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111.
Aleksandra A. Ageeva Ilya M. Magin Alexander B. Doktorov Victor F. Plyusnin Polina S. Kuznetsova Alexander A. Stepanov Alexander A. Alekseev Nikolay E. Polyakov Tatyana V. Leshina 《International journal of molecular sciences》2021,22(12)
The study of the L- and D-amino acid properties in proteins and peptides has attracted considerable attention in recent years, as the replacement of even one L-amino acid by its D-analogue due to aging of the body is resulted in a number of pathological conditions, including Alzheimer’s and Parkinson’s diseases. A recent trend is using short model systems to study the peculiarities of proteins with D-amino acids. In this report, the comparison of the excited states quenching of L- and D-tryptophan (Trp) in a model donor–acceptor dyad with (R)- and (S)-ketoprofen (KP-Trp) was carried out by photochemically induced dynamic nuclear polarization (CIDNP) and fluorescence spectroscopy. Quenching of the Trp excited states, which occurs via two mechanisms: prevailing resonance energy transfer (RET) and electron transfer (ET), indeed demonstrates some peculiarities for all three studied configurations of the dyad: (R,S)-, (S,R)-, and (S,S)-. Thus, the ET efficiency is identical for (S,R)- and (R,S)-enantiomers, while RET differs by 1.6 times. For (S,S)-, the CIDNP coefficient is almost an order of magnitude greater than for (R,S)- and (S,R)-. To understand the source of this difference, hyperpolarization of (S,S)-and (R,S)- has been calculated using theory involving the electron dipole–dipole interaction in the secular equation. 相似文献
112.
Alexander Zimmermann Qais Z. Jaber Dr. Johannes Koch Steffen Riebe Dr. Cecilia Vallet Dr. Kateryna Loza Matthias Hayduk Dr. Kfir B. Steinbuch Prof. Shirley K. Knauer Prof. Micha Fridman Jun.-Prof. Jens Voskuhl 《Chembiochem : a European journal of chemical biology》2021,22(9):1563-1567
We report the characterization of amphiphilic aminoglycoside conjugates containing luminophores with aggregation-induced emission properties as transfection reagents. These inherently luminescent transfection vectors are capable of binding plasmid DNA through electrostatic interactions; this binding results in an emission “on” signal due to restriction of intramolecular motion of the luminophore core. The luminescent cationic amphiphiles effectively transferred plasmid DNA into mammalian cells (HeLa, HEK 293T), as proven by expression of a red fluorescent protein marker. The morphologies of the aggregates were investigated by microscopy as well as ζ-potential and dynamic light-scattering measurements. The transfection efficiencies using luminescent cationic amphiphiles were similar to that of the gold-standard transfection reagent Lipofectamine® 2000. 相似文献
113.
Paula Bracco Hein J. Wijma Bastian Nicolai Jhon Alexander Rodriguez Buitrago Thomas Klünemann Agustina Vila Patrick Schrepfer Wulf Blankenfeldt Dick B. Janssen Prof. Dr. Anett Schallmey 《Chembiochem : a European journal of chemical biology》2021,22(6):1099-1110
CYP154C5 from Nocardia farcinica is a P450 monooxygenase able to hydroxylate a range of steroids with high regio- and stereoselectivity at the 16α-position. Using protein engineering and substrate modifications based on the crystal structure of CYP154C5, an altered regioselectivity of the enzyme in steroid hydroxylation had been achieved. Thus, conversion of progesterone by mutant CYP154C5 F92A resulted in formation of the corresponding 21-hydroxylated product 11-deoxycorticosterone in addition to 16α-hydroxylation. Using MD simulation, this altered regioselectivity appeared to result from an alternative binding mode of the steroid in the active site of mutant F92A. MD simulation further suggested that the entrance of water to the active site caused higher uncoupling in this mutant. Moreover, exclusive 15α-hydroxylation was observed for wild-type CYP154C5 in the conversion of 5α-androstan-3-one, lacking an oxy-functional group at C17. Overall, our data give valuable insight into the structure–function relationship of this cytochrome P450 monooxygenase for steroid hydroxylation. 相似文献
114.
Abstract. We propose the quasi‐maximum likelihood method to estimate the parameters of an RCA(1) process, i.e. a random coefficient autoregressive time series of order 1. The strong consistency and the asymptotic normality of the estimators are derived under optimal conditions. 相似文献
115.
Decomposition of SRC-II middle distillate under surface vaporizing conditions was studied as a function of temperature (heating rate), vapour phase residence time and oxygen level. The stressed and unstressed fuel was analysed by capillary gas chromatography. Decomposition was found to be greatest at low temperature. Boiling mode did not appear to affect the extent of decomposition. Decomposition was weakly related to chemical class and strongly related to component volatility. The effect of gas phase residence time and oxygen level were negligible at the conditions studied. It is concluded that decomposition occurs primarily within the liquid and at the vaporizer surface. 相似文献
116.
