. Prudence Crandall was arrested and suffered three trials before the case was finally dismissed. In 1969 the state bought the building, replicating period rooms to the time of the 19th-century academy, as well as adding exhibitions.
Going north again to Brooklyn we passed apple orchards, Christmas tree farms and graveyards, including that of Old Trinity Church, circa 1771. In Brooklyn we found the New England Center for Contemporary Art or Necca, as it is known. Works of art filled three floors of the red barn. There is a cottage for visiting artists, and a sculpture garden on the former farm. The museum was founded when its spirited now-86-year-old director, Henry Riseman, retired from farming in 1975 and sold his Tiffany glass collection to finance the museum. ''Working is a method of keeping alive,'' said Mr. Riseman. ''You have to get up every day.''


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Read about this in review of best wings in Myrtle Beach. The wing combo appetizers are a great idea! Really enjoyed the house and hot sauces. Wings were good sized and cooked just right. Friendly staff with good service. The staff even brought us an umbrella to get to our car in the pouring rain. A great find!!
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#8845303, By Ka-blamo The Tennis Thread (Wimbleton!)
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The best Pokémon in Pokémon Go How does Charizard rank against Dragonite and Lapras?
Best tips, tricks and cheats for Pokémon Go What you didn't know about catching 'em all.
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