An infrared spectroscopic study of the phase transitions of crystalline aromatic donor-acceptor complexes involving a pseudoplastic state

Variable temperature i.r. spectroscopic studies of weak pi-donor-pi-acceptor complexes in the crystalline state indicate that the complexes undergo order-disorder transitions, the disorder being caused by molecular motion. Thermodynamic data on the phase transitions along with the spectral data suggest that the high-temperature crystalline forms of the complexes are likely to be pseudoplastic.

Coherence transfer via longitudinal spin order generalized pulse pair filtering for pure phase two-dimensional NMR spectroscopy

A generalized pulse pair has been suggested in which the longitudinal spin order is retained and the transverse components cancelled by random variation of the interval between pulses, in successive applications of the two-dimensional NMR algorithm. This method leads to pure phases and has been exploited to provide a simpler scheme for two-spin filtering and for pure phase spectroscopy in multiple-quantum-filtered two-dimensional NMR experiments.

Lead-acid batteries for partial-state-of-charge applications

2 V/40 Ah valve-regulated lead-acid (VRLA) cells have been constructed with negative plates employing carbon black as well as an admixture of carbon black fumed silica as additives in negative active material for partial-state-of-charge (PSoC) applications. Electrical performance of such cells is compared with conventional 2 V/40 Ah VRLA cells for PSoC operation. Active material utilization has been found to be higher for carbon-black fumed-silica mixed negative plates while formation is faster for cells with carbon-black mixed negative plates. Both faradaic efficiency and percentage capacity delivered have been found to be higher for cells with carbon-black + fumed-silica mixed negative plates. However, a high self-discharge rate is observed for cells with carbon-black + fumed-silica mixed negative plates.

Fluorite and Mixed-Metal Kagome-Related Topologies in Metal-Organic Framework Compounds: Synthesis, Structure, and Properties

Two new three-dimensional metal-organic frameworks (MOFs) [Mn-2(mu(3)-OH)(H2O)(2)(BTC)]-2 H2O, I, and [NaMn(BTC)], II (BTC=1,2,4-benzenetricarboxylate = trimellitate) were synthesized and their structures determined by single-crystal X-ray diffraction (XRD). In I, the Mn-4 cluster, [Mn-4(mu(5)-OH)(2)(H2O)(4)O-12], is connected with eight trimellitate anions and each trimellitate anion connects to four different Mn-4 clusters, resulting in a fluorite-like structure. In II, the Mn2O8 dimer is connected with two Na+ ions through carboxylate oxygen to form mixed-metal distorted Kagome-related two-dimensional -M-O-M- layers, which are pillared by the trimellitate anions forming the three-dimensional structure. The extra-framework water molecules in I are reversibly adsorbed and are also corroborated by powder XRD studies. The formation of octameric water clusters involving free and coordinated water molecules appears to be new. Interesting magnetic behavior has been observed for both compounds. Electron spin resonance (ESR) studies indicate a broadening of the signal below the ordering temperature and appear to support the findings of the magnetic studies.

Cyclic Peptide Disulfides - Solution And Solid-State Conformation Of Boc-Cys-Pro-Aib-Cys-S-S-Bridge-Nhme,A Disulfide-Bridged Peptide Helix

The solution and solid-state conformations of the peptide disulfide Boc-Cys-Pro-Aib-Cys-NHMe have been determined by NMR spectroscopy and X-ray diffraction. The Cys(4) and methylamide NH groups are solvent shielded in CDCI3 and (CD,),SO, suggesting their involvement in intramolecular hydrogen bonding. On the basis of known stereochemical preferences of Pro and Aib residues, a consecutive @-turn structure is favored in solution. X-ray diffraction analysis reveals a highly folded 310 helical conformation for the peptide, with the S-S bridge lying approximately parallel to the helix axis, linking residues 1 and 4. The backbone conformational angles are Cys(1) 4 = -121.1', $ = 65.6"; Pro(2) 4 = -58.9', 4 = -34.0'; Aib(3) 4 = -61.8', $ = -17.9'; Cys(4) 4 = -70.5', $ = -18.6'. Two intramolecular hydrogen bonds are observed between Cys(1) CO--HN Cys(4) and Pro(2) CO--HNMe. The disulfide bond has a right-handed chirality, with a dihedral angle (xss) of 82'.

Steady-State Response of Thick Rectangular Plates

The classical theory of plates neglects the effects of rotatory inertia and shear deformation, and due to this assumption it is applicable only for thin plates. Mindlin presented an improved plate theory which is fairly accurate.

Proline ring conformations corresponding to a bistable jump model from 13C spin-lattice relaxation times

A formalism for extracting the conformations of a proline ring based on the bistable jump model of R. E. London [(1978) J. Am. Chem. Soc. 100, 2678-2685] from 13C spin-lattice relaxation times (T1) is given. The method is such that the relaxation data are only partially used to generate the conformations; these conformations are constrained to satisfy the rest of the relaxation data and to yield acceptable ring geometry. An alternate equation for T1 of 13C nuclei to that of London is given. The formalism is illustrated through an example.

Reversible photodimerization of phenylbutadienes in the solid state

Based on x-ray crystallographic studies, it is shown that crystal chemical factors govern the reversible photodimerization of phenylbutadienes in the solid state.

A nuclear magnetic resonance study of tetramethylammonium tribromocadmate

Proton spin lattice relaxation (T1) in (CH3)4NCdBr3 at different Larmor frequencies (10, 20 and 30 MHz) has been studied in the temperature range 77 to 400 K. The variations in T1 at high temperature are independent of frequency and show a maximum due to spin rotation- interaction. The other features are interpreted as being due to isotropic tumbling of the tetramethylammonium ion and random reorientation of the CH3 group. The CW spectrum remained narrow up to 77 K and develops a wing structure at low temperatures. This observation is attributed to a possible tunnelling motion of the CH3 group, which has rather low activation energy as demonstrated by the study of T1.

Theory of the mixed valent state

After briefly discussing the question of a distinct mixed valent state and theoretical models for it, the area of greatest theoretical success, namely the mixed valent impurity, is reviewed. Applications to spectroscopy, energetics and Hall effect are then putlined. The independent impurity approximation is inadequate for many properties of the bulk system, which depend on lattice coherence. A recent auxiliary or slave boson approach with a simple mean field limit and fluctuation corrections is summarized. Finally the mixed valent semiconductor is discussed as an outstanding problem.

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.

7Li Spin-flip satellites in the EPR sectra of NH3+ -doped LiKSO4

EPR spectra of lithium potassium sulfate doped with NH3+ have been recorded at 9.05 GHz. A pair of satellites can be seen symmetrically situated on either side of the main lines. The separation of the satellite lines from the main line corresponds to the 7Li NMR frequency. The distance of the interacting 7Li nucleus from the unpaired electron in NH3+ is estimated to be 3.29 Å.

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.