Raman scattering in impurity-induced anharmonic crystals

The theory of first-, second-, and third-order Raman scattering is investigated for isotopically disordered anharmonic crystals. The theory of time-dependent thermodynamic Zubarev Green's functions is adopted to obtain the Raman tensor, intensity of Raman lines, and differential cross sections of various orders of scatterings. It is observed that each class of scattering can be separated into diagonal and nondiagonal parts. The first-order and nondiagonal parts are absent in the case of chemically pure crystals. The diagonal parts are separated into anharmonic and interference terms. The interference terms arise due to the interactions of anharmonic phonons with the local phonons. The temperature and defect dependencies are discussed in detail along with the nature of continuous and line spectra. It is proposed that very high-power laser sources will reveal the third-order spectra, and that the resulting structure can be explained with the help of temperature-dependent one-, two-, and three-phonon density of states.     

Kinetics and mechanism of silver(I)-catalysed oxidation of malonic acid by peroxodiphosphate in acetate buffers

Summary The kinetics of the silver(I)-catalysed oxidation of malonic acid by peroxodiphosphate (pdp) was studied in acetate buffers. The rate law as represented by-d[pdp]/dt = {(k ₁ K _inf2 ^sup-1 [H⁺]² + k ₂[H⁺] + k ₃ K ₃)/ ([H⁺]²/K ₂ + [H⁺] + K ₃)}[pdp][Ag(I)] conforms to the proposed mechanism. The rate is independent of malonic acid concentrations. Acetate ions do not affect the rate; however, the rate decreases as the ionic strength increases. A probable portrait of reaction events is suggested. A comparative analysis of the reactivity pattern of malonic acid towards peroxodiphosphate and peroxodisulphate in presence of silver(I) has been made.     

Small-angle x-ray scattering studies on epoxidized butadiene-styrene block copolymers

Small-angle x-ray scattering (SAXS) and scanning electron microscopy (SEM) investigations for epoxidized butadiene-styrene (BS) block copolymers were performed. For unepoxidized copolymers, the SAXS curve exhibits a maximum which indicates that the copolymer has heterogeneity domain morphology. Using the standard theory for a two-phase system, mean distances between domains, the correlation length l _p , and the thickness of the phase boundary were calculated from the SAXS data. It was found that the epoxidation of BS copolymers decreases the ability of the copolymer to separate the individual components. As the content of the epoxide groups increases, the dimensions of the domains decrease until they disappear, the boundary between domains and the matrix becomes less and less definite, and the copolymer composes a homogeneous system. The disappearance of the two-phase structure of the BS copolymers indicates an increase in the compatibility of polystyrene and epoxidized polybutadiene. According to the method of Van Krevelen, the solubility parameters of polystyrene and epoxypolybutadiene were calculated. Small differences between these parameters support the conclusions drawn from the SAXS investigations     

Synthesis, structural and electrical properties of La and Nb modified Bi4Ti3O12 ferroelectric ceramics

Polycrystalline ceramic samples of Bi_4−xLa_xTi₃O₁₂ (x=0.0, 0.5 and 1) and Bi_3.5La_0.5Ti_3−yNb_yO₁₂ (y=0.02 and 0.04) have been synthesized by standard high temperature solid state reaction method using high purity oxides and carbonates. The effect of lanthanum doping on Bi-site and Nb doping on Ti-site on the structural and electrical properties of Bi₄Ti₃O₁₂ powders was investigated by X-ray diffraction, scanning electron microscopy, dc conductivity and dielectric studies. A better agreement between the observed and calculated X-ray diffraction pattern was obtained by performing the Rietveld refinement with a structural model using the non-centrosymmetric space group Fmmm in all the cases. A better agreement between observed and calculated d-values also shows that the lattice parameters calculated using the Rietveld refinement analysis are better. The increase in lanthanum and niobium contents does not lead to any secondary phases. It is found that La³⁺ doping reduces the material grain size and changes its morphology from the plate-like form to a spherical staking like form. The substitution of Nb for Ti ions affected the degree of disorder and modified the dielectric properties leading to more resistive ceramic compounds. The shape and size of the grains are strongly influenced by the addition of niobium to the system. The activation energies of all the compounds were calculated by measuring their dc electrical conductivities. The frequency and temperature dependent dielectric behavior of all the compounds have also been studied and the results are discussed in detail. The substitution of La and Nb on the Bi and Ti sites decreased the T_c and improved the dielectric and ferroelectric behavior.     

Immunotherapeutic role of Ag85B as an adjunct to antituberculous chemotherapy

Background

Immunotherapy to enhance the efficiency of the immune response in tuberculosis patients and to eliminate the persisters could be an additional valuable strategy to complement anti-mycobacterial chemotherapy. This study was designed to assess the immunotherapeutic potential of Ag85B as an adjunct to chemotherapy and its effect against active and persister bacteria left after therapy in mouse model of tuberculosis.

