Facile Synthesis of beta-Amino Disulfides, Cystines, and Their Direct Incorporation into Peptides

Herein, we report a simple and efficient methodology for the synthesis of beta-amino disulfides by regioselective ring opening of sulfamidates with benzyltriethylammonium tetrathiomolybdate [BnNEt3](2)MoS4. Stability and reactivity of different protecting groups under the reaction conditions have been discussed. This methodology has also been extended to serine and threonine derived sulfamidates to furnish cystine and 3,3'-dimethyl cystine derivatives.

Synthesis of plane linkages to generate functions of two variables using point position reductionâII. Sliding inputs and outputs

The paper presents simple graphical procedures for the position synthesis of plane linkage mechanisms with sliding inputs and output to generate functions of two independent variables. The procedures are based on point position reduction and permit synthesis of the linkage to satisfy up to five arbitrarily selected precision positions.

Mechanism of aminoacylation of tRNA : Influence of spermine on the kinetics of aminoacyl-tRNA synthesis by isoleucyl- and valyl-tRNA synthetases from Mycobacterium smegmatis

Isoleucyl-tRNA synthetase has been purified to homogeneity from Mycobacterium smegmatis. The influence of spermine on the kinetics of valyl-tRNA and isoleucyl-tRNA formation has been investigated by Cleland's method (Cleland, W.W. (1963) Biochim. Biophys. Acta 67, 104–137, 173–187, 188–196). The results suggest that in the presence of spermine and suboptimal concentration of Mg2+, the formation of valyl-tRNA and isoleucyl-tRNA follows a sequential* mechanism. In the presence of an optimal concentration of Mg2+, both valyl-tRNA and isoleucyl-tRNA formation proceeds by a ping-pong mechanism. However, in the presence of spermine and optimal concentrations of Mg2+, valyl-tRNA formation follows the ping-pong mechanism while isoleucyl-tRNA formation follows the sequential mechanism.

Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.

A Convenient Route for the Synthesis of Complex Metal Oxides Employing Solid-Solution Precursors

Synthesis of complex metal oxides by the thermal decomposition of solid-solution precursors (formed by isomorphous compounds of component metals) has been investigated since the method enables mixing of cations on an atomic scale and drastically reduces diffusion distances to a few angstroms. Several interesting oxides such as Ca2Fe03,5C, aCoz04,C a2C0205a, nd Ca,FeCo05 have been prepared by this technique starting from carbonate solid solutions of the type Ca,-,Fe,C03, Cal-,Co,C03, and Ca,-,,M,M'yC03 (M, M' = Mn, Fe, Co). The method has been extended to oxalate solid-solution precursors, and the possibility of making use of other kinds of precursor solid solutions is indicated.

Amide-catalysed isomerisation of 5,6-dihydroisoquinolines: a novel synthesis of 1,2-dihydroisoquinolines

Knoevenagel condensation of 2-acylcyclohexanones or 2-ethoxycarbonylcyclohexanone with either cyanoacetamide or malononitrile followed by silver salt alkylation gave the 5,6,7,8-tetrahydroisoquinolines (3a–i). Chromic acid oxidation of the 5,6,7,8-tetrahydroisoquinolines (3a–i) to the corresponding tetralones (4a–i) followed by sodium borohydride reduction and p-toluenesulphonic acid-catalysed dehydration of the resulting alcohols (5a–i) gave the 5,6-dihydroisoquinolines (6a–i). Reaction of 5,6-dihydroisoquinolines (6a–g) with potassium amide in liquid ammonia gave a mixture of the 1,3-dihydroisoquinolines (7a–g) and the isoquinolines (8a–g). The C-1 unsubstituted 1,2-dihydroisoquinoline (7c) was found to be very unstable. In the case of the 5,6-dihydroisoquinolines (6h and 6i), reaction of potassium amide in liquid ammonia resulted in a mixture of 1-aminoisoquinoline (9) and the isoquinolines (8h and 8i). All the above compounds have been characterised by spectral data. A probable pathway for the formation of the 1,2-dihydroisoquinolines (7a–g) and the isoquinolines (8a–i) is suggested.

Role of heme in the synthesis of cytochrome c oxidase in Neurospora crassa

The role of heme in the synthesis of cytochrome c oxidase has been investigated in the mold Neurospora crassa. Iron-deficient cultures of the mold have low levels of cytochrome oxidase and delta-aminolevulinate dehydratase, the latter being the rate-limiting enzyme of the heme-biosynthetic pathway in this organism. Addition of iron to the iron-deficient cultures results in an immediate increase in the levels of delta-aminolevulinate dehydratase followed by an increase in the rate of heme synthesis and cytochrome oxidase levels. The rate of precursor labeling of the mitochondrial subunits of cytochrome oxidase is decreased preferentially under conditions of iron deficiency and addition of iron corrects this picture. Exogenous hemin addition which prevents iron-mediated induction of delta-aminolevulinate dehydratase also inhibits the increase in the activity of cytochrome oxidase and the enhanced precursor labeling of the mitochondrial subunits of cytochrome oxidase. Protein synthesis on mitoribosomes measured in vivo and in vitro is decreased under conditions of heme deficiency. Hemin addition in vitro to mitochondrial lysates prepared from heme-deficient mycelia restores a near normal rate of protein synthesis. It is concluded that heme is required for the optimal rate of translation on mitoribosomes.

