Hyperfine interaction experienced by181Ta nuclei at the Hf site in HfFe2−xSix compounds through a decoupling experiment

The time-differential perturbed angular correlation (TDPAC) experiments involving the 133–482 keV γ-γ cascade in¹⁸¹Ta have been performed in the presence of an external magnetic field along the quantization axis to measure the hyperfine magnetic field experienced by¹⁸¹Ta nuclei at the Hf site in the pseudobinary compounds HfFe_2?xSi_x with x=0.1 and x=0.3. The hyperfine magnetic fields measured at 298 K are H_hf=133.1±12.0 kG in the cubic (C15) Laves phase compound HfFe_1.9Si_0.1 and H_hf=76.8±7.0 kG in the hexagonal (C14) Laves phase compound HfFe_1.7Si_0.3. The measured hyperfine fields are discussed within the framework of the Campbell-Blandin model.     

Neutron diffraction study of quasi-one-dimensional spin-chain compounds Ca<Subscript>3</Subscript>Co<Subscript>2–<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>6</Subscript>

We report the results of the DC magnetization, neutron powder diffraction and neutron depolarization studies on the spin-chain compounds Ca₃Co_2–x Fe _x O₆ (x = 0, 0.1, 0.2 and 0.4). Rietveld refinement of neutron powder diffraction patterns at room temperature confirms the single-phase formation for all the compounds in rhombohedral structure with space group Rc. Rietveld refinement also confirms that Fe was doped at the trigonal prism site, 6a (0, 0, 1/4) of Co. The high temperature magnetic susceptibility obeys the Curie-Weiss law; the value of the paramagnetic Curie temperature (θ _p) decreases as the concentration of iron increases and it becomes negative for x = 0.4. No extra Bragg peak as well as no observable enhancement in the intensity of the fundamental (nuclear) Bragg peaks has been observed in the neutron diffraction patterns down to 30 K. No depolarization of neutron beam has been observed down to 3 K confirming the absence of ferro- or ferrimagnetic-like correlation.      

The out-of-plane vibrational modes of chlorobenzene in its ground and first singlet excited states

The study of 2699 Å electronic band system of chlorobenzene has been extended to extract out all the six b₁ and three a₂ modes in both the ground state (^eA₁) and the electronically excited first singlet state (^eB₂). The procedure of the extraction of these modes on the basis of observed sequences, cross-sequences, and overtones has especially been elaborated. Strong Fermi interaction has been observed between the vibrational level ν′_6b and combination level ν′_16a + ν′_16b in ^eB₂ state. The uniqueness of the assignments of the modes has been critically discussed.     

EPR studies of highly pure,pure and doped chromium oxide powders

Abstract

EPR absorption measurements on ‘pure’, highly pure and A1₂O₃ doped Cr₂O₃ powder have been made. The EPR absorption in the ‘pure’ powders obtained below Ntel temperature is shown to be due to background magnetic impurities present in the powders and not due to superparamagnetism as suggested by earlier authors. No EPR absorption could be observed below Nkl temperature in highly pure powders (total background impurity concentration less than 5 ppm). ‘Pure’ powders or highly pure powders mixed with A1₂O₃ powder and annealed at high temperatures showed a symmetrical EPR absorption line at room temperature. The shape and the g value of this line are practically the same as those obtained for Cr³⁺ ions in Cr₂O₃ above Nee1 temperature or in other nonmagnetic crystals. It is concluded from these results that the impurities diffuse into Cr₂O₃ powder, the antiferro-magnetic coupling between some of the Cr³⁺ ions is broken and these Cr³⁺ ions become paramagnetic, even when the bulk of the material is in antiferromagnetic state. The variation of half-width of EPR lines with impurity concentration shows that the dipolar coupling between Cr³⁺ ions decreases with the increase in impurity concentration and when the impurity concentration is high the Néel temperature seems to shift to lower temperatures. A longer heat treatment of the ‘pure’ B powder resulted in the production of shining metal particles in the powder. The EPR of this powder showed excessive increase in the intensity of EPR absorption when the temperature of the powder was raised to a value just above the Néel temperature. A comparison of these reuslts with the work of earlier authors suggests that the shinning metal particles are those of chromium metal and are responsible for this increase in EPR absorption.     

On Markuševič decompositions of Banach spaces

пРОВЕДЕНО сИстЕМАтИ ЧЕскОЕ ИсслЕДОВАНИЕ РАжлИЧНых тИпОВ РАжлОжЕНИИ, А ИМ ЕННО, пО МАРкУшЕВИЧУ, ОБОБЩЕН Ных И РАжлОжЕНИИ пО шА УДЕРУ. УкАжАНы пРИМЕРы, ИллУ стРИРУУЩИЕ ВжАИМООтНОшЕНИь ЁтИ х тИпОВ РАжлОжЕНИИ. Ос НОВНАь цЕль ДАННОИ РАБОты — ИжУЧЕ НИЕ РАжлОжЕНИИ пО МАРкУшЕВИЧУ (M-РАжл ОжЕНИИ). ОтМЕЧАЕтсь, Чт О пОслЕДОВАтЕльНОсть пРОЕкцИИ, сВьжАННАь с ОБОБЩЕНН ыМ РАжлОжЕНИЕМ, ьВльЕ тсь ЕДИНстВЕННОИ тОгДА И тОлькО тОгДА, кОгДА ЁтОM-РАжлОжЕНИЕ. пОлУ ЧЕНА хАРАктЕРИжАцИьM-РАжлОжЕНИИ В тЕРМИН Ах Их пОДпОслЕДОВАтЕ льНОстЕИ. пОлУЧЕНА тАкжЕ хАРАк тЕРИжАцИь пО шАУДЕРУ В тЕРМИНАхM-РАжлОжЕНИИ. НАкОНЕц, пОлУЧЕНы ОтНОшЕНИь Д ВОИстВЕННОстИ МЕжДУM-РАжлОжЕНИьМИ НЕкОтО РОгО пРОстРАНстВА И НЕкОтОРыМИ РАжлОжЕ НИьМИ сОпРьжЕННОгО п РОстРАНстВА.     

