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1.
Marye Anne Fox Arvind C. Ranade Ismail Madany 《Journal of organometallic chemistry》1982,239(2):269-277
High yield nucleophilic addition ensues upon mixing tetrahydrofuran solutions of benzyllithium or cyclooctadienyllithium and anthracene at low temperatures At least part of this addition proceeds by a single electron transfer pathway. Photolysis of the resulting adducts leads to the elimination of lithium hydride, giving net nucleophilic substitution in approximately 50% yield. The analogous reaction fails with naphthalene, where photolysis of the organolithium/ arene mixture leads to dimeric products derived from the organolithium. 相似文献
2.
De Jonghe S Lamote I Venkataraman K Boldin SA Hillaert U Rozenski J Hendrix C Busson R De Keukeleire D Van Calenbergh S Futerman AH Herdewijn P 《The Journal of organic chemistry》2002,67(3):988-996
The synthesis of a new series of D-erythro-homoceramide analogues is described. Several synthetic approaches were investigated. Homoceramides can be successfully synthesized from L-homoserine as chiral building block and a protected Weinreb-amide as a key intermediate. The synthesis of short-chain analogues with a heptyl side chain, as well as with a phenyl residue in the sphingoid part (instead of the naturally occurring tridecyl side chain), was effected. The homoceramides 15-17 and 24 were investigated for their potential to reverse the inhibitory effect of fumonisin B(1) on axonal growth. Unfortunately, none of the tested compounds showed any biological activity due to their lack of metabolism to glucosylhomoceramide. 相似文献
3.
This paper is a straightforward generalization of Maierle-Harris proposal regarding parity implications on the superpositions of chiral states of a molecule. It is shown that the inclusion of electric quadrupole and magnetic dipole interactions removes several of restrictions on the preparation of superpositions of mid R:L and mid R:R states of a chiral molecule. It is also found that the dephasing of mid R:L and mid R:R superpositions, due to the spontaneous emission from the chiral molecule, has opposing contributions from electric quadrupole-magnetic dipole and electric dipole interactions. 相似文献
4.
1:2-Benzanthracene and the 3′-methyl derivative have been prepared by Raney nickel reduction of the sulphuric esters of the leuco derivatives of 1:2-benzanthraquinone and 4′-chloro-3′-methyl-1:2-benzanthraquinone, followed by dehydrogenation. 3-Hydroxy-1:2-benzanthraquinone was methylated in the 4-position by formaldehyde, sodium hydrosulphite and sodium hydroxide solution (the Marschalk reaction). Simultaneous reduction of the nuclear hydroxyl and quinone groups was effected by Raney nickel reduction of the trisulphuric ester of 3:9:10-trihydroxy-4-methyl-1:2-benzanthracene, and the resultant hexahydro-4-methyl-1:2-benzanthracene was dehydrogenated to 4-methyl-1:2-benzanthracene. The preparation of 3:4:9:10-dibenzopyrene from Mayvat brilliant red AF by Raney nickel reduction of the sulphuric ester of the leuco derivative and subsequent dehydrogenation is described. 相似文献
5.
A very simple and highly specific method for the determination of cysteine and penicillamine is presented. Treatment with 1,1'-thiocarbonyldiimidazole in slightly basic solutions converts cysteine rapidly and quantitatively to a very stable derivative, 2-thioxothiazolidine-4-carboxylic acid, which is not formed by thiols or amines. The cyclic derivative has a characteristic UV spectrum with a maximum at 272 nm and it can be quantified by one of two ways. (1) When only inorganic ions and common additives are present, a spectrophotometer or a plate reader capable of handling multiple samples is sufficient to estimate cysteine in the concentration range of 2-150 muM. Penicillamine is determined similarly by cyclization to 5,5-dimethyl-2-thioxothiazolidine-4-carboxylic acid. The method is also applicable to derivatives of cysteine modified only at the carboxyl group. (2) To determine cysteine in complex mixtures, a liquid chromatograph connected to a UV detector is used. The elution is rapid with well-separated peaks for the thiazolidine derivatives. The detection limit is 2 pmole of cysteine or penicillamine per injection and the detector response is linear up to 1 nmole. The usefulness of the method is demonstrated by determining cysteine and penicillamine in capsules and by measuring cysteine in a dietary supplement. 相似文献
6.
John B. Hynes Alenka Tomai
Arvind Kumar Veena Kumar James H. Freisheim 《Journal of heterocyclic chemistry》1991,28(8):1981-1986
A series of thirty eight 2,4-diaminoquinazolines having diverse substitution patterns on the aromatic ring was evaluated for inhibitory activity against dihydrofolate reductase (DHFR) obtained from a human lymphoblast cell line. Many of these compounds were also evaluated as inhibitors of rat liver DHFR under the same experimental conditions. In most instances the results obtained with each enzyme were comparable indicating that the rodent enzyme is a suitable model for the human DHFR as far as the determination of I50 values is concerned. The results demonstrate that relatively simple 5-substituted- or 5,6-disubstituted-2,4-diaminoquinazolines can be potent DHFR inhibitors. The presence of a nonpolar substituent at position 7 or 8 was highly detrimental to inhibitory potency. 相似文献
7.
