Dual role of the six-coordinated molybdenum and lead ions in novel of photochromic properties of the molybdenum–lead–borate glasses

Transparent glasses were prepared by conventional melting–quenching method in the xMoO₃·(100 ? x)[3B₂O₃·PbO] system where 0 ≤ x ≤ 15 mol%. By increasing the MoO₃ content up to 20 mol% the PbMoO₄ crystalline phase appears. These systems exhibit a photochromic effect which can be induced through laser exposures (λ = 633 nm) directly on the bulk sample. Structural investigations by FTIR spectroscopy show that the photosensitive effect is due to a reduction of Mo⁶⁺ to Mo⁴⁺ and/or Mo⁵⁺ promoted by the oxidation of Pb²⁺ and some structural changes of the borate network.     

Surface tension of lead–lithium melts

The temperature and concentration dependences of the surface tension of lithium alloys based on lead are experimentally determined for the first time in a field of compositions with up to 20 at % lithium in lead in the temperature range from the liquidus up to 700 K. The isotherm of surface tension of the studied alloys in the range of compositions with ~10 at % Li in lead contains a minimum, as does the adsorption isotherm of lithium in the sub-eutectic area of PbLi compounds.     

Structural effects of the lone pair on lead(II), and parallels with the coordination geometry of mercury(II). Does the lone pair on lead(II) form H-bonds? Structures of the lead(II) and mercury(II) complexes of the pendant-donor macrocycle DOTAM (1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane)

The synthesis and structures of [Pb(DOTAM)](ClO4)2.4.5H2O (1) and [Hg(DOTAM)](ClO4)2.0.5CH3OH.1.5H2O (2) are reported, where DOTAM is 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane. Compound 1 is triclinic, space group P, a = 12.767(3) A, b = 13.528(2) A, c = 18.385(3) A, alpha = 101.45(2) degrees, beta = 93.32(2) degrees, gamma = 90.53(2) degrees, Z = 4, R = 0.0500. Compound 2 is monoclinic, space group Cc, a = 12.767(3) A, b = 13.528(2) A, c = 18.385(3) A, beta = 101.91(2) degrees, Z = 4, R = 0.0381. The Pb(II) ion in 1 has an average Pb-N = 2.63 A to four N-donors from the macrocyclic ring, and four O-donors (average Pb-O = 2.77 A) from the amide pendant donors of the macrocycle, with a water molecule placed with Pb-O = 3.52 A above the proposed site of the lone pair (Lp) on Pb. The Hg(II) in 2 appears to be only six-coordinate, with four Hg-N bond lengths averaging 2.44 A, and two Hg-O from pendant amide donors at 2.41 A. The other two amide donors appear to be noncoordinating, with Hg-O distances of 2.74 and 2.82 A. A water situated 3.52 A above the proposed site of the lone pair on Pb(II) in 1 is oriented in such a way that it might be thought to be forming a Pb-Lp.H-O-H hydrogen bond. It is concluded that that this is not an H-bond, but that the presence of the lone pair allows a closer approach of the hydrogens to Pb than would be true otherwise. The structural analogy in the VSEPR sense between Pb(II), which has the 5d(10)6s(2) outer electron structure, and the Hg(II) ion, which has the 5d10 structure, is examined. The tendency of Hg(II) toward linear coordination, with two short Hg-L bonds (L = ligand) at 180 degrees to each other, and other donor groups at roughly 90 degrees to this and at much longer bond distances, is paralleled by Pb(II). One of the short Hg-L bonds is replaced in the Pb(II) structures by the lone pair (Lp), which is opposite the short Pb-L bond, or in some cases 2-4 shorter Pb-L bonds.     

New mixed palladium—lead and palladium—tin tellurides of the NiAs type

New ternary mixed nickel arsenide-type palladium and platinum—Group 14 metal tellurides were searched for by the high-temperature ampoule synthesis combined with the X-ray powder diffraction analysis. As a result, new phases of the ternary Pd—Pb—Te and Pd—Sn—Te systems belonging to the NiAs structure type were synthesized. The crystal structure of the compound PdPb_0.304(5)Te_0.695(5) was determined by the Rietveld method (P6₃/mmc, a = 4.151(1) Å, c = 5.680(1) Å, Z = 2, R ₁ = 0.032, R _p = 0.075, wR _all = 0.025). It was shown that no ordering exists in the occupancy of the main-group atom site by lead and tellurium. In the Pd—Sn—Te system, a phase isostructural with the above-mentioned compound was found. In the latter phase, there is also no ordering in the occupancy of the main-group atom site. According to the electron diffraction data, a superstructure derived from the NiAs type exists in a narrow range of the compositions PdSn_0.3Te_0.7—PdSn_0.4Te_0.6.     