Aromatic amines and their derivatives. Part 3. The synthesis and crystal structure of 4,4-NN-tetramethyl-NN-dinitroso-2,2-methylenedianiline

The synthesis of 4,4,N,N-tetramethyl-NN-dinitroso-2,2-methylenedianiline (1) by the route p-MeC6H4NH2+ HCHO + OH–(p-MeC6H4NMe)2CH2(7b); (7b)+ acid at 70 °C 4,N-dimethyl-6-(N-methyl-p-toluidinomethyl)aniline (4b); (4b)+ acid at 130 °C 4,4,NN-tetramethyl-2,2-methylenedianiline (3b); (3b)+ HNO2(1), is described. Aspects of the 1H n.m.r. spectra of the above and related compounds are discussed. A crystal-structure analysis of compound (1) shows one of the N-nitroso-groups to be disordered with the endo-form being in preponderance (4 : 1) over the exo-form. The other N-nitroso-group is exclusively exo in the solid state. There is little or no resonance between the benzene ring and the nitroso-group attached to the ring, the two groups being almost perpendicular to each other. In one of the N-nitroso-groups, the nitrogen atom deviates significantly from the plane of the benzene ring to which it is attached. Both amide nitrogen atoms show some pyramidal character.

Influence of rapid thermal annealing (RTA) on the structural and electrical properties of SnS films

The performance of optoelectronic devices critically depends on the quality of active layer. An effective way to obtain a high quality layers is by creating excess of metal atoms through various heat treatments. Recently, rapid thermal annealing (RTA) has proved a versatile technique for the post-treatment of semiconductor materials as compared to other techniques due to its precise control over the resources. Thus, we carried out a set of experiments on SnS films to explore the influence of RTA treatment on their properties. From these experiments we noticed that the films treated at 400 °C for 1 min in N2 atmosphere have a low electrical resistivity of ~5 Ωcm with relatively high Hall mobility and carrier density of 99 cm2/Vs and 1.3 × 1016 cm−3, respectively. The observed results, therefore, emphasise that it is possible to obtain good quality SnS films through RTA treatment without disturbing their crystal structure.

Interactions of aromatic mannosyl disulfide derivatives with Concanavalin A: synthesis, thermodynamic and NMR spectroscopy studies

α-d-Mannopyranosyl units were attached to an aromatic scaffold through disulfide linkages to obtain mono- to trivalent glycosylated ligands for lectin binding studies. Isothermal titration calorimetric (ITC) measurements indicated that binding affinities of these derivatives to Concanavalin A (Con A) were comparable to or slightly higher than that of methyl α-d-mannopyranoside (Ka values in the range of 104 M−1). The stoichiometries of the lectin-ligand complexes were in agreement with the formal valencies (1–3) of the respective ligands indicating cross-linking in interactions with the di- and trivalent derivatives. Multivalency effects could not, however, be observed with the latter. These ligands were shown to bind to the carbohydrate binding site of Con A using saturation transfer difference (STD) NMR competition experiments.

Macromolecular synthesis in mycobacteriophage I3 infected cells

DNA-, RNA- and protein synthesis have been studied inMycobacterium smegmatis cells infected with phage 13. The macromolecular synthesis continued until the end of latent period. Early RNA and protein synthesis were necessary prior to the commencement of DNA replication. The infecting phage DNA sedimented as larger than unit length of genome, after initiation of DNA synthesis. Although the host DNA was not degraded, 90 percent of the RNA synthesized after phage infection hybridized to phage DNA.

Rapid transfection assay for screening mutagens and carcinogens

Testing for mutagenicity and carcinogenicity has become an integral part of the toxicological evaluation of drugs and chemicals. Standard carcinogenicity tests in vivo require both large numbers of animals and prolonged experiments. To circumvent these problems, several rapid tests have been developed for preliminary screening of mutagens and carcinogens in vitro. Ames and his associates, the first to develop a mutation test, used mutant strains of Salmonella typhimurium [1]. Mutation tests with Escherichia coli, Bacillus subtilis, Neurospora crassa and Saccharomyces cerevisiae, and DNA-repair tests with E. coli and B. subtilis, have been developed. Cytogenetic assays, in vivo as well as in vitro, in both plant and animal systems, are also used to detect potential mutagens and carcinogens. Transfection is inhibited by base mutation, cleavage of DNA, loss of cohesive ends, interaction with histones, spermidine, nalidixic acid, etc. [3]. The efficiency of transfection is affected by temperature, DNA structure and the condition of the competence of the recipient cells [3]. Transfection assays with phages MS: RNA and ~i, x 174-DNA have been reported [15]. A fast and easy transfection assay using colitis bacteriophage DNA is reported in this communication.

Karnaugh map analysis and synthesis of threshold functions

A unate function can easily be identified on a Karnaugh map from the well-known property that it cons ist s only ofess en ti al prime implicante which intersect at a common implicant. The additional property that the plot of a unate function F(x, ... XII) on a Karnaugh map should possess in order that F may also be Ivrealizable (n';:; 6) has been found. It has been sh own that the I- realizability of a unate function F corresponds to the ' compac tness' of the plot of F. No resort to tho inequalities is made, and no pre-processing such as positivizing and ordering of the given function is required.

A note on synthesis of the general, two-degree-of-freedom linkage

A graphical method is presented for synthesis of the general, seven-link, two-degree-of-freedom plane linkage to generate functions of two variables. The method is based on point position reduction and permits synthesis of the linkage to satisfy upto six arbitrarily selected precision positions.