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141.
Phosphorylation reaction in cAPK protein kinase-free energy quantum mechanical/molecular mechanics simulations 总被引:1,自引:0,他引:1
Valiev M Yang J Adams JA Taylor SS Weare JH 《The journal of physical chemistry. B》2007,111(47):13455-13464
We present results of a theoretical analysis of the phosphorylation reaction in cAMP-dependent protein kinase using a combined quantum mechanical and molecular mechanics (QM/MM) approach. Detailed analysis of the reaction pathway is provided using a novel QM/MM implementation of the nudged elastic band method, finite temperature fluctuations of the protein environment are taken into account using free energy calculations, and an analysis of hydrogen bond interactions is performed on the basis of calculated frequency shifts. The late transfer of the substrate proton to the conserved aspartate (D166), the activation free energy of 15 kcal/mol, and the slight exothermic (-3 kcal/mol) character of the reaction are all consistent with the experimental data. The near attack conformation of D166 in the reactant state is maintained by interactions with threonine-201, asparagine-177, and most notably by a conserved water molecule serving as a strong structural link between the primary metal ion and the D166. The secondary Mg ion acts as a Lewis acid, attacking the beta-gamma bridging oxygen of ATP. This interaction, along with a strong hydrogen bond between the D166 and the substrate, contributes to the stabilization of the transition state. Lys-168 maintains a hydrogen bond to a transferring phosphoryl group throughout a reaction process. This interaction increases in the product state and contributes to its stabilization. 相似文献
142.
Sylvestre P. J. T. Bachollet Dean C. Cocker Harry Adams Prof. Joseph P. A. Harrity 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(40):12889-12893
The aza‐Diels–Alder cycloaddition of 1,2,4‐triazines with alkynes offers a rapid and convenient method for the synthesis of highly substituted pyridines, but often requires harsh conditions and long reaction times. The present study offers a solution to these limitations by use of a temporary tether established by a Lewis acid–base complexation of in situ generated alkynylboranes and triazines bearing a Lewis basic donor. The cycloaddition reactions take place within 20 min at 40 °C and provide direct access to a broad range of pyridines with complete and predictable regiocontrol. The carbon?boron bond can be further functionalised by cross‐coupling allowing further functionality to be introduced after cycloaddition. 相似文献
143.
Matthew Wallace Andre Zamith Cardoso Dr. William J. Frith Dr. Jonathan A. Iggo Dr. Dave J. Adams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16484-16487
The magnetic‐field‐induced alignment of the fibrillar structures present in an aqueous solution of a dipeptide gelator, and the subsequent retention of this alignment upon transformation to a hydrogel upon the addition of CaCl2 or upon a reduction in solution pH is reported. Utilising the switchable nature of the magnetic field coupled with the slow diffusion of CaCl2, it is possible to precisely control the extent of anisotropy across a hydrogel, something that is generally very difficult to do using alternative methods. The approach is readily extended to other compounds that form viscous solutions at high pH. It is expected that this work will greatly expand the utility of such low‐molecular‐weight gelators (LMWG) in areas where alignment is key. 相似文献
144.
De Vita R Anghinolfi M Burkert VD Dodge GE Minehart R Taiuti M Weller H Adams G Amaryan MJ Anciant E Armstrong DS Asavapibhop B Asryan G Audit G Auger T Avakian H Bagdasaryan H Ball JP Barrow S Battaglieri M Beard K Bektasoglu M Bianchi N Biselli AS Boiarinov S Bonner BE Bosted P Bouchigny S Branford D Brooks WK Bueltmann S Calarco JR Capitani GP Carman DS Carnahan B Cazes A Ciciani L Cole PL Coleman A Connelly J Cords D Corvisiero P Crabb D Crannell H Cummings JP De Sanctis E Degtyarenko PV 《Physical review letters》2002,88(8):082001
The double spin asymmetry in the (-->)e(-->)p --> e(prime)pi(+)n reaction has been measured for the first time in the resonance region for four-momentum transfer Q2 = 0.35-1.5 GeV(2). Data were taken at Jefferson Lab with the CLAS detector using a 2.6 GeV polarized electron beam incident on a polarized solid NH3 target. Comparison with predictions of phenomenological models shows strong sensitivity to resonance contributions. Helicity-1/2 transitions are found to be dominant in the second and third resonance regions. The measured asymmetry is consistent with a faster rise with Q(2) of the helicity asymmetry A1 for the F(15)(1680) resonance than expected from the analysis of the unpolarized data. 相似文献
145.