Methods

6-8 week old female Balb/c mice were infected with Mycobacterium tuberculosis and treated with chemotherapy or immunotherapy. Protective efficacy was measured in terms of bacterial counts in lungs and spleen. Immune correlates of protection in terms of Th1 and Th2 cytokines were measured by ELISA.

Results

Therapeutic effect of Ag85B was found to be comparable to that of short term dosage of antituberculous drugs (ATDs). The therapeutic effect of ATDs was augmented by the simultaneous treatment with rAg85B and moreover therapy with this protein allowed us to reduce ATD dosage. This therapy was found to be effective even in case of drug persisters. The levels of antigen specific IFNγ and IL-12 were significantly increased after immunotherapy as compared to the basal levels; moreover antigen specific IL-4 levels were depressed on immunotherapy with Ag85B.

Conclusion

We demonstrated in this study that the new combination approach using immunotherapy and concurrent chemotherapy should offer several improvements over the existing regimens to treat tuberculosis. The therapeutic effect is associated not only with initiating a Th1 response but also with switching the insufficient Th2 immune status to the more protective Th1 response.     

Trapping a Silicon(I) Radical with Carbenes: A Cationic cAAC–Silicon(I) Radical and an NHC–Parent-Silyliumylidene Cation

The trapping of a silicon(I) radical with N-heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAAC_Me] (cAAC_Me=:C(CMe₂)₂(CH₂)NAr, Ar=2,6-iPr₂C₆H₃) with H₂SiI₂ in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAAC_Me)₂Si:^.]⁺I⁻ ( 1 ), which features a cationic cAAC–silicon(I) radical, and [cAAC_Me−H]⁺I⁻. In addition, the reaction of the NHC–iodosilicon(I) dimer [I_Ar(I)Si:]₂ (I_Ar=:C{N(Ar)CH}₂) with 4 equiv of I_Me (:C{N(Me)CMe}₂), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(I_Me)₂SiH]⁺I⁻ ( 2 ) comprising the first NHC–parent-silyliumylidene cation. Its further reaction with fluorobenzene afforded the C_Ar−H bond activation product [1-F-2-I_Me-C₆H₄]⁺I⁻ ( 3 ). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1 . Compounds 1 – 3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X-ray crystallography.     

Competition between hydrogen bonding and dispersion interactions in the indole···pyridine dimer and (indole)2···pyridine trimer studied in a supersonic jet

Structures of the indole···pyridine dimer and (indole)2···pyridine trimer have been investigated in a supersonic jet using resonant two-photon ionization (R2PI) and IR-UV double resonance spectroscopic techniques combined with quantum chemistry calculations. R2PI spectra of the dimer and the trimer recorded by electronic excitation of the indole moiety show that the red-shift in the band origin of the dimer with respect to the 0(0)(0) band of the monomer is larger compared to that of the trimer. The presence of only one conformer in the case of both the dimer and the trimer has been confirmed from IR-UV hole-burning spectroscopy. The structures of the dimer and the trimer have been determined from resonant ion dip infrared (RIDIR) spectra combined with ab initio as well as DFT/M05-2X and DFT/M06-2X calculations. It has been found that the dimer, observed in the experiment, has a V-shaped geometry stabilized by N–H···N and C–H···N hydrogen bonding interactions, as well as C–H···π and π···π dispersion interactions. The geometry of the trimer has been found to be a cyclic one stabilized by N–H···N, N–H···π, C–H···π, and C–H···N interactions. The most important finding of this current study is the observation of the mixed dimer and trimer, which are stabilized by hydrogen bonding as well as dispersion interactions.     

Thermal analyses of organic powders made from precipitation polymerization of triallyl monomers

Organic solids have been prepared from radical-initiated activation of solutions composed of tetradecane and triallyl trimesate (TAM) monomer or triallyl phosphate (TAP) monomer using a recently developed variation of precipitation polymerization methods. The powders, which comprise fused aggregates, are shown to be rich in monomer (83–88 wt% TAM or 86–92 wt% TAP), and are believed to be formed by a combination of hydrocarbon addition and allyl group oligomerization. TAM-g-tetradecane primary particles are on the order of 500 nm in diameter, while TAP-g-tetradecane particles are on the order of 100–200 nm diameter. These products are thermochemically assessed using a combination of differential scanning calorimetry, thermogravimetry and pyrolysis combustion flow calorimetry. The phosphorus-containing TAP-g-tetradecane shows exothermic activity around 230 °C, likely due to thermal decomposition of the trialkyl phosphate moiety, and may find use in advanced materials applications.