Time-resolved fluorescence study of the single tryptophan in thiocyanate and azide derivatives of horseradish peroxidase: Implication for a p H-induced conformational change in the heme cavity

Detailed pH-dependent steady state and picosecond time-resolved tryptophan fluorescence studies on thiocyanate and azide complexes of horseradish peroxidase have been carried out. The fluorescence decay of the single tryptophan in these species was fitted to a discrete three exponential model. Maximum entropy method analysis also gave three distinct regions of lifetime distributions. The fast subnanosecond lifetime component was found to have > 97% amplitude contribution while other two longer lifetime components have small contributions. Small contributions from the nanosecond lifetime components possibly arise from apoprotein impurity or some small amount of disordered heme conformer of the protein. pH dependence of the fast picosecond lifetime components was found to show a systematic behavior which has been interpreted in the light of obligatory conformation change associated with activation of the enzyme at low pH.     

Theoretical and experimental investigation of the linear optical response of YBa2Cu4O8 The relevance of LDA calculations

We report results of ellipsometric measurements of the dielectric tensor of YBa₂Cu₄O₈ as well as calculations employing density functional theory in the local density approximation (LDA). For the computation of the one-electron eigenvalues and states the linear-muffin-tin-orbital method (LMTO) was used. Measured and calculated results show good agreement. In particular, the calculation predicts different band structures for YBa₂Cu₃O₇ and YBa₂Cu₄O₈ in the vicinity of the Fermi energy which lead to significant differences in the optical spectra. One such difference is a region of small ε₂ in the near infrared which is a fingerprint of the high (relative to the top of the highest fully occupied band) Fermi energy as compared to the situation in YBa₂Cu₃O₇. Our experimental results confirm the theoretical findings.     

Thermoplastic polymers quality control

A technique is proposed for improving the accuracy of the heat of fusion of semicrystalline polymers by DSC. The results of three commercially available instruments are compared.     

1,3-dipolar cycloaddition as a method for synthesis of fullerene C60 derivatives containing heterocyclic moieties

We generalize literature data and our own experimental data on using 1,3-dipolar cycloaddition reactions for synthesis of fullerene C₆₀ derivatives containing annelated heterocyclic moieties.M. V. Lomonosov Moscow State University, Moscow 119899, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 291–297, March, 1998.     

Influence of layer and anisotropic fluctuations of the refractive index on the beyond-the-horizon SHF propagation in the troposphere over the sea when there is an evaporation duct

On the basis of the invariant imbedding method the disturbance theory for complex constants of propagation is proposed. This approach allows us to consider the influence of layer and anisotropic fluctuations of refractive index on the beyond-the-horizon propagation in the adiabatic approximation with the existence of an evaporation duct. Finally, the authors consider some examples of the calculations and investigate stochastic effects connected with the interaction between fluctuating and regular waveguides.     

X-ray diffraction study of 'side-on fixed' homopolysiloxanes from nematic to smectic C phases

The X-ray patterns for the nematic phase in a series of side-on fixed polysiloxanes show different kinds of diffuse elements which imply complex short range ordering. A systematic structural study of the evolution of the patterns versus two molecular parameters, namely the spacer length and the length of the terminal aliphatic tails, suggests the possible occurrence of a smectic C phase for certain values of these parameters. Taking into account these tendencies, new synthesis led to a nematic-smectic C polymorphism observed for the first time in side-on fixed polysiloxanes.     

Contributions to the synthesis of some ferrocene-containing antibiotics

This Review discusses the synthesis and characterization by our Group of new antibiotics belonging to the class of penicillins, cephalosporins and rifamycins with ferrocenyl and 1, 1′-ferrocenilene residues in the molecule. As reactants for 6-aminopenicillanic acid (6-APA) and 7-aminocephalosporanic acid (7-ACA) the following were used: 1, 1-bis(chlorocarbonyl)ferrocene, ferrocenyl sulfochloride, 1, 1′-ferrocenylenedisulfochloride and thioglycolic acids S-modified with ferrocene. In the synthesis of rifamycins, the hydrazides of the thioglycolic acids, S-modified with ferrocene, were employed as nucleophilic agents. The synthesized intermediates were characterized by elemental analysis, TLC, IR, UV and ¹H NMR spectra. The characterization of new antibiotics was made by TLC, IR and UV spectral analysis. Biological activity was tested on Gram-negative and Gram-positive bacteria. Good activity is reported towards Gram-positive bacteria in the case of derivatives containing residues of thioglycolic acid S-modified with ferrocene, the antibacterial activity being similar to that of amoxicillin, carbenicillin and cephalothin. All compounds are inactive towards Gram-negative bacteria.     

Linear optical switching in a FLC/waveguide composite device

A fast electrooptic modulation in a polymer waveguide using a ferroelectric liquid crystal has been proposed. In this device, the surface stabilized ferroelectric liquid crystal and the soft mode ferroelectric liquid crystal are used as an active material on the passive polymer waveguide, and electrooptic switching is realized by controlling the total reflection at the polymer waveguide-liquid crystal interface. The response time is of the order of several microseconds. The analogue electrooptic modulation in the waveguide is realized using the field induced linear molecular tilt of the electroclinic effect in the soft mode ferroelectric liquid crystal.