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951.
Bell AF Feng Y Hofstein HA Parikh S Wu J Rudolph MJ Kisker C Whitty A Tonge PJ 《Chemistry & biology》2002,9(11):1247-1255
Enoyl-CoA hydratase catalyzes the hydration of trans-2-crotonyl-CoA to 3(S)- and 3(R)-hydroxybutyryl-CoA with a stereoselectivity (3(S)/3(R)) of 400,000 to 1. Importantly, Raman spectroscopy reveals that both the s-cis and s-trans conformers of the substrate analog hexadienoyl-CoA are bound to the enzyme, but that only the s-cis conformer is polarized. This selective polarization is an example of ground state strain, indicating the existence of catalytically relevant ground state destabilization arising from the selective complementarity of the enzyme toward the transition state rather than the ground state. Consequently, the stereoselectivity of the enzyme-catalyzed reaction results from the selective activation of one of two bound substrate conformers rather than from selective binding of a single conformer. These findings have important implications for inhibitor design and the role of ground state interactions in enzyme catalysis. 相似文献
952.
The title compounds BaIn3.1Hg3.9 (x = 3.1) (I) and BaInxHg11‐x (x = 0—2.8) (II) are prepared from stoichiometric mixtures of the elements (Ta crucible, 825 K, cooling rate of 5 K/h). 相似文献
953.
For feeding of working dogs during their daily life, illness, routine jobs or sporting activities, an accurate determination of their nutritional requirements is essential to ensure their optimal health and performance. To predict the appropriate guidelines about how to feed dogs, it appears essential to determine the energy expenditure (EE) in a reliable and feasible way. In the present experiment, the non-invasive oral 13C-bicarbonate tracer technique (o13CT), i.e. collection of breath samples after oral administration of NaH13CO3, was used for the estimation of CO2 production and EE in dogs. Measurements were conducted during two days of rest, and during three days with 3 h of exercise per day. Average EE was 483 and 876 kJ kg?0.75 d?1 during rest and exercise, respectively. The o13CT seems appropriate to use as a minimal restrictive and non-invasive method to obtain reliable estimates of EE in dogs at different activity levels under near natural conditions. 相似文献
954.
Sandra V M de Moraes Mateus M Tisott Caroline D Milcharek Jorge L Brasil Tania M H Costa Márcia R Gallas Edilson V Benvenutti Eder C Lima 《Analytical sciences》2005,21(5):573-577
A new sorbent was synthesized by anchoring 7-amino-4-azaheptyltrimetoxisilane, freshly prepared, to silica gel, producing 7-amino-4-azaheptyl anchored silica gel (AAHSG). This material was characterized by infrared spectroscopy (IR), elemental analysis (CHN), and nitrogen adsorption-desorption isotherms. Isotherms of the adsorption of Fe3+, Fe2+ and Cu2+ on AAHSG were recorded, which indicated that Fe3+ presents a higher affinity by the sorbent. Therefore, AAHSG was successfully employed as a sorbent in a simple flow system for the preconcentration of Fe3+ in natural water samples, such as, river water, lagoonwater, springwater, stream water, well water and two water reference materials (NIST-SRM 1640, NIST-SRM 1643d). The obtained preconcentration factor was 82.2, and the detection limit achieved was 5.9 ng ml(-1). The recovery of spiked water samples ranged from 95.0 - 103.1%. 相似文献
955.
956.
Camille Bathellier Guillaume Tcherkez Caroline Mauve Richard Bligny Elizabeth Gout Jaleh Ghashghaie 《Rapid communications in mass spectrometry : RCM》2009,23(18):2847-2856
The response of root metabolism to variations in carbon source availability is critical for whole‐plant nitrogen (N) assimilation and growth. However, the effect of changes in the carbohydrate input to intact roots is currently not well understood and, for example, both smaller and larger values of root:shoot ratios or root N uptake have been observed so far under elevated CO2. In addition, previous studies on sugar starvation mainly focused on senescent or excised organs while an increasing body of data suggests that intact roots may behave differently with, for example, little protein remobilization. Here, we investigated the carbon and nitrogen primary metabolism in intact roots of French bean (Phaseolus vulgaris L.) plants maintained under continuous darkness for 4 days. We combined natural isotopic 15N/14N measurements, metabolomic and 13C‐labeling data and show that intact roots continued nitrate assimilation to glutamate for at least 3 days while the respiration rate decreased. The activity of the tricarboxylic acid cycle diminished so that glutamate synthesis was sustained by the anaplerotic phosphoenolpyruvate carboxylase fixation. Presumably, the pentose phosphate pathway contributed to provide reducing power for nitrate reduction. All the biosynthetic metabolic fluxes were nevertheless down‐regulated and, consequently, the concentration of all amino acids decreased. This is the case of asparagine, strongly suggesting that, as opposed to excised root tips, protein remobilization in intact roots remained very low for 3 days in spite of the restriction of respiratory substrates. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
957.
