Sequential superparamagnetic clustering for unbiased classification of high-dimensional chemical data

For the clustering of chemical structures that are described by the Similog, ISIS count, and ISIS binary fingerprints, we propose a sequential superparamagnetic clustering approach. To appropriately handle nonbinary feature keys, we introduce an extension of the binary Tanimoto similarity measure. In our applications, data sets composed of structures from seven chemically distinct compound classes are evaluated and correctly clustered. The comparison, with results from leading methods, indicates the superiority of our sequential superparamagnetic clustering approach.     

Calculation of the carrier-induced refractive index change in InSb

We report a theoretical model for an estimate of carrier-induced changes in the refractive index of InSb at room temperature. The dispersion of n within the photon-energy interval of 0.12–0.24 eV is investigated for nonequilibrium carrier concentrations of 10¹⁵–10¹⁸ cm^–3. An analysis of the influence of the initial carrier density on n is performed. The obtained results can help to develop InSb opto-electronic devices.     

Grafting of poly-<Emphasis Type="Italic">N</Emphasis>-methacryloylaminodeoxyglucose on poly-<Emphasis Type="Italic">N</Emphasis>-vinylpyrrolidone

A graft copolymer simulating glycoprotein was prepared by reaction of poly-N-methacryloylaminodeoxyglucose containing terminal amino group with a copolymer of N-vinylpyrrolidone and acrylic acid N-hydroxysuccinimide ester.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1356–1359.Original Russian Text Copyright © 2004 by Nazarova, Pavlov, Kever, Afanaseva, Panarin.     

Bifunctional activation of amine-boranes by the W/Pd bimetallic analogs of “frustrated Lewis pairs”

The reaction between basic [(PCP)Pd(H)] (PCP = 2,6-(CH₂P(t-C₄H₉)₂)₂C₆H₄) and acidic [LWH(CO)₃] (L = Cp (1a), Tp (1b); Cp = η⁵-cyclopentadienyl, Tp = κ³-hydridotris(pyrazolyl)borate) leads to the formation of bimolecular complexes [LW(CO)₂(μ-CO)⋯Pd(PCP)] (4a, 4b), which catalyze amine-borane (Me₂NHBH₃, ^tBuNH₂BH₃) dehydrogenation. The combination of variable-temperature (¹H, ³¹P{¹H}, ¹¹B NMR and IR) spectroscopies and computational (ωB97XD/def2-TZVP) studies reveal the formation of an η¹-borane complex [(PCP)Pd(Me₂NHBH₃)]⁺[LW(CO₃)]⁻ (5) in the first step, where a BH bond strongly binds palladium and an amine group is hydrogen-bonded to tungsten. The subsequent intracomplex proton transfer is the rate-determining step, followed by an almost barrierless hydride transfer. Bimetallic species 4 are easily regenerated through hydrogen evolution in the reaction between two hydrides.

Bimetallic complexes [LW(CO)₂(μ-CO)⋯Pd(PCP)] cooperatively activate amine-boranes for their dehydrogenation via N–H proton tunneling at RDS and H₂ evolution from two neutral hydrides.     

Platinum(IV)-mediated nitrile-sulfimide coupling: a route to heterodiazadienes

Pt(IV)-mediated addition of the sulfimide Ph2S = NH and the mixed sulfide/sulfimides o- and p-[PhS(=NH)](PhS)-C6H4 by the S=NH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4[NH=C(R)N=SR'Ph]2] (R' = Ph, R = Me, Et, CH2Ph, Ph; R' = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2S=NH leads exclusively to trans-[PtCl4[NH=C(R)N=SPh2]2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4[NH=C(Me)N=SPh2]2] and the latter have been separated by column chromatography. Theoretical calculations at both HF/HF and MP2//HF levels for the cis and trans isomers of [PtCl4[NH=C(Me)N=SMe2]2] indicate a higher stability for the latter. Compounds trans-[PtCl4[E-NH=C(R)N=SPh2]2] (R = Me, Et) and cis-[PtCl4[E-NH=C(Me)N=SPh2][Z-NH=C(Me)N=SPh2]] have been characterized by X-ray crystallography. The complexes [PtCl4[NH=C(R)N=SPh2]2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4[NH=C(NH2)R]2] the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4[NH=C(R)N=SR'Ph]2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NH=C(R)=SR'Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-[PhS(=NH)](PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the coupling--in contrast to the Pt(IV) species--gives the chelates [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh]]. The X-ray crystal structure of [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh-o]] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum.     

Electrooptical and Conformational Properties of Poly(1-Trimethylsilyl-1-Propynes) with Different Chain Microstructures

The methods of the Kerr effect and solution hydrodynamics were applied to study the electrooptical and hydrodynamic properties of samples of disubstituted polyacetylenes, poly(1-trimethylsilyl-1-propynes), prepared by polymerization of 1-trimethylsilyl-1-propyne with NbCl₅ and TaCl₅/BuLi as catalysts. The experimental electrooptical characteristics of polymers were compared with those calculated by PM3 semiempirical quantum-chemical method.     

Nuclear orientation of156Tb in gadolinium matrix

The anisotropy of the angular distribution of gamma-rays from the decay of¹⁵⁶Tb, oriented in a gadolinium matrix at low temperatures, has been measured at the angles of 0 and π/2 with respect to the applied magnetic field direction in the range of temperatures from 14·6 to 68·4 mK. The temperature dependence of anisotropy was measured for the first time. The parameters of hyperfine magnetic dipole and electric quadrupole splittings have been determined and the values of the magnetic dipole moment ¦Μ¹⁵⁶¦=(9·6±1·3)×10^?27 J/T and the electric quadrupole momentQ ¹⁵⁶=(2·9±0·9)×10^?28 m² of the¹⁵⁶Tb ground state have been calculated. Multipole mixing ratios andB(E2) branching ratios of many gamma-ray transitions occurring in¹⁵⁶Gd have been found and the results have been discussed in terms of the rotational-vibration and pairing-plus-quadrupole models.