A study in Crystal engineering: Solid-state photodimerization of chloro- and methyl-coumarins

Use of chloro and methyl substitution in crystal engineering and their interchangeability in terms of mode of packing have been examined in a series of substituted coumarins. Photoreactivity in the solid state lists been correlated with the crystallograhic structures of these coumarins. The packing of chloro-substituted aromatic compounds has been investigated by analysing the arrangement of 132 compounds. Results substantiate the use of the chloro group as a steering agent and show that the chloro and methyl groups are not always interchangeable.

A solid state pulsed NMR spectrometer

A 10 MHz pulsed NMR spectrometer, built using mostly solid state devices, is described. The pulse programmer provides 2-pulse, 3-pulse, saturation burst and Carr-Purcell sequences both in repetitive and manual modes of operation. The transmitter has a maximum power output of ∼ 2 kW with a 75 Ω output impedance termination. The total gain of the receiver system is around 120 dB with a minimum band width of 2 MHz. The recovery time of the receiver is ∼ 7 µsec. A two-channel boxcar integrator capable of working in the single channel, differential and double boxcar modes provides signal to noise ratio improvement. The sensitivity and the linearity of the boxcar integrator are ∼ 2 mV and ∼ 0.1% respectively.

On a linear steady-state system of equations in microcontinuum fluid mechanics

Galerkin representations and integral representations are obtained for the linearized system of coupled differential equations governing steady incompressible flow of a micropolar fluid. The special case of 2-dimensional Stokes flows is then examined and further representation formulae as well as asymptotic expressions, are generated for both the microrotation and velocity vectors. With the aid of these formulae, the Stokes Paradox for micropolar fluids is established.

Steady state design of a sequence of sparger reactors

Abstract is not available.

A detailed study of Li-DNA fibres at various salt concentrations reveals a non-helical B-DNA and a possible similarity of solution and solid state structures

A thorough investigation of salt concentration dependence of lithium DNA fibres is made using X-ray diffraction. While for low salt the C-form pattern is obtained, crystalline B-type diffraction patterns result on increasing the salt concentration. The salt content in the gel (from which fibres are drawn) is estimated by equilibrium dialysis using the Donnan equilibrium principle. The salt range giving the best crystalline B pattern is determined. It is found that in this range meridional reflections occur on the fourth and sixth layer lines. In addition, the tenth layer meridian is absent at a particular salt concentration. These results strongly suggest the presence of non-helical features in the DNA molecule. Preliminary analysis of the diffraction patterns indicates a structural variability within the B-form itself. Further, the possibility of the structural parameters of DNA being similar in solid state and in solution is discussed.

State Dependent Attempt Rate Modeling of Single Cell IEEE 802.11 WLANs with Homogeneous Nodes and Poisson Arrivals

Analytical models of IEEE 802.11-based WLANs are invariably based on approximations, such as the well-known mean-field approximations proposed by Bianchi for saturated nodes. In this paper, we provide a new approach for modeling the situation when the nodes are not saturated. We study a State Dependent Attempt Rate (SDAR) approximation to model M queues (one queue per node) served by the CSMA/CA protocol as standardized in the IEEE 802.11 DCF. The approximation is that, when n of the M queues are non-empty, the attempt probability of the n non-empty nodes is given by the long-term attempt probability of n saturated nodes as provided by Bianchi's model. This yields a coupled queue system. When packets arrive to the M queues according to independent Poisson processes, we provide an exact model for the coupled queue system with SDAR service. The main contribution of this paper is to provide an analysis of the coupled queue process by studying a lower dimensional process and by introducing a certain conditional independence approximation. We show that the numerical results obtained from our finite buffer analysis are in excellent agreement with the corresponding results obtained from ns-2 simulations. We replace the CSMA/CA protocol as implemented in the ns-2 simulator with the SDAR service model to show that the SDAR approximation provides an accurate model for the CSMA/CA protocol. We also report the simulation speed-ups thus obtained by our model-based simulation.

