Prop-2-ynyl as a protective group for carboxylic acids: A mild method for the highly selective deprotection of prop-2-ynyl esters using tetrathiomolybdate

It is shown that prop-2-ynyl esters are useful protecting groups for carboxylic acids and that they are selectively deprotected in the presence of other esters on treatment with tetrathiomolybdate under mild conditions.

Gauge theory of a group of diffeomorphisms. II. The conformal and de Sitter groups

The extension of Hehl's Poincaré gauge theory to more general groups that include space-time diffeomorphisms is worked out for two particular examples, one corresponding to the action of the conformal group on Minkowski space, and the other to the action of the de Sitter group on de Sitter space, and the effect of these groups on physical fields.

Systematic stability analysis of the renormalization group flow for the normal-superconductor-normal junction of Luttinger liquid wires

We study the renormalization group flows of the two terminal conductance of a superconducting junction of two Luttinger liquid wires. We compute the power laws associated with the renormalization group flow around the various fixed points of this system using the generators of the SU(4) group to generate the appropriate parametrization of an matrix representing small deviations from a given fixed point matrix [obtained earlier in S. Das, S. Rao, and A. Saha, Phys. Rev. B 77, 155418 (2008)], and we then perform a comprehensive stability analysis. In particular, for the nontrivial fixed point which has intermediate values of transmission, reflection, Andreev reflection, and crossed Andreev reflection, we show that there are eleven independent directions in which the system can be perturbed, which are relevant or irrelevant, and five directions which are marginal. We obtain power laws associated with these relevant and irrelevant perturbations. Unlike the case of the two-wire charge-conserving junction, here we show that there are power laws which are nonlinear functions of V(0) and V(2kF) [where V(k) represents the Fourier transform of the interelectron interaction potential at momentum k]. We also obtain the power law dependence of linear response conductance on voltage bias or temperature around this fixed point.

Watson-Crick pairing, the Heisenberg group and Milnor invariants

We study the secondary structure of RNA determined by Watson-Crick pairing without pseudo-knots using Milnor invariants of links. We focus on the first non-trivial invariant, which we call the Heisenber invariant. The Heisenberg invariant, which is an integer, can be interpreted in terms of the Heisenberg group as well as in terms of lattice paths. We show that the Heisenberg invariant gives a lower bound on the number of unpaired bases in an RNA secondary structure. We also show that the Heisenberg invariant can predict allosteric structures for RNA. Namely, if the Heisenberg invariant is large, then there are widely separated local maxima (i.e., allosteric structures) for the number of Watson-Crick pairs found.

Microbial transformation of a fungicide-derived amine, dimethyl-p-phenylene diamine by Alcaligenes DM4

Abstract Microbial transformation of N, N-dimethyl-p-phenylene diamine (DMPDA), a microbial product formed from the fungicide fenaminosulf (p-dimethylaminobenzenediazo sodium sulfonate) was studied by enriching microbes in soils treated with the amine. Microorganisms isolated from DMPDA-treated soil belonged to the genera of Micrococcus, Alcaligenes, and Corynebacterium. Of the various isolates, Alcaligenes DM4 showed maximal growth on DMPDA utilizing it as sources of carbon and nitrogen. When grown in mineral salts basal medium containing 0.05% DMPDA to serve as carbon and nitrogen sources, Alcaligenes DM4 grew exponentially up to 18 h. Even though the characterization of the complete pathway of microbial degradation of DMPDA could not be carried out due to the auto-oxidation of the compound, the initial transformation product of DMPDA by Alcaligenes DM4 has been identified as a dimer. The dimer is generated into the culture medium presumably by the extra-cellular oxidase of Alcaligenes DM4. It is suggested that the risk-benefit evaluation on the use of fenaminosulf is to be made taking into consideration the microbial transformations of the fungicide.

Gauge theory of a group of diffeomorphisms. I. General principles

Any (N+M)-parameter Lie group G with an N-parameter subgroup H can be realized as a global group of diffeomorphisms on an M-dimensional base space B, with representations in terms of transformation laws of fields on B belonging to linear representations of H. The gauged generalization of the global diffeomorphisms consists of general diffeomorphisms (or coordinate transformations) on a base space together with a local action of H on the fields. The particular applications of the scheme to space-time symmetries is discussed in terms of Lagrangians, field equations, currents, and source identities. Journal of Mathematical Physics is copyrighted by The American Institute of Physics.

Topochemical photodimerization of 7-acetoxycoumarin: the acetoxy group as a steering agent

Among the various substituted coumarins investigated only 7-acetoxycoumarin is observed to photodimerize topochemically in the crystalline state and this observation may be of importance in the context of "crystal engineering".

Partial purification and properties of a transamidinase from Lathyrus sativus seedlings. Involvement in homoarginine metabolism and amine interconversions

A transamidinase was purified 463-fold from Lathyrus sativus seedlings by affinity chromatography on homoarginine--Sepharose. The enzyme exhibited a wide substrate specificity, and catalysed the reversible transfer of the amidino groups from donors such as arginine, homoarginine and canavanine to acceptors such as lysine, putrescine, agmatine, cadaverine and hydroxylamine. The enzyme could not be detected in the seeds, and attained the highest specific activity in the embryo axis on day 10 after seed germination. Its thiol nature was established by strong inhibition by several thiol blockers and thiol compounds in the presence of ferricyanide. In the absence of an exogenous acceptor, it exhibited weak hydrolytic activity towards arginine. It had apparent mol.wt. 210000, and exhibited Michaelis--Menten kinetics with Km 3.0 mM for arginine. Ornithine competitively inhibited the enzyme, with Ki 1.0 mM in the arginine--hydroxylamine amidino-transfer reaction. Conversion experiments with labelled compounds suggest that the enzyme is involved in homoarginine catabolism during the development of plant embryo to give rise to important amino acids and amine metabolites. Presumptive evidence is also provided for its involvement in the biosynthesis of the guanidino amino acid during seed development. The natural occurrence of arcain in L. sativus and mediation of its synthesis in vitro from agmatine by the transamidinase are demonstrated.

