Aqueous crystallization

Figure 16. Surface grafting of polypropylene film strips after 10 sec. irradiation measured as light absorption after dipping in aqueous crystal violet solution. The presoaking solutions contain 0.2 M benzophenone (all) and 1.3 M acrylamide (1), 0.8 M (2),...

Two methods are employed industrially to produce crystalline fructose, aqueous crystallization and alcoholic crystallization. Yields of fructose crystallized from water syrups are only of the order of 50%, due to the very high water solubility of the sugar, while the high viscosity of the concentrated solution results in long crystallization times, typically 50 hours or more (2). The second process requires the addition of lower alcohols (eg. ethanol) to a concentrated fructose syrup, generally 90% total solids or more, at temperatures of 50 C to 80""c and then cooling to cause crystallization. Fructose yields are from 70 to 80% and the total time involved is 8 to 12 hours (3). However, large quantities of... 

The third approach to solving this problem (Farber, 1999) involves the preparation of an enzyme-intermediate complex at high substrate concentration for X-ray data collection. Under such a condition active sites in the crystal lattice will be filled with intermediates. Using a combination of flow cell experiments and equilibrium experiments, it is possible to obtain the structure of important intermediates in an enzyme reaction (Bolduc et al., 1995). It was also discovered that some enzyme crystals can be transformed from their aqueous crystallization buffer to nonaqueous solvents without cross-linking the crystals before the transfer (Yennawar et. al., 1995). It is then possible to regulate the water concentration in the active site. The structure of the first tetrahedral intermediate, tetrapeptide -Pro-Gly-Ala-Tyr- in the y-chymotrypsin active site obtained by this method is shown in Fig. 1.1. 

Kovacs AF, Obitz P, Wagner M. Monocomponent chemoembolization m oral and oropharyngeal cancer usmg an aqueous crystal suspension of cisplatin. Br J Cancer 2002 86(2) 196-202. 

Aqueous crystal violet, 0.25% (g 100 mH) (prefiltered through Whatman No. 1 paper)... 

After removal of medium, rinse 96-well plates with 100 pi welL of PBS and stain with 100 pi of 0.25% (g 100 mL ) aqueous crystal violet for 10 min. 

One notable difference between crystals of small molecules and macromolecular crystals is the very large solvent content of the latter. Protein crystals typically contain at least 30% and up to 80% (v/v) solvent (in fact, aqueous crystallization buffer). Only a fraction of the protein... 

One issue with the use of sodium hydride as a reagent in pilot and commercial operations is the storage and handling requirements for this material. Sodium hydride is typically obtained commercially as a 60% amalgam in mineral oil to stabilize the reagent. In the nevirapine process, the mineral oil tends to agglomerate with the product upon precipitation from the reaction mixture. An intermediate purification step was developed through use of DMF as a crystallization medium. The crude product was dissolved in hot DMF followed by charcoal treatment to absorb the residual mineral oil associated with the product. The charcoal was then removed by filtration followed by evaporative crystallization of the product. A final aqueous crystallization was carried out to remove residual quantities of DMF from the product by acidification with hydrochloric acid followed by treatment with caustic to precipitate the product. 

The sodium salt of this Wells-Dawson-derived sandwich polyoxoanion is a yellow crystalline solid that is soluble in water. It is characterized in solution by P NMR (9 mM solution in H2O, D2O in a capillary insert) one resonance for the distal P atoms at —11.1 ppm (Aj/]/2 = 70 Hz). In the solid state the compound always contains NaCl as it must be crystallized from aqueous NaCl solution. If NaBr is substituted for NaCl in the aqueous crystallization process, crystals of the compound still form but now contain NaBr in place of NaCl. This sandwich complex is characterized in the solid state by IR (2% KBr pellet, 1300-400 cm ) 1091(s), 1017(w), 951(s,sh), 917(m), 826(s), 757(s), 695(s), 630(m,sh), 526(w). The crystal data for Nai2[Fe 4(H20)2(P2Wi5056)2] -58H20... 

Cobalt chloride, C0CI2. Obtained as red crystals of CoCl2 6H20 from aqueous solution, CoCU HiO and C0CI2 are blue as is the (CoCU) " ion. No higher chloride is known although cobalt-haloammines, e.g. (Co(NH3)5C1) are stable. 

Colourless crystals m.p. I25°C, soluble in water and alcohol. In aqueous solution forms equilibrium with its lactones. Gluconic acid is made by the oxidation of glucose by halogens, by electrolysis, by various moulds or by bacteria of the Acetobacter groups. 