Solid state and solution conformation of Boc-L-Met-Aib-L-Phe-OMe. Beta-turn conformation of a sequence related to an active chemotactic peptide analog

The conformation of the peptide Boc-L-Met-Aib-L-Phe-OMe has been studied in the solid state and solution by X-ray diffraction and 1H n.m.r., respectively. The peptide differs only in the N-terminal protecting group from the biologically active chemotactic peptide analog formyl-L-Met-Aib-L-Phe-OMe. The molecules adopt a type-II beta-turn in the solid state with Met and Aib as the corner residues (phi Met = -51.8 degrees, psi Met = 139.5 degrees, phi Aib = 58.1 degrees, psi Aib = 37.0 degrees). A single, weak 4----1 intramolecular hydrogen bond is observed between the Boc CO and Phe NH groups (N---O 3.25 A, N-H---O 128.4 degrees). 1H n.m.r. studies, using solvent and temperature dependencies of NH chemical shifts and paramagnetic radical induced line broadening of NH resonances, suggest that the Phe NH is solvent shielded in CDCl3 and (CD3)2SO. Nuclear Overhauser effects observed between Met C alpha H and Aib NH protons provide evidence of the occurrence of Met-Aib type-II beta-turns in these solvents.

Triplet-state Photophysics and Transient Photochemistry of Cyclic Enethiones A Laser Flash Photolysis Study

The triplets of four cyclic enethiones, including thiocoumarin, have been investigated by nanosecond laser flash photolysis. Data are presented for transient spectra and kinetics associated with triplets, quantum yields of intersystem crossing and singlet oxygen photosensitization. The quenching of the thiocoumarin triplet (A:, = 485 nm, E:,, = 8.8 x lo3 dm3 mol-' cm-'in benzene) by several olefins, amines and hydrogen donors occurs with rate constants of 107-5 x lo9 dm3 mol-' s-'; the lower limits of quantum yields ( c#+~) for the related photoreactions, estimated from ground-state depletion, are generally small (0.0-0.1 1 in benzene, except for good hydrogen donors, namely, p-methoxythiophenol and tri-n-butylstannane) . The radical anion of thiocoumarin (A,,, = 405-435 nm) is formed in two stages upon triplet quenching by triethylamine in acetonitrile; the fast component is the result of direct electron transfer to the triplet and the slower component is assigned to secondary photoreduction of the thione ground state by the a-aminoalkyl radical derived from the triethylamine radical-cation.

Preparative solid state chemistry. Recent developments

A survey of recent developments in preparative solid state chemistry shows that, with a knowledge of structural chemistry and reactivity patterns of solids, it is possible to synthesize a variety of new solids possessing novel structures. A distinction is made between synthesis ofnew solids and synthesis of solids bynew methods. Three new routes to solid state synthesis are recognized: the precursor method, and topochemical methods involving redox and ion-exchange reactions. The low-temperature topochemical methods enable synthesis of metastable phases that are inaccessible by the high temperature route. Several illustrative examples of solid state synthesis from the recent literature are presented.

Inbreeding in the State of Karnataka, South India

The inbreeding patterns and coefficient of inbreeding (F) of 3,350 new-borns in Bangalore, Karnataka were determined. A total of 29.24% were born of consanguineous marriages, F = 0.02313. Inbreeding was most common among the Hindus: 23.56% of their marriages were uncle-niece, F for the group was 0.02670.

Binding of three molecules in the excited state

t is shown that three neutral molecules can form a stable trimer if one of them is in the excited state. The formation of termolecular electron donor-acceptor complexes of sequence DDA and DAA arises from charge-resonance interaction.

Role of conformational dynamics in kinetics of an enzymatic cycle in a nonequilibrium steady state

Enzyme is a dynamic entity with diverse time scales, ranging from picoseconds to seconds or even longer. Here we develop a rate theory for enzyme catalysis that includes conformational dynamics as cycling on a two-dimensional (2D) reaction free energy surface involving an intrinsic reaction coordinate (X) and an enzyme conformational coordinate (Q). The validity of Michaelis-Menten (MM) equation, i.e., substrate concentration dependence of enzymatic velocity, is examined under a nonequilibrium steady state. Under certain conditions, the classic MM equation holds but with generalized microscopic interpretations of kinetic parameters. However, under other conditions, our rate theory predicts either positive (sigmoidal-like) or negative (biphasic-like) kinetic cooperativity due to the modified effective 2D reaction pathway on X-Q surface, which can explain non-MM dependence previously observed on many monomeric enzymes that involve slow or hysteretic conformational transitions. Furthermore, we find that a slow conformational relaxation during product release could retain the enzyme in a favorable configuration, such that enzymatic turnover is dynamically accelerated at high substrate concentrations. The effect of such conformation retainment in a nonequilibrium steady state is evaluated.

The study of oxidation state of manganese in lead oxyhalide glasses by optical spectroscopy

Abstaract is not available.

Photodimerization of coumarins in the solid state

Photochemical dimerization of 7-methoxycoumarin occurs in the solid state to give high yields of a syn-head-to-tail dimer although the potentially reactive double bonds are not favourably oriented in the crystal of the monomer.