High levels of soluble herpes virus entry mediator in sera of patients with allergic and autoimmune diseases

Herpes virus entry mediator (HVEM) is a newly discovered member of the tumor necrosis factor receptor (TNFR) superfamily that has a role in herpes simplex virus entry, in T cell activation and in tumor immunity. We generated mAb against HVEM and detected soluble HVEM (SHVEM) in the sera of patients with various autoimmune diseases. HVEM was constitutively expressed on CD4(+) and CD8(+) T cells, CD19(+) B cells, CD14(+) monocytes, neutrophils and dendritic cells. In three-way MLR, mAb 122 and 139 were agonists and mAb 108 had blocking activity. An ELISA was developed to detect sHVEM in patient sera. sHVEM levels were elevated in sera of patients with allergic asthma, atopic dermatitis and rheumatoid arthritis. The mAbs discussed here may be useful for studies of the role of HVEM in immune responses. Detection of soluble HVEM might have diagnostic and prognostic value in certain immunological disorders.     

Infrared study of adsorption of methanol,deuterated methanol and ethylene on the surface of ZSM-5 type zeolite

The surface species resulting in exposing of the ZSM-5 zeolite at elevated temperatures to methanol, deuterated methanol or ethylene have been studied by IR method.The three-step adsorption at 150°, 300°, 420° C or one-step adsorption at 420° C have been carried out in order to prepare the samples for IR. In all cases the most prominent band appeared in the range 1495–1515 cm^?1; besides two bands at about 1470 and 1370 cm^?1 have been observed. On the basis of Greenler's results and of the shift values of the bands in our spectrum of adsorbed deuterated methanol it was supposed that the band 1495–1515 cm^?1 is due to the OCO group from the surface species. Moreover these species would involve both oxygen atoms from the surface of zeolite but not from OH groups of methanol.     

Ramanspektroskopische Untersuchungen an PCl5 II. Das System PCl5—ZrCl4

Raman spectra of some solid and molten PCl₅–ZrCl₄ mixtures have been recorded. ZrCl₆ ^2– complex ions accompanied by at least one more chlorozirconate species are present in the solid as well as in the melt. The newRaman frequencies are attributed to ZrCl₅ ^–, which fundamentals are given and assignment is proposed to be analogous to TiCl₅ ^–. The presence of ZrCl₆ ^2– and ZrCl₅ ^– can be explained by the equilibrium ZrCl₆ ^2–+PCl₄ ⁺ZrCl₅ ^–+PCl₅.

     

A new electrolytic dissolution of aluminum alloys and determination of some constituents by inductively coupled plasma optical emission spectrometry

The new electrolytic dissolution in batch of aluminum alloys samples as grains or turns and the determination of Fe, Cu, Mn, Mg, Cr, Ni, Zn, Pb and Ti by ICP OES was investigated. In on-line electrodissolution procedures described in the literature, samples were restricted to be in the form of solid blocks or plates with one polished flat face. Here, the sample was loaded in the barrel of a modified disposable syringe (the anodic semi-cell) and pressed with a modified plunger fitted with a platinum disk to establish electrical contact with the analyte. This arrangement was introduced in a beaker containing the electrolyte (1 mol L⁻¹ HNO₃) and a platinum wire as the cathode. The resulting solution from electrodissolution (0.6 A) was used for the ICP OES determinations. The influence of the aluminum concentration increase on the determination of the elements was evaluated. Electrodissolution of certified reference materials and commercial samples revealed relative errors lower than 10% for the elements Fe, Cu, Mg, Ni, Cr, Zn and Ti (when their content is above 0.1%). Higher inaccuracies (>10%) were observed for Mn and for Fe in B.C.S. 268/1 reference material certified. The proposed method presented a relative standard deviations (R.S.D.) lower or circa 10% to all of the elements (except Pb). In comparison with traditional acid dissolution, the proposed electrodissolution method is relatively fast (about 30 min), it is clean (there is no projection of solution) and simple (heating and fumes exhaust system were not necessaries).     

Structural-chemical disorder of manganese dioxides 1. Influence on surface properties at the solid-electrolyte interface

Relationships between lattice parameters of manganese dioxides and their surface properties at the solid-aqueous solution interface were investigated. The studied series ranged from ramsdellite to pyrolusite and encompassed disordered MD samples. The structural model used takes into account structural defects: Pr (rate of pyrolusite intergrowth) and Tw (rate of microtwinning). Water adsorption isotherms showed that the cross sectional area of water molecules adsorbed in the first monolayer is positively correlated to Pr. Titration of the surface charge of the MD series evidenced a positive linear relationship between the PZC and Pr (Pr=0, Tw=0, PZC=1 for ramsdellite; Pr=1, Tw=0, PZC=7.3 for pyrolusite; gamma-MD with intermediate values of Pr (0.2 to 0.45) have increasing PZC values). The rate of microtwinning appeared as a secondary factor for the increase of the PZC. The above correlations are explained by the chemical defects at the origin of the structural disorder, respectively Mn(3+)/Mn4+ substitution for Pr and Mn vacancies for Tw, which result in proton affinity and thus in increased PZC. The experimental results are compared with data collected in the literature for manganese dioxides as well as for dioxides of transition elements with tetragonal structure.     

