A Study of copper-compounds by x-Ray Absorption-spectroscopy

Chemical shifts, ΔE, of the K-absorption discontinuity in several compounds of copper possessing formal oxidation states between 0 and III have been measured. The shifts show a parabolic dependence on the formal oxidation state as well as on the effective atomic charge, q, on copper. Anomalous chemical shifts shown by some of the compounds are discussed in terms of the bonding in these compounds. The ΔE values have also been correlated with the core electron binding energies obtained from X-ray photoelectron spectroscopy.

Single‐gate deep level transient spectroscopy technique

A new deep level transient spectroscopy technique is suggested which allows the deep level parameters to be obtained from a single temperature scan. Using large ratio t2/t1 of the measurement gate positions t1 and t2 and analyzing the steep high‐temperature side of the peak, it is demonstrated that the deep level activation energy can be determined with high accuracy.

Raman induced phase conjugation spectroscopy

Raman induced phase conjugation (RIPC) spectroscopy is a relatively new coherent Raman spectroscopic (CRS) technique using optical phase conjugation (OPC), with which complete Raman spectra of transparent media can be obtained. It is a non-degenerate four-wave mixing technique in which two pulsed laser beams at Ω1 and Ω1 ± Δ where A corresponds to a vibrational frequency of a nonlinear medium mix with a third laser beam at Ω1 to generate a fourth beam Ω1 ± Δ, which is nearly phase conjugate to one of the beams at Ω1. With this technique one can measure the ratio of the resonant and nonresonant components of the third-order nonlinear susceptibilities of the nonlinear media. We have used this technique to get Raman spectra of well-known organic solvents like benzene etc., using pulsed Nd: YAG -dye laser systems. We have also studied the effect of delaying one of the interacting beams with respect to the others and the phase conjugate property of RIPC signals.

An Investigation Of Alkali Aluminosilicate Glasses By Si-29 And Al-27 Magic-Angle-Spinning Nmr-Spectroscopy

Alkali aluminosilicate glasses prepared by the gel and the melt routes have been investigated by Si-29 and Al-27 MAS NMR spectroscopy. It is found that Al has a tetrahedral coordination in the gel glasses modified with equivalent proportions of alkalis unlike in a pure aluminosilicate glass where Al has both four and six coordinations. Silicon is present as Q4 units in all the 5M2O 5Al2O3 9OSiO2 ( M = Li, Na and K) gel glasses studied whereas it is present in Q2 or Q3 species in the lithium aluminosilicate glasses of compositions 40Li2O x Al2O3 (1-x)SiO2 (1 less-than-or-equal-to x less-than-or-equal-to 15) and xLi2O 10Al2O3 (1-x)SiO2 (20 less-than-or-equal-to x less-than-or-equal-to 40). The combination of Q2 and Q3 is also found in certain sodium aluminosilicate glasses, but they change to Q2 and Q1 as the concentration of SiO2 decreases.

Circular dichroism and 13C nuclear magnetic resonance spectroscopy of pennisetin from pearl millet

The conformation and stability of pearl millet prolamin (pennisetin) were examined by using circular dichroism and C-13 nuclear magnetic resonance spectroscopy. The far UV spectrum of pennisetin in 70% (v/v) aqueous ethanol showed the presence of predominant alpha-helical structure and its occurrence in the alpha + beta class of protein. The far and near UV spectra of pennisetin in ethanol: trifluoroethanol also supported this observation. However pennisetin showed the presence of some helical structure in 8 M urea which is known to be a highly unordered structure forming solvent. A decrease in alpha helical content of native pennisetin was observed with rise in temperature from 5-75-degrees-C and this effect of temperature was found to be reversible. A C-13 NMR spectrum of pennisetin in 70% ethanol suggested a high degree of molecular mobility in ethanol. Comparison of the cross polarization spectrum with the single pulse excitation spectrum suggested pennisetin to be a heterogeneous protein.

