Molecular dynamics simulation of the aqueous solvation shell of cellulose and xanthate ester derivatives

Gonzalo Riadi, Fernando González-Nilo. Centro de Bioinformática y Simulación Molecular, Universidad de Talca, Casilla 721, Talca, Chile.MD simulations of a pentasaccharide having D-glucopyranoside residues connected by (14)- glycosidic linkages, as a model of cellulose solvated in water, were carried out comparing the solvation of the hydroxyl group at C2 of the central ring of the pentamer and that of a single glucopyranose ring. MD simulations of 10 nsec were carried under NPT and periodic boundary conditions at 298 K and 1 atm. Explicit solvent (TIP3) and the force field CHARMM27 (modified for xanthate ester derivatives) were used in the molecular dynamics simulations. RDF calculations with respect to O2 of the central ring of the pentamer showed a well structured first solvation shell followed by secondary shells. When comparing the simulations of the pentamer to a single glucopyranose ring, it was observed that the solvation of O2 was lower for one repetitive unit, indicating that the pentamer had a stronger H-bond structure of water around O2 due to the cooperative effect of the neighboring residues. When the O2 of the central ring of the pentamer was substituted by a p-nitrobenzylxanthate moiety (pentXNB) there was a strong decrease in the hydration of the substituted O2 but the carbon and the sulfur of the thiocarbonyl group were clearly hydrated compared to the sulfur bridge. The global minimum energy conformation showed the p-nitrobenzyl group folded over the neighboring glucose ring. However, the simulations showed that the XNB group oscillates over the pentamer in periods of ca. 3000 psec

Intramolecular Amino-thiolysis Cyclization of Graphene Oxide Modified with Sulfur Dioxide: XPS and Solid-State NMR Studies

Graphite microparticles were oxidized to graphene oxide (MPGO) by Hummers’ method followed by thermal exfoliation (C/O ratio 1.53). Graphene oxide was modified with SO2 (mMPGO) at 600 °C and by subsequent treatment at 200 °C having a sulfur content of 10.9% (C/O ratio 16.94) and manganese content 9.39 μmol·g–1. The XPS spectrum of MPGO showed the presence of carbonyl and epoxide groups. The reactivity of mMPGO toward alkyl thiol and alkyl amine showed the same selectivity as other carbons and suggested that oxidation did not modify deeply the edging structure of graphite. Therefore, the tetradehydrogenated-benzo[α]anthracene (TBA) reactive site model is valid. From XPS and solid-state NMR, amino-thiolysis occurred via cyclization. On the basis of the joint analysis of solid-state 1H and 13C NMR spectra of mMPGOs treated with mono- and difunctionalized alkanes, a preferred conformation of the alicyclic moiety of aminothiol over the graphene matrix occurred via binding to mMPGO at both amine and thiol ends. It was found that paramagnetic manganese ions in mMPGO can lead to cross-polarization inefficiency in the 13C CPMAS detection of alkyl chains bound to mMPGO, while ring currents from graphene aromatic layers can shift alkyl 1H NMR signals to lower frequencies by up to 4 ppm

Molecular gas in the Galactic center region .1. Data from a large scale (CO)-O-18(J=1->0) survey

Artículo de publicación ISIA large scale survey of the Galactic center region in the (CO)-O-18(J = 1 --> 0) transition is presented. This survey was obtained with the 1.2 m Southern Millimeter-Wave Telescope (SMWT) at the Cerro Tololo Interamerican Observatory (CTIO) near La Serena, Chile. It covers the region 1.degrees 05 less than or equal to iota less than or equal to +3.degrees 6 and -0.degrees 9 less than or equal to b less than or equal to +0.degrees 75 with a grid spacing of 9', i.e. the sampling is at full FWHP beamwidth. 357 positions were in total observed. After reviewing the instrumentation of the 1.2m SMWT, the observing techniques, and the methods used in the data reduction, the data of the survey are presented and morphologically described. In addition, data of the HNCO(5(0,5) -4(0,4)) line are presented, which was also included in the large bandwidth of the spectrometer. (CO)-C-12(1 - 0) measurements performed for comparison purposes are presented and compared with other (CO)-C-12 results The maps of the (CO)-O-18(1 - 0) survey demonstrate that there are great differences between the distribution of the optically thin (CO)-O-18(1 - 0) emission and the usually optically thick (CO)-C-12(1 - 0) emission

Multimetallic complexes and functionalized gold nanoparticles based on a combination of d- and f-elements

The new DO3A-derived dithiocarbamate ligand, DO3A-tBu-CS2K, is formed by treatment of the ammonium salt [DO3A-tBu]HBr with K2CO3 and carbon disulfide. DO3A-tBu-CS2K reacts with the ruthenium complexes cis-[RuCl2(dppm)2] and [Ru(CH═CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) to yield [Ru(S2C-DO3A-tBu)(dppm)2]+ and [Ru(CH═CHC6H4Me-4)(S2C-DO3A-tBu)(CO)(PPh3)2], respectively. Similarly, the group 10 metal complexes [Pd(C,N-C6H4CH2NMe2)Cl]2 and [PtCl2(PPh3)2] form the dithiocarbamate compounds, [Pd(C,N-C6H4CH2NMe2)(S2C-DO3A-tBu)] and [Pt(S2C-DO3A-tBu)(PPh3)2]+, under the same conditions. The linear gold complexes [Au(S2C-DO3A-tBu)(PR3)] are formed by reaction of [AuCl(PR3)] (R = Ph, Cy) with DO3A-tBu-CS2K. However, on reaction with [AuCl(tht)] (tht = tetrahydrothiophene), the homoleptic digold complex [Au(S2C-DO3A-tBu)]2 is formed. Further homoleptic examples, [M(S2C-DO3A-tBu)2] (M = Ni, Cu) and [Co(S2C-DO3A-tBu)3], are formed from treatment of NiCl2·6H2O, Cu(OAc)2, or Co(OAc)2, respectively, with DO3A-tBu-CS2K. The molecular structure of [Ni(S2C-DO3A-tBu)2] was determined crystallographically. The tert-butyl ester protecting groups of [M(S2C-DO3A-tBu)2] (M = Ni, Cu) and [Co(S2C-DO3A-tBu)3] are cleaved by trifluoroacetic acid to afford the carboxylic acid products, [M(S2C-DO3A)2] (M = Ni, Cu) and [Co(S2C-DO3A)3]. Complexation with Gd(III) salts yields trimetallic [M(S2C-DO3A-Gd)2] (M = Ni, Cu) and tetrametallic [Co(S2C-DO3A-Gd)3], with r1 values of 11.5 (Co) and 11.0 (Cu) mM–1 s–1 per Gd center. DO3A-tBu-CS2K can also be used to prepare gold nanoparticles, Au@S2C-DO3A-tBu, by displacement of the surface units from citrate-stabilized nanoparticles. This material can be transformed into the carboxylic acid derivative Au@S2C-DO3A by treatment with trifluoroacetic acid. Complexation with Gd(OTf)3 or GdCl3 affords Au@S2C-DO3A-Gd with an r1 value of 4.7 mM–1 s–1 per chelate and 1500 mM–1 s–1 per object