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61.
A theoretical study of the electronic structure of the photoactive yellow protein (PYP) model chromophore, para-coumaric acid (p-CA), is presented. Electronically excited states of the phenolate and carboxylate isomers of the deprotonated p-CA are characterized by high-level ab initio methods including state-specific and multistate multireference pertrubation theory (SS-CASPT2, and MS-CASPT2), equation-of-motion coupled-cluster methods with single and double substitutions (EOM-CCSD) and with an approximate account of triple excitations (CC3). We found that the two isomers have distinctly different patterns of ionization and excitation energies. Their excitation energies differ by more than 1 eV, in contradiction to the experimental report [Rocha-Rinza et al., J. Phys. Chem. A 113, 9442 (2009)]. The calculations confirm metastable (autoionizing) character of the valence excited states of both phenolate and carboxylate isomers of p-CA(-) in the gas phase. The type of resonance is different in the two forms. In the phenolate, the excited state lies above the detachment continuum (a shape resonance), whereas in the carboxylate the excited π→π(*) state lies below the π-orbital ionization continuum, but is above the states derived from ionization from three other orbitals (Feshbach resonance). The computed oscillator strength of the bright electronic state in the phenolate is higher than in the carboxylate, in agreement with Hu?ckel's model predictions. The analysis of photofragmentation channels shows that the most probable products for the methylated derivatives of the phenolate and carboxylate forms of p-CA(-) are CH(3), CH(2)O and CH(3), CH(2)O, CO(2), respectively, thus suggesting an experimental probe that may discriminate between the two isomers. 相似文献
62.
Shetty Kalidas Korus roger A. Crawford Dom L. 《Applied biochemistry and biotechnology》1989,(1):825-843
Glycine max was used as a model plant cell suspension culture to establish relationships among growth kinetics, phenolics production,
elicitor action, and peroxidase activity. Timing of elictor addition through monitoring of peroxidase provided an excellent
means of optimizing yields of phenolics and reduced the time span during which phenolics were formed, negating the need for
a secondary production medium. We have also determined that calcium and other cellular effectors like polyamines and organic
osmolytes, when used in conjunction with elicitors, enhance phenolics production. Calcium directly enhanced elicitation, whereas
polyamines and other osmolytes such as glycerol and proline extended cell viability. The study also demonstrated potential
for enhancing secondary metabolite production by a combination of elicitation, cell viability stabilizers, and by addition
of nutrients at the time of elicitation. 相似文献
63.
64.
Gupta Rajinder K. Deobald Lee A. Crawford Don L. 《Applied biochemistry and biotechnology》1990,24(1):899-911
Applied Biochemistry and Biotechnology - Coal metabolizingPseudomonas cepacia DLC-07 was isolated from soil and shown to use soluble lignite coal as a carbon/energy source.Pseudomonas modified coal... 相似文献
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E. Man�� J. A. Behr J. Billowes T. Brunner M. Brodeur F. Buchinger J. E. Crawford J. Dilling S. Ettenauer C. D. P. Levy A. Voss M. R. Pearson 《Hyperfine Interactions》2011,199(1-3):357-363
Collinear laser spectroscopy with reverse-extracted cooled bunched beams was performed at TRIUMF with radioactive ion beams. Surface-ionized 78,78mRb ions were injected into TITAN??s cooler-buncher, and reverse-extracted to the laser beam line. There they were neutralised and excited with a counter-propagating laser beam. The fluorescence signal from the D 2 line was recorded with a photomultiplier tube. The cooler provided typically 50 ion bunches per second, with each bunch containing approximately 105 ions, temporally distributed with a 1.6 ??s width. A hardware gate was set on the signal, suppressing the background by four orders of magnitude. 相似文献
68.
James H. Hunter Matthew J. Anderson Isaline F. S. F. Castan Jessica S. Graham Catherine L. A. Salvini Harriet A. Stanway-Gordon James J. Crawford Andrew Madin Garry Pairaudeau Michael J. Waring 《Chemical science》2021,12(27):9475
DNA encoded libraries (DELs) represent powerful new technology for finding small molecule ligands for proteins and are increasingly being applied to hit finding in medicinal chemistry. Crucial to the synthesis of high quality DELs is the identification of chemical reactions for their assembly that proceed with very high conversion across a range of different substrates, under conditions compatible with DNA-tagged substrates. Many current chemistries used in DEL synthesis do not meet this requirement, resulting in libraries of low fidelity. Amide couplings are the most commonly used reaction in synthesis of screening libraries and also in DELs. The ability to carry out highly efficient, widely applicable amide couplings in DEL synthesis would therefore be highly desirable. We report a method for amide coupling using micelle forming surfactants, promoted by a modified linker, that is broadly applicable across a wide range of substrates. Most significantly, this works exceptionally well for coupling of DNA-conjugated carboxylic acids (N-to-C) with amines in solution, a procedure that is currently very inefficient. The optimisation of separate procedures for coupling of DNA-conjugated acids and amines by reagent screening and statistically driven optimisation is described. The generality of the method is illustrated by the application to a wide range of examples with unprecedented levels of conversion. The utility of the (N-to-C) coupling of DNA-conjugated acids in DEL synthesis is illustrated by the three cycle synthesis of a fully DNA-encoded compound by two cycles of coupling of an aminoester, with intermediate ester hydrolysis, followed by capping with an amine. This methodology will be of great utility in the synthesis of high fidelity DELs.Highly efficient forward and reverse on-DNA amide couplings were developed exploiting hydrophobic linkers in combination with the micelle forming surfactant TPGS-750M. The method is highly effective for a wide range of substrates in the synthesis of DNA-encoded libraries. 相似文献
69.
We study the structure of a uniformly randomly chosen partial order of width 2 on n elements. We show that under the appropriate scaling, the number of incomparable elements converges to the height of a one dimensional Brownian excursion at a uniformly chosen random time in the interval [0, 1], which follows the Rayleigh distribution. 相似文献
70.
An investigation of inclusivepp→π?+? in terms of the covariant Boltzmann factor (BF) including the chemical potential μ indicates a) that the temperatureT increases less rapidly than expected from Stefan's law, b) that a scaling property holds for the fibreball velocity of π? secondaries, leading to a multiplicity law like ~E cm 1/2 at high energy, and c) that μπ is related to the quark mass: μπ=2m q ?m π the quark massm q determined by \(T_{\pi ^ - } \) at \(\bar pp\) threshold beingm q =3Tπ?330 MeV. Because ofthreshold effects \(T_{\bar p}< T_{\pi ^ - } \) , whereas \({{\mu _p } \mathord{\left/ {\vphantom {{\mu _p } {\mu _{\pi ^ - } }}} \right. \kern-0em} {\mu _{\pi ^ - } }} \simeq {3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-0em} 2}\) as expected from the quark contents of \(\bar p\) and π. The antinuclei \(\bar d\) and \({{\bar t} \mathord{\left/ {\vphantom {{\bar t} {\overline {He^3 } }}} \right. \kern-0em} {\overline {He^3 } }}\) observed inpp events are formed by coalescence of \(\bar p\) and \(\bar n\) produced in thepp collision. Semi-empirical formulae are proposed to estimate multiplicities of π?, \(\bar p\) and antinuclei. 相似文献