Linalyl Acetate Is Metabolized by Pseudomonas incognita with the Acetoxy Group Intact

Metabolism of linalyl acetate by Pseudomonas incognita isolated by enrichment culture on the acyclic monoterpene alcohol linalool was studied. Biodegradation of linalyl acetate by this strain resulted in the formation of linalool, linalool- 8-carboxylic acid, oleuropeic acid, and A5-4-acetoxy-4-methyl hexenoic acid. Cells adapted to linalyl acetate metabolized linalyl acetate-8-aldehyde to linalool- 8-carboxylic acid, linalyl acetate-8-carboxylic acid, A5-4-acetoxy-4-methyl hexenoic acid, and geraniol-8-carboxylic acid. Resting cell suspensions previously grown with linalyl acetate oxidized linalyl acetate-8-aldehyde to linalyl acetate-8- carboxylic acid, A5-4-acetoxy-4-methyl hexenoic acid, and pyruvic acid. The crude cell-free extract (10,000 g of supernatant), obtained from the sonicate of linalyl acetate-grown cells, was shown to contain enzyme systems responsible for the formation of linalyl acetate-8-carboxylic acid and linalool-8-carboxylic acid from linalyl acetate. The same supernatant contained NAD-linked alcohol and aldehyde dehydrogenases involved in the formation of linalyl acetate-8-aldehyde and linalyl acetate-8-carboxylic acid, respectively. On the basis of various metabolites isolated from the culture medium, resting cell experiments, growth and manometric studies carried out with the isolated metabolites as well as related synthetic analogs, and the preliminary enzymatic studies performed with the cellfree extract, a probable pathway for the microbial degradation of linalyl acetate with the acetoxy group intact is suggested.

1- and 2-Chloromorphine. Halogenation of Morphine meta to the Free Phenolic Hydroxyl Group

Treatment of morphine in aqueous HCl at 70° with KIO3 yields a monochloromorphine, identified as 1-chloromorphine by spectroscopic means and by the fact that it, and its methyl ether 1-chlorocodeine, are different from 2-chloromorphine and 2-chlorocodeine prepared from 2-aminomorphine of unequivocally established structure. Formation of 1-chloromorphine and the previously known 1-bromomorphine involves entry of the halogen into the position meta to the free phenolic hydroxyl. Possible mechanistic interpretations of this unusual orientation are discussed.

Theoretical studies of lithium bonding in lithium chloride/aliphatic amine complexes

In the systematic study of amine … LiCl [amines = NH3, CH3NH2, (CH3)2NH] complexes the possibility of an ion-pair structure and the effect of methylation on the stabilization energy is investigated. ΔEis evaluated by the SCF/4-31G method and augmented by the approximate dispersion energy calculated perturbationally. The interaction energy decreases with the increasing number of methyl groups in the amine. The dispersion energy plays a negligible role in the stabilization of complexes. None of the systems studied are ion pairs; their Li bonds are of a so-called molecular type. Due to the divergence of the multipole expansion, the attempt to correct the 4-31G stabilization energies via the electrostatic energy fails. The relative order of the ΔE in the series of complexes is verified instead in the extended basis set calculation. The lithium bonds are compared with their H-bonded analogues.

Topochemical photo-dimerization of 7-acetoxycoumarin - the acetoxy group as a steering agent

Among the various substituted coumarins investigated only 7-acetoxycoumarin is observed to photodimerize topochemically in the crystalline state and this observation may be of importance in the context of "crystal engineering".

Thermal decomposition of ethyl and isopropyl amine perchlorates

Thermal decomposition of ethyl and isopropyl amine perchlorates has been studied by methods such as DTA, TG, isothermal weight loss measurements and the decomposition products have been analyzed in a mass spectrometer. Activation energy values for thermal decomposition have been calculated fromagr-t plots. The proton transfer dissociation mechanism proposed for the thermal decomposition of ammonium perchlorate (AP) has been extended to explain the decomposition products of these twosubstituted amine perchlorates.

Invariance group properties and exact solutions of equations describing time-dependent free surface flows under gravity

Using the method of infinitesimal transformations, a 6-parameter family of exact solutions describing nonlinear sheared flows with a free surface are found. These solutions are a hybrid between the earlier self-propagating simple wave solutions of Freeman, and decaying solutions of Sachdev. Simple wave solutions are also derived via the method of infinitesimal transformations. Incomplete beta functions seem to characterize these (nonlinear) sheared flows in the absence of critical levels.

Study of linear and nonlinear optical properties of dendrimers using density matrix renormalization group method

We have used the density matrix renormalization group (DMRG) method to study the linear and nonlinear optical responses of first generation nitrogen based dendrimers with donor acceptor groups. We have employed Pariser–Parr–Pople Hamiltonian to model the interacting pi electrons in these systems. Within the DMRG method we have used an innovative scheme to target excited states with large transition dipole to the ground state. This method reproduces exact optical gaps and polarization in systems where exact diagonalization of the Hamiltonian is possible. We have used a correction vector method which tacitly takes into account the contribution of all excited states, to obtain the ground state polarizibility, first hyperpolarizibility, and two photon absorption cross sections. We find that the lowest optical excitations as well as the lowest excited triplet states are localized. It is interesting to note that the first hyperpolarizibility saturates more rapidly with system size compared to linear polarizibility unlike that of linear polyenes.