Induced crystallization

Analysis of the lanthanide-induced crystalline arrays by negative staining (Fig. 5) or freeze-fracture electron microscopy reveals obliquely oriented rows of particles, corresponding to individual Ca -ATPase molecules [119]. The unit cell dimensions for the gadolinium-induced Ca -ATPase crystals are a = 6. l A, b = 54.4 A and y = 111°. Similar cell constants were obtained for the crystals induced by lanthanum, praseodymium and calcium. The unit cell dimensions of the Ei crystals are consistent with a single Ca -ATPase monomer per unit cell. The space group of the Eptype crystals is PI [119], while that of the E2 crystals is P2 [88,90]. 

Fig. 5. Image and optical diffraction pattern of praseodymium-induced crystals, (A). Crystallization was induced with 8 PrCU. Doublet tracks so prominent in vanadate-induced crystals are not evident in crystals induced with lanthanides. This results in an approximate halving of the A-axis of the unit cell. Magnification x 222000. (B) The image of the superimposed top and bottom lattices of the flattened cylinder give rise to two separate diffraction patterns. (C) Projection map of praseodymium-induced crystals. Map scale 0.55 mm per A. From Dux et al. [119].

Under all ordinary circumstances the average lengths of terminal chains and of internal chains will be the same, or nearly so hence represents the weight fraction of the structure which is active in deformation. For certain applications, as for example to crystallization induced by stretching, 8a is an appropriate measure of the effective portion of the... 

The technique of purification based on seeded crystallization of the desired isomer and simultaneous racemisation of the undesired isomer, termed crystallization induced asymmetric transformation , has been covered by Davey (1994) with the example of a chiral pesticide, paclobutrazol (P). 

AOSD, adult onset Still disease AS, ankylosing spondylitis CA, crystal-induced arthritis ERA, enthesitis-related arthritis JA, juvenile arthritis PA, psoriatic arthritis RA, rheumatoid arthritis SE, synovium explants SLE, systemic lupus erythematosus SPCIA, solid phase 2 site chemiluminescent immunometric assay RP, relapsing polychondritis. 

Yoshioka R (2007) Racemization, Optical Resolution and Crystallization-Induced Asymmetric Transformation of Amino Acids and Pharmaceutical Intermediates. 269 83-132 You C-C, Dobrawa R, Saha-Moller CR, Wiirthner F (2005) Metallosupramolecular Dye Assemblies. 258 39-82 Yu J, see Dittrich M (2007) 268 319-347... 

Cavitation bubbles work as nucleation sites of particles. For example, in a supercooled sucrose solution, nucleation of ice crystals induced by cavitation bubbles has been experimentally observed [72], This phenomenon has been called sonocrys-tallization [73]. Although there are some papers on the mechanism of sonocrystal-lization, it has not yet been fully understood [74, 75]. It has been reported that the distribution of crystal size in sonocrystallization is narrower than that without ultrasound [73]. It may be related to the narrower size distribution of sonochemi-cally synthesized particles compared to that without ultrasound [76, 77]. Further studies are required for the mechanism of particle nucleation by ultrasound. 

Figures 11.8-11.10 and Tables 11.8-11.10 explain the sono-photochemical degradation of phenol under sonicated and normal conditions and in the presence of photocatalyst (n-BuO Ti with and without Cu-Dy, Mn-Dy and Co-Dy composites respectively. These Figs. 11.8-11.10 show the percentage degradation of phenol during a period of 2 h through an interval of 30 min under sonicated, photocatalytic, sonophotocatalytic and crystal induced sono-photo-catalytic conditions.

Vedejs, E. and Donde, Y., Stereogenic P-trisubstituted phosphorus by crystallization-induced asymmetric transformation A practical synthesis of phe-nyl(o-anisyl)methylphosphine borane, /. Am. Chem. Soc., 119, 9293, 1997. 

Deoxy-a-D-ribosyl-l-phosphate 20, a key substrate in the preparation of 2 -deoxynucleosides, was stereoselectively prepared by crystallization-induced asymmetric transformation in the presence of an excess of ortho-phosphoric acid and tri( -butyl)amine under strictly anhydrous conditions (Scheme 2).7 Initial Sn2 displacement of Cl in ot-glycosyl chloride 16 by phosphoric acid resulted in a 1 1 a/p anomeric mixture of 17 and 18 due to the rapid anomerisation of the a-chloride in polar solvents. Under acidic conditions, in the presence of an excess of H3P04, an equilibration between the a and p anomers gradually changed in favour of the thermodynamically more stable a-counterpart. By selective crystallization of the mono tri( -butyl)ammonium salt of the a-phosphate from the mixture, the equilibrium could be shifted towards the desired a-D-ribosyl phosphate 18 (oc/p = 98.5 1.5), which was isolated as bis-cyclohexylammonium salt 19 and deprotected to furnish compound 20. 

When p-chlorobenzophenone dichloride reacts with methylamine there results an oil consisting of similar amounts of the syn and anti Schiff base 19. This oil, on standing at room temperature for 2 weeks, transforms to crystals of only the syn isomer. If these crystals are heated above their melting point (125°) for a few minutes, or are dissolved in cyclohexane and allowed to stand at room temperature for 2 weeks, the syn isomer reconverts to a mixture of the two isomers (61a). [This seems to be an example of the so-called second-order or crystallization-induced asymmetric transformations (61b).] A number of systems of this series were known, from previous work, to be dimorphic however, Curtin and Hausser found no case in which it was established that two crystal forms correspond to different isomers (61a). 