Electronic properties of aluminum clusters compared with the jellium model

The experimental polarizabilities, ionization potentials and electron affinities of aluminum clusters are compared with jellium predictions. It is found that the clusters have radii and work functions which are close to the jellium model predictions for clusters with more than 13 atoms. The polarizabilities of Al _n correspond with the jellium only forn>40 and the shell structure features in the ionization potentials are anomalous up to 37. We conclude that nonjellium effects are important up ton=40.     

Synthesis of new derivatives of 4-amino-2,4-dihydro-1,2,4-triazol-3-one as potential antibacterial agents

Thirty new 2-substituted-4-amino-5-alkyl or aryl-2,4-dihydro-1,2,4-triazol-3-ones and ten 2-substituted-5-alkyl or aryl-4-(5-nitro-2-furfurylidene)amino-2,4-dihydro-1,2,4-triazol-3-ones were synthesized and characterised by their sharp melting points, elemental analysis, ir and ¹H nmr spectra. These new derivatives of 5-nitro-2-furaldehyde were screened for their antibacterial activities. Most of the compounds showed good activity against one test organism, Staphylococcus aureus. For a few compounds, C.M.I. ranged from 4 to 8 μg/ml (higher results than nitrofurantoin).     

Vertical distribution of the natural and artificial radionuclides in various soil profiles to investigate soil erosion

Vertical distributions of ¹³⁷Cs and ²¹⁰Pb in soil profiles were examined to study their availability in soil erosion at Gökova region where there exists intensive agricultural activities on sloppy fields. Since the mobility of these radionuclides depend on soil characteristics, soil samples were analyzed also for their physical and chemical properties. From ¹³⁷Cs inventories measured, erosion rates for cultivated and disturbed (no cultivation) soils were calculated to range from 79.1 to 6.5 t^.ha^-1.y^-1 and from 79.9 to 3.5 t^.ha^-1.y^-1, respectively. The ²¹⁰Pb technique is found to be not suitable for erosion determination for this area, presumably due to the coal-fired power plants operating in the region.     

Thermal and electrochemical C-X activation (X = Cl,Br, I) by the strong Lewis acid Pd3(dppm)3(CO)2+ cluster and its catalytic applications

The stoichiometric and catalytic activations of alkyl halides and acid chlorides by the unsatured Pd(3)(dppm)(3)(CO)(2+) cluster (Pd(3)(2+)) are investigated in detail. A series of alkyl halides (R-X; R = t-Bu, Et, Pr, Bu, allyl; X = Cl, Br, I) react slowly with Pd(3)(2+) to form the corresponding Pd(3)(X)(+) adduct and "R(+)". This activation can proceed much faster if it is electrochemically induced via the formation of the paramagnetic species Pd(3)(+). The latter is the first confidently identified paramagnetic Pd cluster. The kinetic constants extracted from the evolution of the UV-vis spectra for the thermal activation, as well as the amount of electricity to bring the activation to completion for the electrochemically induced reactions, correlate the relative C-X bond strength and the steric factors. The highly reactive "R(+)" species has been trapped using phenol to afford the corresponding ether. On the other hand, the acid chlorides react rapidly with Pd(3)(2+) where no induction is necessary. The analysis of the cyclic voltammograms (CV) establishes that a dissociative mechanism operates (RCOCl --> RCO(+) + Cl(-); R = t-Bu, Ph) prior to Cl(-) scavenging by the Pd(3)(2+) species. For the other acid chlorides (R = n-C(6)H(13), Me(2)CH, Et, Me, Pr), a second associative process (Pd(3)(2+) + RCOCl --> Pd(3)(2+.....)Cl(CO)(R)) is seen. Addition of Cu(NCMe)(4)(+) or Ag(+) leads to the abstraction of Cl(-) from Pd(3)(Cl)(+) to form Pd(3)(2+) and the insoluble MCl materials (M = Cu, Ag) allowing to regenerate the starting unsaturated cluster, where the precipitation of MX drives the reaction. By using a copper anode, the quasi-quantitative catalytic generation of the acylium ion ("RCO(+)") operates cleanly and rapidly. The trapping of "RCO(+)" with PF(6)(-) or BF(4)(-) leads to the corresponding acid fluorides and, with an alcohol (R'OH), to the corresponding ester catalytically, under mild conditions. Attempts were made to trap the key intermediates "Pd(3)(Cl)(+)...M(+)" (M(+) = Cu(+), Ag(+)), which was successfully performed for Pd(3)(ClAg)(2+), as characterized by (31)P NMR, IR, and FAB mass spectrometry. During the course of this investigation, the rare case of PF(6)(-) hydrolysis has been observed, where the product PF(2)O(2)(-) anion is observed in the complex Pd(3)(PF(2)O(2))(+), where the substrate is well-located inside the cavity formed by the dppm-Ph groups above the unsatured face of the Pd(3)(2+) center. This work shows that Pd(3)(2+) is a stronger Lewis acid in CH(2)Cl(2) and THF than AlCl(3), Ag(+), Cu(+), and Tl(+).