Experimental characterization of hexatic smectic phases through electro-optic studies and dielectric relaxation spectroscopy

The electro-optic and complex dielectric behaviour of an antiferroelectric liquid crystal 4-(1-methylheptyloxycarbonyl)phenyl 4'-(n-butanoyloxyprop-1-oxy)biphenyl-4-carboxylate, having chiral SmC_A* and hexatic smectic phases, have been investigated. Complex dielectric permittivities were measured as a function of frequency, d.c. bias field and temperature. Spontaneous polarization was measured by the current reversal technique; tilt angle was measured under a polarizing microscope using a low frequency electric field. The electro-optic properties and dielectric behaviour of the material are compared with results obtained by DSC and polarizing optical microscopy. Dielectric relaxation processes in SmC_A* and hexatic smectic phases were determined. The dielectric strength at the SmC_A* to hexatic smectic phase transition is discussed in terms of coupling between the long range bond orientational order and smectic C director. It seems from the results of spontaneous polarization and dielectric relaxation spectroscopy that the material might possess an additional phase between the SmC_A* and hexatic smectic I* phases.     

Synthesis of Polysiloxane Xerogels Using Tetraethoxysilane/(Diethylphosphatoethyl)triethoxysilane System

The xerogels, containing phosphonic acid groups ≡Si(CH₂)₂P(O)(OC₂H₅)₂ in the surface layer of their particles, are synthesized by the sol-gel method (ethanol as a solvent and fluoride ion as a catalyst). It is shown that, when 2 : 1, 3 : 1, and 4 : 1 tetraethoxysilane/(diethylphosphatoethyl)triethoxysilane ratios are used, nonporous substances are formed, whereas, at 6 : 1, 8 : 1, and 10 : 1 ratios, the xerogels with highly porous structures are produced (the specific surface area is 505–534 m²/g, the sorption pore volume is 0.34–0.53 cm³/g, and the pore diameter is 3.6–4.6 nm).     

The preparation of polysiloxane xerogels containing amide derivatives of phosphonic and thiophosphonic acids in the surface layer

Xerogels containing residues of amide derivatives of phosphonic and thiophosphonic acids, ≡Si(CH₂)₃NHP(S, O)(OC₂H₅)₂ (functional group concentration of 1.3–2.2 mmol/g) have been prepared by a sol-gel method. It has been shown that xerogels having a developed porous structure (with specific surface areas of 240–485 m²/g, pore volumes of 0.20–0.50 cm³/g, and pore diameters of 3.6–6.5 nm) are formed at tetraethoxysilane-to-trifunctional silane ratios of 4: 1 (and above) and 6: 1 (and above) for the derivatives of phosphonic and thiophosphonic acids, respectively. The IR and ¹³C CP/MAS NMR spectroscopy data have demonstrated that the surface layer of the xerogels contains not only (thio)phosphonic acid residues, but also silanol groups and water molecules participating in hydrogen bonding. The ²⁹Si CP/MAS NMR spectroscopy data have indicated that structural groups are, for the most part, contained in structural units T³ [(≡SiO)₃Si(CH₂)₃NHP(O, S)(OC₂H₅)₂] and T² [(≡SiO)₂Si(OR)[(CH₂)₃NHP(O, S)(OC₂H₅)₂] (R = H or C₂H₅).     

Multiplex polymerase chain reaction analysis of Glu-1 high-molecular-mass glutenin genes from wheat by capillary electrophoresis with laser-induced fluorescence detection

The unique bread-making properties of wheat are closely correlated with composition and quantity of high-molecular-mass (HMW) glutenin subunits encoded by the Glu-1 genes. We report the development of a multiplex polymerase chain reaction (PCR) method to identify bread wheat genotypes carrying HMW glutenin allele composition of Glu-1 complex loci (Glu-A1, Glu-B1 and Glu-D1) by capillary electrophoresis(CE) with laser-induced fluorescence (LIF) detection. Two triplex primer sets of HMW glutenin subunit genes were examined. An automated and rapid CE-LIF technique is helpful in the multiplex PCR optimization process. Two fluorescent intercalating dyes (EnhanCE, and YO-PRO-1) are compared for detection of DNA fragments. Amplified DNA fragments of HMW glutenin Glu-1 genes were well separated both by agarose slab-gel electrophoresis and CE, and revealed minor differences between the sequences of 1Ax2*, 1Axnull, 1Bx6, 1Bx7, 1Bx17 and 1Dx5 genes. Moreover, CE technique requires samples of smaller volumes in comparison to slab-gel electrophoresis, and data can be obtained in less than 20 min. There was a very high concordance in the assessment of the molecular size of PCR-generated DNA markers. Fast and accurate identification of molecular markers of Glu-1 genes by CE-LIF can be an efficient alternative to standard procedure separation for early selection of useful wheat genotypes with good bread-making quality.     

Pyrene.pyrene complexes at the active site of cytochrome P450 3A4: evidence for a multiple substrate binding site

Cytochrome P450 monooxygenases (CYPs) metabolize nearly all drugs and toxins. Recently, it has become clear that CYPs exhibit both homotropic and heterotropic allosteric kinetics for many substrates. However, the mechanism of cooperative kinetics has not been established for any specific human CYP/substrate combination. Suggested mechanisms include binding of multiple substrates within distinct, static, subsites of a single large active site or binding of multiple substrates within a single fluid active site. CYP3A4 hydroxylates pyrene with positive cooperativity. Therefore, experiments were designed to exploit the fluorescence properties of pyrene, which diagnostically distinguish between pyrene.pyrene complexes versus spatially separated pyrene substrates. Pyrene complexes (excimers) yield an emission spectrum clearly distinct from pyrene monomers. In lipid-free aqueous/glycerol solutions of CYP3A4, addition of pyrene affords a concentration-dependent low-spin to high-spin conversion of the CYP3A4 heme prosthetic group, indicating occupancy of the active site by pyrene. Under the same conditions, in the presence of CYP3A4 but not other heme proteins, the excimer/monomer ratio (E/M) of pyrene was decreased in emission spectra, compared to pyrene alone. However, excitation spectra indicate a CYP3A4-dependent increase in the wavelength shift for the excimer excitation spectrum versus the monomer excitation spectrum, as well as changes in the excimer excitation peak shape and vibronic structure. These changes are reversed by the CYP3A4 substrate testosterone. Together, the results demonstrate that pyrene.pyrene ground-state complexes occupy the CYP3A4 active site, and they provide the first spectroscopic evidence for substrate complexes within a single fluid active site. Functional implications include the possibility that turnover rate, regioselectivity, and stereoselectivity of the reaction are determined by the substrate.substrate complex rather than individual substrates.     

Komplexbildende Eigenschaften des 3,5-Dimethylpyrazols

Zusammenfassung 3,5-Dimethylpyrazol bildet in Anwesenheit von Rhodanid mit Kupfer(II) einen gefärbten Komplex, der in Chloroform leicht löslich ist. Diese Reaktion wurde zur photometrischen Bestimmung von 10 bis 100g Cu/5 ml verwendet.

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Summary A colored complex, that is readily soluble in chloroform, is formed by copper(II) with 3,5-dimethylpyrazole in the presence of thiocyanate. This reaction was employed for the photometric determination of 10 to 100g Cu/5 ml.

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Résumé Le diméthyl-3,5 pyrazol forme avec le cuivre-II en présence de thiocyanate, un complexe coloré, facilement soluble dans le chloroforme. On a utilisé cette réaction pour le dosage photométrique de 10 à 100g Cu/5 ml.