Photothermal deflection microscopy for imaging sub-micronic defects in optical materials 总被引:2,自引:0,他引:2
Photothermal deflection is widely used to study defects in optical coatings and role of these defects in laser damage. Because defects responsible for laser damage are assumed to be nanometer-sized and lowly absorbing, both high spatial resolution and high sensitivity are required to detect them. In this work we theoretically and experimentally explore the capability of collinear photothermal deflection to give micronic resolution by reduction of the pump beam diameter. Thanks to a model describing temperature distribution and photothermal deflection, we have studied the effects of pump beam focusing on photothermal deflection. Then, we have developed a high resolution, high sensitivity microscope based on the photothermal deflection of a transmitted probe beam. The setup is characterized and the theoretical predictions are checked. We present a test of lateral spatial resolution obtained on specially prepared absorbing resolution targets and show that a lateral spatial resolution of 1 μm is reached on non-isolated defects. In case of single defects, we expect that 10 nm sized defects could be detected. 相似文献
958.
Design of the First‐in‐Class,Highly Potent Irreversible Inhibitor Targeting the Menin‐MLL Protein–Protein Interaction
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Dr. Shilin Xu Dr. Angelo Aguilar Dr. Tianfeng Xu Dr. Ke Zheng Dr. Liyue Huang Prof. Dr. Jeanne Stuckey Dr. Krishnapriya Chinnaswamy Dr. Denzil Bernard Dr. Ester Fernández‐Salas Dr. Liu Liu Dr. Mi Wang Donna McEachern Sally Przybranowski Caroline Foster Prof. Dr. Shaomeng Wang 《Angewandte Chemie (International ed. in English)》2018,57(6):1601-1605
The structure‐based design of M‐525 as the first‐in‐class, highly potent, irreversible small‐molecule inhibitor of the menin‐MLL interaction is presented. M‐525 targets cellular menin protein at sub‐nanomolar concentrations and achieves low nanomolar potencies in cell growth inhibition and in the suppression of MLL‐regulated gene expression in MLL leukemia cells. M‐525 demonstrates high cellular specificity over non‐MLL leukemia cells and is more than 30 times more potent than its corresponding reversible inhibitors. Mass spectrometric analysis and co‐crystal structure of M‐525 in complex with menin firmly establish its mode of action. A single administration of M‐525 effectively suppresses MLL‐regulated gene expression in tumor tissue. An efficient procedure was developed to synthesize M‐525. This study demonstrates that irreversible inhibition of menin may be a promising therapeutic strategy for MLL leukemia. 相似文献
959.
Terminal Alkyne Coupling Reactions through a Ring: Mechanistic Insights and Regiochemical Switching
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Caroline M. Storey Dr. Matthew R. Gyton Dr. Rhiann E. Andrew Dr. Adrian B. Chaplin 《Angewandte Chemie (International ed. in English)》2018,57(37):12003-12006
The mechanism and selectivity of terminal alkyne coupling reactions promoted by rhodium(I) complexes of NHC‐based CNC pincer ligands have been investigated. Synthetic and kinetic experiments support E‐ and gem‐enyne formation through a common reaction sequence involving hydrometallation and rate‐determining C?C bond reductive elimination. The latter is significantly affected by the ligand topology: Employment of a macrocyclic variant enforced exclusive head‐to‐head coupling, contrasting the high selectivity for head‐to‐tail coupling observed for the corresponding acyclic pincer ligand. 相似文献
960.
Caroline Rita Venturi Srgio Augusto De Loreto Bordignon Samuel Paulo Cibulski Grace Gosmann 《Natural product research》2018,32(16):1960-1962
The chemical composition and antiviral activity of aqueous extract from Baccharis anomala was studied by bioactivity-guided fractionation. Ethanol precipitation and fractionation by molecular permeation allowed the separation of the anti-herpes simplex virus 1 (HSV-1) active fraction from aqueous extract (Fraction B). Natural Product Reagent A, FeCl3 and thin-layer chromatography indicated the presence of phenolic compounds in the aqueous extract. Fraction B showed pronounced antiviral activity when tested with HSV-1 strains VR733/ATCC and Acyclovir-resistant 29-R, displaying virucidal but not virustatic activity. 相似文献