Oximidobenzotetronic acid as a reagent for the separation and gravimetric determination of palladium and cobalt

Oximidobenzotetronic acid is recommended for the separation and gravimetric determination of palladium and cobalt An ethanolic solution of the reagent quantitatively precipitates palladium(II) from solutions which are 0.75 N in acid up to pH 5.1, the complex is weighed as Pd(C₉H₅NO₄)₂. Cobalt(II) can be determined in the filtrate after the precipitation of palladium. With 0.5 N acid solutions, no interference was found from Pt(IV), Ir(IV), Rh(III), Ru(III), Os(IV), Au(III), Ag(I), Cu(II), Fe(III), Ni(II), Hg(II). Pb(II), Bi(III), Cd(II), As(V), Se(VI), Te(IV), Mo(VI), Sb(III), Al(III), Cr(III), Zn(II), Ti(IV), Zr(IV). acetate, oxalate, citrate, tartrate, phosphate and fluoride.     

Effect of hydrophilic polymer on complexing efficiency of cyclodextrins towards efavirenz-characterization and thermodynamic parameters

The present work describes the effect of PVP on the complexation efficiency of cyclodextrins towards efavirenz, a poorly soluble antiretroviral agent imparting irritating sensation to buccal cavity. The phase solubility study indicates 1:1 stoichiometry for binary and ternary systems. DSC and XRPD revealed complete inclusion only in the lyophilized systems. The ternary systems were autoclaved before being lyophilized for the best results. Proton NMR suggests that the chlorobenzene part of benzoxazinone ring of the drug is involved in inclusion and was confirmed by 2D-COESY. The thermodynamic parameters, indicative of complexation efficiency were calculated calorimetrically by determining the interaction enthalpy of efavirenz with cyclodextrins in the presence and absence of PVP. The value of stability constants increased in the order β-CD?<?HP-β-CD?<?M-β-CD and is still higher in the presence of PVP illustrating the facilitation of the inclusion. Molar enthalpy of interaction of autoclaved solid formulation determined calorimetrically indicated stronger interaction for efavirenz:M-βCD-PVP system (?12.20?kJ/mol) which showed highest solubility and dissolution rate. The in vitro measurement of permeability showed a ten fold increase in the flux for the autoclaved formulation containing efavirenz-M-β-CD-PVP. In conclusion, encapsulation by cyclodextrins increases the solubility and suppresses the oral irritation of efavirenz. PVP further increases the complexation efficiency and decreases the bulk of cyclodextrins.     

Formation of HO2 radicals from the 248 nm two-photon excitation of different aromatic hydrocarbons in the presence of O2

The excitation energy dependence of HO(2) radical formation from the 248 nm irradiation of four different aromatic hydrocarbons (benzene, toluene, o-xylene, and mesitylene) in the presence of O(2) has been studied. HO(2) has been monitored at 6638.20 cm(-1) by cw-CRDS, and the formation of a short-lived, unidentified species, showing broad-band absorption around the HO(2) absorption line, has been observed. For all four hydrocarbons, the same HO(2) formation pattern has been observed: HO(2) is formed immediately on our time scale after the excitation pulse, followed by a formation of more HO(2) on a much longer time scale. Taking into account the absorption of the short-lived species, the yields of both types of HO(2) radicals are in agreement with a formation following 2-photon absorption by the aromatic hydrocarbons. The yields do not much depend on the nature of the aromatic hydrocarbon. For practical use in past and future experiments on aromatic hydrocarbons, an empirical value is given, allowing the estimation of the total concentration of HO(2) radicals formed at 40 Torr He in the presence of around [O(2)] = 1 × 10(17)cm(-3) as a function of the 248 nm excitation energy: [HO(2)]/[aromatic hydrocarbon] ≈ 2 × 10(-6) × E(2) (with E in mJ cm(-2)).     

Thermal analysis of interaction between 2-PAM chloride and various excipients in some binary mixtures by TGA and DSC

Pralidoxime chloride known as 2-PAM chloride is used as antidote for nerve agent’s poisoning. This study was undertaken to establish the compatibility of 2-PAM chloride with a number of commonly used excipients by using thermoanalytical technique viz., differential scanning calorimetry (DSC) and thermogravimetry/differential thermogravimetry (TG/DTG) used in pharmaceutical formulation. The TG and DSC both results demonstrated that polyvinyl alcohol, polyacrylamide, microcrestline cellulose, hydroxypropyl cellulose, cellulose acetate, ethyl cellulose found to be compatible with 2-PAM chloride and chosen for the preparation of antidote against chemical warfare agents.