The heat capacity of lead from 300 to 850°k: conversion of cp to cv for liquid lead

Abstract

Recent measurements of the heat capacity at constant pressure C_p for lead from 300 to 850°K have shown that C_p for liquid lead decreases continuously from the melting point to 850°K. Using data in the literature of density and velocity of sound, the dilation correction has been applied to C_p to obtain the heat capacity at constant volume C_v for liquid lead. Application of the dilation correction to solid lead gives a C_v curve which uncreases only about one joule/gm-atom-°K from 300 to 600°K, whereas the C_v curve for liquid lead decreases almost 5 joules/gm-atom-°K from 600 to 850°K. A careful assessment of the uncertainty in the quantities used in the dilation correction leads to an uncertainty in C_v of ± 2.5% (about one joule/gm-atom-°K), and thus the decrease in C_v for liquid lead is quite real.     

Adsorption–photometric determination of lead in cattle liver

A styrene–maleic anhydride copolymer is synthesized, modified in the presence of p-sulfoaniline and formaldehyde, and a new polymer adsorbent is obtained and identified by IR spectroscopy. The ionization constants of ionogenic groups in the adsorbent are determined by the potentiometric method. The adsorption and desorption of lead(II) on the obtained adsorbent are investigated, and optimal conditions of preconcentration are determined. An adsorption–photometric procedure for the determination of lead is proposed, including the adsorption preconcentration of lead(II) from a buffer solution with pH 6 and desorption with a solution of HCl (with the desorption rate of up to 99%). The procedure was used to determine lead in the cattle liver.     

Does double electron capture lead to the formation of biradicals? An ECD-SORI-CID study on lacticin 481

We studied lacticin 481, a small lantibiotic with three lanthionine bridges, by electron capture dissociation (ECD) in a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. Following electron capture, very little fragmentation was observed, but species formed by nondissociative single and multiple electron capture were abundant. Ions formed by double electron capture were subjected to sustained off resonance irradiation collision induced dissociation (SORI-CID) to determine whether stable biradicals were formed. In the SORI-CID spectra of the ions formed by double electron capture, some, but minor, H* radical loss was observed, which was not observed at all for regularly protonated ions. A small part of the ions formed by double electron capture are thus long-lived biradicals. Apart from the observed H* loss, the SORI-CID spectra of ions that captured two electrons was similar to that of regularly protonated ions and quite different from the SORI-CID spectra of radical ions formed by single electron capture. This implies that recombination of the two radical sites is the dominant process in biradical lacticin 481 ions, at least on the time scale of our SORI-CID experiments.     

Thermal Analysis of Binary Systems. Explosive – lead compound

The thermal decomposition of explosives: pentaerythrol tetranitrate (PETN), 2,4,6-trinitrotoluene(TNT), cyclo-1,3,5-trimethylene-2,4,6-trinitroamine (RDX) and their two-component mixtures with 40% of lead compounds [PbO, Pb₃O₄, Pb(NO₃)₂] were performed. The simple method of determination of stability changes in the mixtures described above, in comparison with pure explosives was presented. The lead oxides accelerated significantly the thermal decomposition of explosives. Pb(NO₃)₂ acts as a catalyst in the mixture containing TNT degradation, but not in a case of PETN and RDX. This revised version was published online in August 2006 with corrections to the Cover Date.     

International comparison of the determination of the mass fraction of cadmium, chromium, mercury and lead in polypropylene: the Comité Consultatif pour la Quantité de Matière pilot study CCQM-P106

The CCQM-P106 pilot study was organized by the inorganic working group of the Comité Consultatif pour la Quantité de Matière (CCQM) as a feasibility comparison to study the applicability of different analysis methods to the polypropylene sample and test the abilities of the participants for measuring the Cd, Cr, Hg and Pb in polypropylene. National Institute of Metrology P.R. China (NIM) acted as the coordinating laboratory of this pilot study. There were 21 laboratories that submitted the final results. The median values of the mass fraction of Cd, Cr, Hg and Pb were 36.12 mg kg^?1 (the median absolute deviation about the median (MADe) = 0.46 mg kg^?1), 252.5 mg kg^?1 (MADe = 3.4 mg kg^?1), 387.0 mg kg^?1 (MADe = 10.1 mg kg^?1) and 466.2 mg kg^?1 (MADe = 8.9 mg kg^?1), respectively. Isotope dilution mass spectrometry (IDMS), inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-optical emission spectrometry (ICP-OES), atomic absorption spectrometry (AAS), instrumental neutron activation analysis (INAA) and X-ray fluorescence (XRF) measurement methods were used, and microwave digestion was used by the most of the participants. In general, very good agreement of the results was observed. Moreover, compared to the results of other methods, the results of IDMS still showed less spread amongst laboratories and had a smaller uncertainty. In addition, the results of some analytes used by XRF and INAA also got satisfactory agreement with the median value.     

Anionic polymerization of ϵ-caprolactam-lix effect of the ratio of reacting components,of the medium and of the ring size on the initial stage of the anionic polymerization of lactams

Effects of the concentrations and ratio of reacting components and of temperature on the kinetics of reaction of N-propionyllactam (I) with potassium salt of lactam (KL) were studied for derivatives of ϵ-caprolactam, 8-octanelactam and 12-dodecanelactam. For ϵ-caprolactam, the initial rates of propagation, acylation of open-chain amide groups and condensation of growth centres were estimated. At the ratio of the starting components [I]₀/[KL]₀ = 0.5-3, the participation of the polymerization reaction is constant, amounting to ca 45% of the overall consumption of 1. The condensation reaction is 14–36% of the total consumption of I; its initial rate passes through a maximum at [I]₀/[KL]₀ = 2. With increasing permittivity of the medium, the total rate of consumption of I increases; in two media with the same bulk permittivity, however, the rates may differ by as much as one order of magnitude.     