1, 2-Bis (diphenylphosphino) etane bridged dinuclear copper (I) complexes: Investigations of solid state and solution structures by CP/MAS31P NMR spectroscopy, X-ray crystallography, IR spectroscopy and solution 31P NMR and 63Cu NMR spectroscopy

Three different complexes of copper (I) with bridging 1, 2-bis(diphenylphosphino)ethane (dppe), namely [Cu2 (mu-dppe) (CH3CN)6] (ClO4)2 (1), [Cu2 (mu-dppe)2 (CH3 CN)2] (ClO4)2 (2), and [Cu2 (mu-dppe) (dppe)2 (CH3CN)2] (ClO4)2 (3) have been prepared. The structure of [Cu2 (mu-dppe) (dPPe)2 (CH3CH)2] (ClO4)2 has been determined by X-ray crystallography. It crystallizes in the space group PT with a=12.984(6) angstrom, b=13.180(6) angstrom, c=14.001(3) angstrom, alpha=105.23(3), beta=105.60(2), gamma=112.53 (4), V=1944 (3) angstrom3, and Z=1. The structure was refined by least-squares method with R=0.0365; R(w)=0.0451 for 6321 reflections with F0 greater-than-or-equal-to 3 sigma (F0). The CP/MAS P-31 and IR spectra of the complexes have been analysed in the light of available crystallographic data. IR spectroscopy is particularly helpful in identifying the presence of chelating dppe. P-31 chemical shifts observed in solid state are very different from those observed in solution, and change significantly with slight changes in structure. In solution, complex 1 remains undissociated but complexes 2 and 3 undergo extensive dissociation. With a combination of room temperature H-1, Cu-63, and variable temperature P-31 NMR spectra, it is possible to understand the various processes occurring in solution.

Analysis of the evanescent field coupling between a fiber and a planar waveguide using the explicit finite difference method with a nonuniform mesh (Journal Paper)

We investigate an optical waveguide system consisting of an unclad fiber core suspended at a constant distance parallel to the surface of a planar waveguide. The coupling and propagation of light in the combined system is studied using the three-dimensional explicit finite difference beam propagation method with a nonuniform mesh configuration. The power loss in the fiber and the field distribution in the waveguide are studied as a function of various parameters, such as index changes, index profile, and propagation distance, for the combined system.

An investigation of well-characterized small gold clusters by photoelectron spectroscopy, tunneling spectroscopy, and cognate techniques

After microscopic characterization of the size distributions of gold clusters, deposited on carbon substrates by vacuum evaporation or by soft landing, Au(4f') binding energy of the clusters has been measured as a function of the mean cluster size. Similar measurements have been carried out on Au clusters prepared from sols by chemical means and high-nuclearity cluster compounds. In general, small clusters with a mean diameter of $2 nm show significantly larger binding energies than the bulk metal value, due to the onset of nonmetallicity. Nonmetallicity manifests itself in terms of a tunneling conductance gap only in clusters of diameter ;5 1 nm containing 40 atoms or fewer.

Characterization and evaluation of melibiose as novel excipient in tablet compaction

Lactose is probably the most used tablet excipient in the field of pharmacy. Although lactose is thoroughly characterized and available in many different forms there is a need to find a replacer for lactose as a filler/binder in tablet formulations because it has some downsides. Melibiose is a relatively unknown disaccharide that has not been thoroughly characterized and not previously used as an excipient in tablets. Structurally melibiose is close to lactose as it is also formed from the same two monosaccharides, glucose and galactose. Aim of this research is to characterize and to study physicochemical properties of melibiose. Also the potential of melibiose to be used as pharmaceutical tablet excipient, even as a substitute for lactose is evaluated. Current knowledge about fundamentals of tableting and methods for determinating of deformation behavior and tabletability are reviewed. In this research Raman spectroscopy, X-ray powder diffraction (XRPD), near-infrared spectroscopy (NIR) and Fourier-transform infrared spectroscopy (FT-IR) were used to study differences between two melibiose batches purchased from two suppliers. In NIR and FT-IR measurements no difference between materials could be observed. XPRD and Raman however found differences between the two melibiose batches. Also the effects of moisture content and heating to material properties were studied and moisture content of materials seems to cause some differences. Thermal analytical methods, differential scanning calorimetry (DSC) and thermogravimetry (TG) were used to study thermal behaviour of melibiose and difference between materials was found. Other melibiose batch contains residual water which evaporates at higher temperatures causing the differences in thermal behaviour. Scanning electron microscopy images were used to evaluate particle size, particle shape and morphology. Bulk, tapped and true densities and flow properties of melibiose was measured. Particle size of the melibiose batches are quite different resulting causing differences in the flowability. Instrumented tableting machine and compression simulator were used to evaluate tableting properties of melbiose compared to α-lactose monohydrate. Heckel analysis and strain-rate sensitivity index were used to determine deformation mechanism of melibiose monohydrate in relation to α–lactose monohydrate during compaction. Melibiose seems to have similar deformation behaviour than α-lactose monohydrate. Melibiose is most likely fragmenting material. Melibiose has better compactibility than α – lactose monohydrate as it produces tablets with higher tensile strength with similar compression pressures. More compression studies are however needed to confirm these results because limitations of this study.