Joo K Smith LC Burkert VD Minehart R Aznauryan IG Elouadrhiri L Stepanyan S Adams GS Amaryan MJ Anciant E Anghinolfi M Armstrong DS Asavapibhop B Audit G Auger T Avakian H Barrow S Bagdasaryan H Battaglieri M Beard K Bektasoglu M Bertozzi W Bianchi N Biselli AS Boiarinov S Bonner BE Brooks WK Calarco JR Capitani GP Carman DS Carnahan B Cole PL Coleman A Cords D Corvisiero P Crabb D Crannell H Cummings J De Sanctis E De Vita R Degtyarenko PV Demirchyan RA Denizli H Dennis LC Deppman A 《Physical review letters》2002,88(12):122001
Models of baryon structure predict a small quadrupole deformation of the nucleon due to residual tensor forces between quarks or distortions from the pion cloud. Sensitivity to quark versus pion degrees of freedom occurs through the Q2 dependence of the magnetic (M1+), electric (E1+), and scalar (S1+) multipoles in the gamma*p-->Delta(+)-->p pi(0) transition. We report new experimental values for the ratios E(1+)/M(1+) and S(1+)/M(1+) over the range Q2 = 0.4-1.8 GeV2, extracted from precision p(e,e(')p)pi(0) data using a truncated multipole expansion. Results are best described by recent unitary models in which the pion cloud plays a dominant role. 相似文献
146.
Low-molecular-weight organoiodine and organobromine compounds released by polar macroalgae--the influence of abiotic factors 总被引:1,自引:0,他引:1
Laturnus F Giese B Wiencke C Adams FC 《Fresenius' Journal of Analytical Chemistry》2000,368(2-3):297-302
The influence of temperature, light, salinity and nutrient availability on the release of volatile halogenated hydrocarbons was investigated in the Antarctic red macroalgal species Gymnogongrus antarcticus Skottsberg. Compared to standard culture condition, an increase in the release rates of iodocompounds was generally found for the exposure of the alga to altered environmental conditions. Macroalgae exhibited higher release rates after adaptation for two months to the changed factors, than after short-term exposure. Monitoring the release rates during a 24 h incubation period (8.25 h light, 15.75 h darkness) showed that changes between light and dark periods had no influence on the release of volatile halocarbons. Compounds like bromoform and 1-iodobutane exhibited constant release rates during the 24 h period. The formation mechanisms and biological role of volatile organohalogens are discussed. Although marine macroalgae are not considered to be the major source of biogenically-produced volatile organohalogens, they contribute significantly to the bromine and iodine cycles in the environment. Under possible environmental changes like global warming and uncontrolled entrophication of the oceans their significance may be increase. 相似文献
147.
We explore possible effects of vacuum energy on the evolution of black holes. If the universe contains a cosmological constant, and if black holes can absorb energy from the vacuum, then black hole evaporation could be greatly suppressed. For the magnitude of the cosmological constant suggested by current observations, black holes larger than 4×1024 g would accrete energy rather than evaporate. In this scenario, all stellar and supermassive black holes would grow with time until they reach a maximum mass scale of 6×1055 g, comparable to the mass contained within the present day cosmological horizon. 相似文献
148.
M.J.A. Van craen F.C. Adams L.J.A. Van Beek R.A.L. Vanden Berghe 《Spectrochimica Acta Part B: Atomic Spectroscopy》1984,39(12):1579-1581
Corrosion phenomena of Al-1 % Si bond wires, observed after life testing of certain transistors, are studied. The following information is derived from laboratory simulation tests: the kinetics of the corrosion process, information about the corrosion mechanism and critical parameters, especially the influence of the environmental gas and Si content and finally the identification of the corrosion products and their comparison with those found for the transistor. It is demonstrated, using a combination of several surface analytical techniques, that the A1 pitting corrosion is induced and enhanced by the presence of water as a transport medium and surface electrolyte in an oxygen-rich atmosphere, with chloride ions as a stimulating and activating species. The effect of 1 % Si in the wire consists in acceleration of the corrosion rate, and is probably due to grain boundary effects. All critical corrosion parameters could be traced in the transistor system by electron microscopy, laser microprobe mass analysis and residual gas (and moisture) analysis by mass spectrometry. 相似文献
149.
150.
David B. Adams 《Journal of Electron Spectroscopy and Related Phenomena》1978,13(2):123-130
A relaxation potential model has been used to study relaxation energies and shifts in core electron binding energies for some substituted alkenes and carbonyl compounds in terms of σ- and π-contributions.The conclusions from this study may be summarized as follows:(A) For the series R1R2C*CH2 and R1R2C*O: (i) The total shifts vary in a regular manner, similar to the shifts in saturated systems; (ii) The variation in σ-relaxation energies is greater than the variation in π-relaxation energies.(B) For the series R1R2CCH2 and R1R2CO: (i) There is little variation in the σ-relaxation energies; (ii) The π-relaxation energies show moderately large variations and the higher values are associated with unsaturated substituents which can donate π-electrons to the core-ionized atom via the conjugated π-system; (iii) The π-relaxation energies in the fluorinated systems are similar to those in the unsubstituted molecules; and (iv) The large -ve π-shift in the fluorinated systems results from a ground state build up of electron density at the site of core ionization. 相似文献