A. Miele B. P. Mohanty P. Venkataraman Y. M. Kuo 《Journal of Optimization Theory and Applications》1982,38(1):97-109
This paper contains general transformation techniques useful to convert minimax problems of optimal control into the Mayer-Bolza problem of the calculus of variations [Problem (P)]. We consider two types of minimax problems: minimax problems of Type (Q), in which the minimax function depends on the state and does not depend on the control; and minimax problems of Type (R), in which the minimax function depends on both the state and the control. Both Problem (Q) and Problem (R) can be reduced to Problem (P).For Problem (Q), we exploit the analogy with a bounded-state problem in combination with a transformation of the Jacobson type. This requires the proper augmentation of the state vectorx(t), the control vectoru(t), and the parameter vector , as well as the proper augmentation of the constraining relations. As a result of the transformation, the unknown minimax value of the performance index becomes a component of the parameter vector being optimized.For Problem (R), we exploit the analogy with a bounded-control problem in combination with a transformation of the Valentine type. This requires the proper augmentation of the control vectoru(t) and the parameter vector , as well as the proper augmentation of the constraining relations. As a result of the transformation, the unknown minimax value of the performance index becomes a component of the parameter vector being optimized.In a subsequent paper (Part 2), the transformation techniques presented here are employed in conjunction with the sequential gradient-restoration algorithm for solving optimal control problems on a digital computer; both the single-subarc approach and the multiple-subarc approach are discussed.This research was supported by the National Science Foundation, Grant No. ENG-79-18667, and by Wright-Patterson Air Force Base, Contract No. F33615-80-C3000. This paper is a condensation of the investigations reported in Refs. 1–7. The authors are indebted to E. M. Coker and E. M. Sims for analytical and computational assistance. 相似文献
8.
Gerd Wellenreuther Venkataraman Parthasarathy Wolfram Meyer‐Klaucke 《Journal of synchrotron radiation》2010,17(1):25-35
In biological systems, X‐ray absorption spectroscopy (XAS) can determine structural details of metal binding sites with high resolution. Here a method enabling an automated analysis of the corresponding EXAFS data is presented, utilizing in addition to least‐squares refinement the prior knowledge about structural details and important fit parameters. A metal binding motif is characterized by the type of donor atoms and their bond lengths. These fit results are compared by bond valance sum analysis and target distances with established structures of metal binding sites. Other parameters such as the Debye–Waller factor and shift of the Fermi energy provide further insights into the quality of a fit. The introduction of mathematical criteria, their combination and calibration allows an automated analysis of XAS data as demonstrated for a number of examples. This presents a starting point for future applications to all kinds of systems studied by XAS and allows the algorithm to be transferred to data analysis in other fields. 相似文献
9.
Ravishankar Bhat Sharanabasava Ganachari Raghunandan Deshpande G. Ravindra A. Venkataraman 《Journal of Cluster Science》2013,24(1):107-114
In this research paper, we report on the rapid synthesis of silver nanoparticles using dried areca nut (Areca catechu). The microwave exposed aqueous areca nut powder when treated with the aqueous silver salt solution yielded irregular shaped silver nanoparticles. The formation and morphology of the nanoparticles are studied using UV–visible spectroscopy, field emission scanning electron microscopy, transmission electron microscopy and atomic force microscopy. The X-ray diffraction studies and energy dispersive X-ray analysis indicate that the particles are crystalline in nature. The understanding of capping of biological moiety is derived from Fourier transform infrared spectroscopy and the thermogravimetric analysis. The green chemistry approach for the synthesis of silver nanoparticles is modest, amenable for large scale commercial production. Further the biologically synthesized silver nanoparticles are known for their potential antibacterial activity. 相似文献
10.
J. M. Kirkpatrick R. Venkataraman B. M. Young 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(2):1005-1010
The Currie formulation for minimum detectable activity (MDA) has served for decades as the standard method for estimating radiological detection limits-it is simple and statistically defendable. It does, however, lack a means to account for the effects of systematic uncertainties. In recent years we have seen various efforts to incorporate systematic uncertainties into an MDA framework. Perhaps most notable of these is the recent ISO standard 11929 for the determination of characteristic limits in ionizing radiation measurements. This standard brings a Bayesian perspective to the problem of characteristic limits in radiation measurements that are in many ways both welcome and long overdue. In this paper, however, we note some apparent drawbacks to the ISO 11929 approach. Namely, for small values of the systematic uncertainty the correction it makes to the Currie MDA is negligible, while for large systematic uncertainties the calculated MDA values can become infinite. In between these two extremes, the user has little basis for evaluating the reliability of the result. To address these issues, we consider the problem from a new approach, developing a straightforward phenomenological statistical model of the MDA that treats systematic uncertainties explicitly. We compare predictions from our model with results of the ISO 11929 formulation as well as the traditional Currie approach. Finally, some recommendations for alternative handling of the MDA in the face of significant systematic uncertainties are presented. 相似文献