Although disordered structure is fairly common in the known protein structures, this is undoubtedly one of the cases in which the process of crystallization induces a bias on the results observed. Since extensive disorder makes crystals much harder to obtain, it seems probable that disordered regions are even more prevalent on the proteins that do not crystallize. 

A. Vega-Gonzalez, P. Marteau and P. Subra-Patemault, Monitoring a crystallization induced by compressed CO2 with Raman spectroscopy, AIChE J., 52, 1308-1317 (2006). 

Selection-coupled analysis/phase segregation. One strategy for simplifying the analytical challenge is to use phase segregation. Three subclasses are possible. In the first of these, a phase transition is part of the selection process. This includes not only the familiar crystallization-induced enantiomeric enrichment discussed above but also the experiments (primarily employed in experiments directed toward the production of novel materials) such as those described by Lehn and coworkers in 2005. In this study, an acylhydrazone library was created from guanosine hydrazide and a mixture of aldehydes (Fig. 1.22) in the presence of metal ions, formation of G-quartet structures led to the production of a gel. 

Iwasawa, N. Takahagi, H. Boronic esters as a system for crystallization-induced dynamic self-assembly equipped with an on-off switch for equilibration. J. Am. Chem. Soc. 2007,129, 7754-7755. 

Angelin, M. Fischer, A. Ramstrom, O. Crystallization-induced secondary selection from a tandem driven dynamic combinatorial resolution process. J. Org. Chem. 2008, 73, 3693-3595. 

Figure 5.21. Possible scenarios for partial coalescence, (a) Crystallization induced by contact between soUd particle and undercooled droplet, (b) Partial coalescence between two semiUquid droplets.

Asymmetric Strecker Synthesis of a-Amino Acids via a Crystallization-Induced Asymmetric Transformation Using (/Q-Phenylglycine Amide as Chiral Auxiliary... 

Diastereoselective Slrecker reactions based on (R)-phenylglycine amide as chiral auxiliary are reported. The Strecker reaction is accompanied by an In situ crystallization-induced asymmetric transformation, whereby one diastereomer selecliveiy precipitates and can be isolated in 76-33% yield and dr > gsti. The diastereomeilcaily pure a-amino nitrtie obtained from pivaidehyde (R, = t-Bu, Rj = H) was converted in three steps to (S)-tert-leucine in 73% yieid and >98% ee. 

Because in methanol crystallization of amino nitrile 3 did not take place, first the solvent was varied in order to attempt to find conditions for a crystallization-induced asymmetric transformation. At a MeOH/2-PrOH ratio of 1/9, the amino nitrile (R,S)-3 was isolated in 51% yield and dr 99/1 (entry 2). Other combinations of alcoholic solvents failed to lead to a higher yield of precipitated (R,S)-3 in high dr (entries 3 and 4). On further screening of solvents, it was observed that upon addition of HjO to the methanol solution selective precipitation of amino nitrile (R,S)-3 occurred giving (R,S)-3 and (R,R)-3 in a ratio of 81 19 and 69% yield (entry 5). The asymmetric Strecker reaction was further studied in HjO alone using temperature as a variable. The results of these experiments are given in Table 1 (entries 6-9). After addition of NaCN/AcOH at 23-28 °C... 

Figure2. Crystallization-induced asymmetric transformation of amino nitrile 3.

The observed diastereoselectivity in the asymmetric Strecker step via the crystallization-induced asymmetric transformation can be explained as shown in Figure 2. Apparently, the re face addition of CN to the intermediate imine 4 is preferred at room temperature in methanol and results in a dr 65/35. At elevated temperatures in water, the diastereomeric outcome and yield of the process are controlled by the reversible reaction of the amino nitriles 3 to the intermediate imine and by the difference in solubilities of both diastereomers under the applied conditions. . .. 

In summary, (R)-phenylglycine amide 1 is an excellent chiral auxiliary in the asymmetric Strecker reaction with pivaldehyde or 3,4-dimethoxyphenylacetone. Nearly diastereomerically pure amino nitriles can be obtained via a crystallization-induced asymmetric transformation in water or water/methanol. This practical one-pot asymmetric Strecker synthesis of (R,S)-3 in water leads to the straightforward synthesis of (S)-tert-leucine 7. Because (S)-phenylglycine amide is also available, this can be used if the other enantiomer of a target molecule is required. More examples are currently under investigation to extend the scope of this procedure. ... 

Diastereoselective Strecker reactions based on (R)-phenylglycine amide as chiral auxiliary are reported. The Strecker reaction is accompanied by an in situ crystallization-induced asymmetric transformation, whereby one diastereomer selectively precipitates and... 

Overview. To solve these problems, we present the first example of a crystallization-induced asymmetric transformation using optically pure (R)-phenylglycine amide 1 as a chiral auxiliary. The (R,S)-3 diastereomer precipitates out of solution in 76-93% yield with a diastereomeric ratio (dr) > 99/1. (106 words)... 

We present the hrst example of a crystallization-induced asymmetric synthesis. 

The asymmetric synthesis of a-amino acids is an important topic due to their extensive use in pharmaceuticals and agrochemicals and as chiral ligands. The Strecker reaction is historically one of the most versatile ways to produce a-amino acids, but this method has a maximum yield of only 50% for a single enantiomer. Higher yields can be achieved by using chiral auxiliaries, but auxiliaries have other drawbacks, such as high cost, low availability, the need for purification, and high loss rates. A possible solution to these problems would be to use a chiral auxiliary in a crystallization-induced asymmetric transformation. 

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