A novel technique for the preparation of secondary fatty amides 总被引:1,自引:0,他引:1
Alexander Bilyk Raymond G. Bistline Jr. George J. Piazza Stephen H. Feairheller Michael J. Haas 《Journal of the American Oil Chemists' Society》1992,69(5):488-491
A technique for the synthesis of monosubstituted fatty amides at low temperature and ambient pressure was developed. This
method involved the condensation of an amine with a triacylglycerol. The primary amine (ethyl,n-butyl,n-hexyl andn-octyl were tested) acted as reagent and solvent for the fatty substrates. No additional organic solvent or catalyst was added.
Tallow, vegetable oils and fish oil all served well as substrates, as did pure tripalmitin. The rate of amidation was dependent
upon temperature and the ratio of fat to amine. In a series of experiments conducted with tallow andn-butylamine at a fat:amine molar ratio of 1:16, amidation could be carried out at 20°C, producingn-butyltallowamide in 83% yield in 24 hr. When the fat:amine molar ratio was reduced to 1:8, and the temperature raised to
45°C, the amide yield was 87.6% in 24 hr. When the reaction was carried out at the boiling point ofn-butylamine (78°C) and at a fat:amine ratio of 1:8, the amide yield was 93.2% in 4 hr. The reaction progressed more rapidly
with higher molecular weight amines. The identity and purity of the amides was assessed by thin-layer chromatography and confirmed
by elemental analyses and infrared and C13 nuclear magnetic resonance spectroscopy. 相似文献
117.
A surfactant‐free method to produce responsive polymer microgels is introduced. As an example, poly(methacrylic acid) hydrogels with varying crosslinking density have been synthesized in bulk and then chopped using a high shear mechanical cutter to form microgel particles dispersed in water. The mechanical cutting technique enables the concentration and particle size distribution of the microgel suspensions to be easily controlled, therefore making the rheology of the suspensions tuneable. The particle size distribution of the dispersions, characterized using light scattering, was dependent on the speed and duration of mechanical cutting. The particle size distribution also depended on the degree of crosslinking of the hydrogel. The higher the crosslinking density, the lower the average mean diameter of the resulting microgel particles. The lower the crosslinking density of the hydrogel, the larger the difference between the maximum and minimum particle size. The time to complete swelling of the particles upon change in pH was measured to be up to 45 s, depending on the particle size. The rheology of the resulting suspensions as a function of pH was investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 104: 1912–1919, 2007 相似文献
118.
VNIISV, Tver'. Institute of Chemical Physics, Moscow. Translated from Khimicheskie Volokna, No. 3, pp. 42–43, May–June, 1992. 相似文献
119.
Reactor blends of polyethylene/poly(ethylene-co-1-octene) resins with bimodal molecular weight and bimodal short chain branching distributions were synthesized in a two-step polymerization process. The compositions of these blends range from low molecular weight (LMW) homopolymer to high molecular weight (HMW) copolymer and vice versa HMW homopolymer to LMW copolymer. The shear flow characteristics of these polymers in the typical processing range mostly depend on the molecular weight and MWD of the polymer and are independent of the short chain branch content. From oscillatory shear measurements, it was observed that the viscosity of HMW polymers was reduced with the addition of LMW material. For the polymers produced with this two-step polymerization process, the LMW homopolymer and HMW copolymer blends and HMW homopolymer and LMW copolymer blends were melt miscible, despite the large viscosity differences of the pure components. 相似文献
120.
Dan Raviv Alexander M. Bronstein Michael M. Bronstein Dan Waisman Nir Sochen Ron Kimmel 《Journal of Mathematical Imaging and Vision》2014,50(1-2):144-163
Traditional models of bendable surfaces are based on the exact or approximate invariance to deformations that do not tear or stretch the shape, leaving intact an intrinsic geometry associated with it. These geometries are typically defined using either the shortest path length (geodesic distance), or properties of heat diffusion (diffusion distance) on the surface. Both measures are implicitly derived from the metric induced by the ambient Euclidean space. In this paper, we depart from this restrictive assumption by observing that a different choice of the metric results in a richer set of geometric invariants. We apply equi-affine geometry for analyzing arbitrary shapes with positive Gaussian curvature. The potential of the proposed framework is explored in a range of applications such as shape matching and retrieval, symmetry detection, and computation of Voroni tessellation. We show that in some shape analysis tasks, equi-affine-invariant intrinsic geometries often outperform their Euclidean-based counterparts. We further explore the potential of this metric in facial anthropometry of newborns. We show that intrinsic properties of this homogeneous group are better captured using the equi-affine metric. 相似文献