Chiral polyhydroxylated tetrahydrothiophene derivatives: novel synthesis and structural elucidation by X-ray crystallography, NMR spectroscopy and molecular mechanics calculations

The dideoxygenation reaction of 1,3;4,6-di-O-alkylidene-2,5-di-S-methylthiocarbonyl-D-mannitol derivatives under Barton-McCombie reaction conditions gave the hexahydrodipyranothiophenes 4 and 7 instead of the expected 2,5-dideoxy products. Structural and conformational information on these novel derivatives has been obtained by NMR spectroscopy, single-crystal X-ray crystallography and molecular mechanics calculations.

Syntheses, spectroscopy, structures, and conformations of .lambda.3-cyclotriphosphazanes: role of negative hyperconjugation

The reactions of As-chlorocyclotriphosphazane [EtNPCl], with phenols or trifluoroethanol yield the respective aryloxy- or trifluoroethoxy-containingX 3-cyclotriphosphazanes [EtNP(OR)]3 (R = C6H4Br-4 (2),C 6H5 (3C,6 H3-Mez-3,5 (4), C6H3Mez-2,6 (5), CH2CF3 (6)) as their cis-transisomericmixtures. The products have beencharacterized by IRand NMRspectroscopy. Thecrystalstructuresofboth thecis (2a) and trans(2b) isomer_softhep-bromophenoxy derivative have been determined by X-ray diffraction. Crystal data for 2a: triclinic, P1, a = 9.872(4) A, b = 13.438(6) A, c = 13.548(8) A, CY = 117.02(5)', 0 = 96.00(6)', y = 105.38(4)O, Z = 2, final R = 0.080. Crystal data for 2b: monoclinic, P21/n, a = 12.721(6) A, b = 13.468(7) A, c = 17.882(5) A, /3 = 101.62(3)O, Z = 4, final R = 0.066. The cis isomer exhibits a chair-triaxial conformation and the trans isomer a boat-triaxial conformation. Conformational preferences of X3-cyclotriphosphazanes have been probed by both MNDO and ab initio calculations on model systems [HNPXIp (X = H, F). In addition to vicinal lone pair repulsions, negative hyperconjugative interactions involving the nitrogen lone pairs and adjacent P-X Q* orbitals are found to be important (especially when X is an electronegative substituent) in determining the conformational preferences of X3-cyclotriphosphazanes. The calculations also show that the axial - equatorial conversion at phosphorus has a large activation barrier in these systems

Conformation of polymerizable diacetylenic lecithin, DC8,9PC, by 1H-NMR spectroscopy

Diacetylenic phospholipid, 1,2 bis-(tricosa-10,12-diynoyl)-sn-glycero-3-phosphocholine (DC8,9PC), forms helices and tubules in addition to liposomes. The diacetylenic moiety responsible for the transformation is probed by 2-D NMR correlated spectroscopy. Chemical shift assignments and the analysis of 2D-COSY measurements were done on the lipid in chloroform-d solution. Based on this analysis, a model for the lipid is proposed. The geometry of the headgroup, glycerol backbone and acyl chains up to three methylenes from glycerol backbone [-(CH2)(3)-] is similar to that of dipalmitoyl phosphatidylcholine. The estimated torsional angle for methylene groups adjacent to diacetylenic moieties suggested an overall tilt of the diacetylenic lipid molecule from the bilayer axis of 25-30 degrees. This tilt could be negative or positive depending on the handedness of the resultant microstructures.