CJH4O5, H02CCH(0H)C02H. Colourless crystals with IH O lost at 60 C. M.p. IhO C (decomp.). Prepared by heating dinitrotartaric acid in aqueous alcohol, taurine, aminoethylsulpbonic acid, C2H7NO3S, NHj CHj CH SOjH. Crystallizes in columns, decomposing at 317 C. In combination with cholic acid it forms one of the bile acids. It is formed in the liver from cysteine. 

Horn R G, Clarke D R and Clarkson M T 1988 Direct measurement of surface forces between sapphire crystals in aqueous solutions J. Mater. Res. 3 413-6... 

Experimentally, tire hard-sphere phase transition was observed using non-aqueous polymer lattices [79, 80]. Samples are prepared, brought into the fluid state by tumbling and tlien left to stand. Depending on particle size and concentration, colloidal crystals tlien fonn on a time scale from minutes to days. Experimentally, tliere is always some uncertainty in the actual volume fraction. Often tire concentrations are tlierefore rescaled so freezing occurs at ( )p = 0.49. The widtli of tire coexistence region agrees well witli simulations [Jd, 80]. 

Landau E M, Rummel G, Cowan-Jacob S W and Rosenbusch J P 1997 Crystallization of a polar protein and small molecules from the aqueous compartment of lipidic cubic phases J. Phys. Chem. B 101 1935-7... 

Addition of halide ions to aqueous copper(II) solutions can give a variety of halo-complexes for example [CuCl4] (yellow square-planar, but in crystals with large cations becomes a flattened tetrahedron) [CuClj] (red, units linked together in crystals to give tetrahedral or distorted octahedral coordination around each copper). 

Decolorisation by Animal Charcoal. It sometimes hap pens (particularly with aromatic and heterocyclic compounds) that a crude product may contain a coloured impurity, which on recrystallisation dissolves in the boiling solvent, but is then partly occluded by crystals as they form and grow in the cooling solution. Sometimes a very tenacious occlusion may thus occur, and repeated and very wasteful recrystallisation may be necessary to eliminate the impurity. Moreover, the amount of the impurity present may be so small that the melting-point and analytical values of the compound are not sensibly affected, yet the appearance of the sample is ruined. Such impurities can usually be readily removed by boiling the substance in solution with a small quantity of finely powdered animal charcoal for a short time, and then filtering the solution while hot. The animal charcoal adsorbs the coloured impurity, and the filtrate is usually almost free from extraneous colour and deposits therefore pure crystals. This decolorisation by animal charcoal occurs most readily in aqueous solution, but can be performed in almost any organic solvent. Care should be taken not to use an excessive quantity... 

Reactions of Aspirin, (i) Distinction from Salicylic acid. Shake up with water in two clean test-tubes a few crystals of a) salicylic acid, (0) aspirin, a very dilute aqueous solution of each substance being thus obtained. Note that the addition of i drop of ferric chloride solution to (a) gives an immediate purple coloration, due to the free —OH group, whereas (b) gives no coloration if the aspirin is pure. 

Succinamide. NHoCOCH2 CH2CONH2. (Method 2(a)). Add 5 ml. (5 8 g.) of dimethyl succinate to a mixture of 50 ml. of water and 25 ml. of concentrated [dy o-88o) aqueous ammonia solution in a 150 ml. conical flask. Cork the flask and shake the contents the dimethyl succinate rapidly dissolves to give a clear solution. Allow the solution to stand after about i hour the succinamide starts to crystallise, and then continues to separate for some time. Next day, filter off the succinamide at the pump, wash with cold water, and drain. Recrystallise from water, from which the succinamide separates as colourless crystals the latter soften at 240° and melt at 254 -255° with... 

Place I g. of benzamide and 15 ml. of 10% aqueous sodium hydroxide solution in a 100 ml. conical flask fitted with a reflux water-condenser, and boil the mixture gently for 30 minutes, during which period ammonia is freely evolved. Now cool the solution in ice-water, and add concentrated hydrochloric acid until the mixture is strongly acid. Benzoic acid immediately separates. Allow the mixture to stand in the ice-water for a few minutes, and then filter off the benzoic add at the pump, wash with cold water, and drain. Recrystallise from hot water. The benzoic acid is obtained as colourless crystals, m.p. 121°, almost insoluble in cold water yield, o 8 g. (almost theoretical). Confirm the identity of the benzoic acid by the tests given on p. 347. 

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