Construction of the Skeleton of Phthalascidin, Mechanism of the Formation of the Key Tricyclic Lactam Intermediate

Phthalascidin is a structurally simplified version of Et-743, which is a potent anti-tumor marine natural product isolated from Ecteinascidia turbinata. Its antiproliferative activity is greater than that of the agents taxol, camptothecin, adriamycin, mitomycin C, cisplatin, bleomycin, and etoposide by 1-3 orders of magnitude. An elegant synthesis of Et-743 and phthalascidin has been reported by E. J. Corey and co-workers1,2. As part of our continuing program, we have also engaged in dev…     

Synthesis of two peptides of α-bungarotoxin and the participation of the amino acid residue Trp-28 of the neurotoxin in the antigenicity of the molecule

Using the method of solid-phase peptide synthesis, two peptides have been synthesized, one of which corresponds to the central ring structure of -bungarotoxin (-BTX), while the second has in position 28 a Gly residue in place of the Trp in the first peptide, and their interrelationship with antitoxin antibodies has been investigated. It has been shown that the amino acid residue Trp-28 of -BTX, which is the contact residue in binding with the acetylcholine receptor, also participates directly in binding with the active centers of antibodies to -BTX.Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 628–631, July–August, 1997.     

Studies of the dissociation and the protonation of TB-chlorosulphophenol

The dissociation constant of each step for TB-chlorosulphophenol has been determined by potentiometric method, and the thermodynamic constants, △G°, △H° and △S°, of the dissociation process have been calculated. The protonation constants were measured by the spectrophotometric method. The pH values of various forms of anions of the chromogenic reagent at their concentrations were also calculated.     

Does nanoclay addition always lead to amelioration? Dual effects of the nanoclay on the PA‐6/EVOH/SEBS ternary blends

This work presents the investigation of properties of polyamide‐6 (PA‐6)/ethylene vinyl alcohol (EVOH)/styrene‐ethylene‐butylene‐styrene (SEBS) ternary blends and related nanocomposites with nanoclays. In this way, the effect of the mixing protocol and nanoclay type on the morphology, mechanical, and rheological properties of the blends was comprehensively studied. Scanning electron microscopy (SEM) observation revealed that, for the neat ternary blends, core‐shell droplets were formed in which SEBS droplets were encapsulated by EVOH phase in the PA‐6 matrix. In this regard, experimental observations were compared and discussed with the predictions of phenomenological models. According to the X‐ray diffraction analysis, the distribution and degree of dispersion of the nanoclays were significantly influenced by mixing protocol. It was demonstrated that competition between the intrinsic effect of the nanoclay on the physical properties and its inhibiting effect on the interactions between PA‐6 and EVOH phases led to some interesting observations for the rheological and mechanical properties of the ternary blends. The results revealed that optimum properties could be obtained by selecting appropriate nanoclay and mixing protocol.     

Synthesis and characterization of lead oxide nano-powders by sol–gel method

Our goal in this research was to obtain lead oxide nano-powders by sol–gel method. In this method, lead oxide nano-powders were synthesized through the reaction of citric acid (C₆H₇O₈·H₂O) solution and lead acetate [Pb(C₂H₃O₂)₂] solution as stabilizer and precursor, respectively. The effect of different parameters including calcination temperature, (molar ratio of citric acid to lead acetate) and drying conditions were investigated. The prepared lead oxide nano-powders were characterized by FT-IR spectroscopy, X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. The prepared PbO samples consist of the particles in the range of 50–120 nm or the thick plate like structures with thickness of 53 nm depending on the drying conditions.     

Determination of the equilibrium melting point of the β-form of polypropylene

The melting behavior of the -form of isotactic polypropylene (-iPP) was investigated as a function of crystallization time and temperature. Calcium suberate, a selective -nucleating agent was used to produce samples that consist entirely of -form i-PP. The experimental melting points were recorded at different crystallization times and were extrapolated to the start of the crystallization process in order to eliminate the effect of lamellar thickening. Using the non-linear Hoffman—Weeks approach to correlate these extrapolated experimental melting temperatures with the corresponding crystallization temperatures, an equilibrium melting point of 209°C was obtained for -iPP. The equilibrium melting point estimated through the non-linear Hoffman—Weeks analysis is about 30°C higher than that (T _m ⁰=177°C) obtained on the basis of the linear extrapolation. These results are consistent with earlier claims that a linear extrapolation of T _m–T _c data leads to an underestimation of the equilibrium melting point. The results obtained for -iPP exemplify the importance of accounting for both the isothermal lamellar thickening effects and the non-linearity in the T _m–T _c correlation, when the determination of an equilibrium melting point is carried out using a procedure based on the predictions of the Lauritzen—Hoffman secondary nucleation theory.This revised version was published online in November 2005 with corrections to the Cover Date.