Role of tin in a PtSb alloy and a Pt-Sn/Al2O3 reforming catalyst

The conversion of n-hexane was studied on a Pt-Sn/Al₂O₃ catalyst, a PtSn alloy and on the corresponding Pt catalysts. The results indicate the same catalytic effect of tin in supported and unsupported catalysts. It is concluded that the role of tin is connected with alloy formation.

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- Pt-Sn/Al₂O₃, PtSn Pt-. . , .

     

Synthesis of N,N-diethyldithiocarbamate functionalized 1,4-polyisoprene, from natural rubber and synthetic 1,4-polyisoprene

N,N-Diethyldithiocarbamate functionnalized 1,4-polyisoprenes were prepared from 1,4-polyisoprenes (natural or synthetic). The syntheses were performed by nucleophilic addition of N,N-diethyldithiocarbamate salts upon oxirane rings of epoxidized units according to a SN2 mechanism with ring opening. Studies on model molecules of epoxidized 1,4-polyisoprene units (1,2-epoxy-1-methylcyclohexane and 4,5-epoxy-4-methyloctane) were previously achieved to develop the procedure. The best yields were obtained at low temperature in polar medium, and more especially in water with sodium N,N-diethyldithiocarbamate (DEDT-Na) as reagent. A diastereospecific addition was noted when reaction was performed in water with DEDT-Na. Afterwards, the developed procedure was successfully generalized to epoxidized synthetic polyisoprenes and epoxidized natural rubber (in THF, then in latex medium). Excellent results were obtained in latex medium with epoxidized natural rubber (ENR) latices. As with the models, a diastereospecific addition of sodium N,N-diethyldithiocarbamate trihydrate onto epoxidized 1,4-polyisoprene units of ENR was observed at the condition to bring the latex medium to pH 8 before introduction of DEDT-Na. Influence of temperature, drc, and DEDT-Na concentration were successively examined to determine the best conditions of the addition on ENR latices.     

Purification of a synthetic myristylated peptide by counter-current chromatography

A preparative purification of myristyl-Gly-Asn-Ile-Phe-Ala-Asn-Leu-Phe-Lys-Gly-Leu-Phe-Gly-Lys-Lys-Glu -NH2 was accomplished using the multi-coil counter-current chromatograph. A partition coefficient was determined in the n-butanol-acetic acid-water (4:1:5) system. Chromatographic runs were made in this system and one modified with ethyl acetate. The peptide material showed anomalous elution behavior due to its surfactant properties. It was found that by loading the sample exclusively in the stationary phase, satisfactory retention of the compound occurred. Finally, conditions utilizing the upper phase as the mobile phase successfully separated the impurities.     

水／AOT／正庚烷微乳体系中磺酸根水化作用的FT—IR研究

运用傅立叶变换红外光谱（FT－IR）对水／琥珀酸（乙基已基）磺酸钠（AOT）／正庚烷微乳体系中磺酸根的水化作用进行了研究．由于微乳体系中水分子与表面活性剂分子的相互作用，S＝O对称伸缩振动的红外吸收峰向低频方向移动．体系中的加水量W0（水与AOT的摩尔比）由0.5增大至25时，磺酸根对称伸缩振动的红外吸收峰由1051．39cm－1向低频移动至1046．15cm－1．同时，由于Na 的不对称作用，AOT分子中磺酸根反对称伸缩振动分裂成两个吸收峰，分别位于正215cm-1及1245cm－1附近，两个劈裂峰的距离及各自的峰面积均随体系中加水量的变化而变化，应用二阶导数、傅立叶退卷积及曲线拟会等分辨率增强技术可更清楚地反映出这个二重峰的变化情况．固体AOT分子中碳酸根反对称伸缩振动分裂的两个峰之间频率的差值约为42cm－1，形成微乳液以后，这两个峰的差值变小，W0为20时，这两个峰频率的差值逐渐减小到29cm-1，这些变化与磺酸根的水化程度直接相关     

Engineering reactions in crystalline solids: predicting photochemical decarbonylation from calculated thermochemical parameters

A detailed thermochemical analysis of the alpha-cleavage and decarbonylation reactions of acetone and several ketodiesters was carried out with the B3LYP/6-31G* density functional method. The heats of formation of several ground-state ketones and radicals were calculated at 298 K to determine bond dissociation energies (BDE) and radical stabilization energies (RSE) as a function of substituents. Results show that the radical-stabilizing abilities of the ketone substituents play a very important role on the thermodynamics of the alpha-cleavage and decarbonylation steps. An excellent correlation between calculated values and previous experimental observations suggests that photochemical alpha-cleavage and decarbonylation in crystals should be predictable from knowledge of excitation energies and the RSE of the substituent.     

Synthesis and Catalytic Application of Homo-bimetallic Metallocene Complexes as Ethylene Polymerization Catalysts

ＩｎｔｒｏｄｕｃｔｉｏｎＩｔｉｓｗｅｌｌｋｎｏｗｎｔｈａｔｍｅｔａｌｌｏｃｅｎｅｓａｃｔｉｖａｔｅｄｗｉｔｈｍｅｔｈｙｌａｌｕｍｉｎｏｘａｎｅ (ＭＡＯ)ａｒｅｈｉｇｈｌｙａｃｔｉｖｅｈｏｍｏｇｅｎｅｏｕｓＺｉｅｇｌｅｒ Ｎａｔｔａｃａｔａｌｙｓｔｓｔｈａｔｐｒｏｄｕｃｅｐｏｌｙｏｌｅｆｉｎｗｉｔｈｃｏｎ ｔｒｏｌｌｅｄｓｔｅｒｅｏｒｅｇｕｌａｒｉｔｙａｎｄｎａｒｒｏｗｍｏｌｅｃｕｌａｒｗｅｉｇｈｔｄｉｓｔｒｉ ｂｕｔｉｏｎ ,1 4 ｈｏｗｅｖｅｒ,ｔｈｅｍｏｌｅｃｕｌａｒｗｅｉｇｈｔｏｆｔｈｅｐｏｌｙｍ…     

Ni的掺入对复合氧化物LaFeO3的结构及性质的影响

合成子Ｎｉ替代铁酸稀土复合氧化物ＬａＦ３１－ｘＮｉｘＯ３（ｘ＝０．１－０．６），对样品进行了ＸＲＤ、ＩＲ及Ｍｏｓｓｂａｕｅｒ谱测试，结果表明：ｘ＝０＼１，０＼２，０＼３的样品为正交相，ｘ＝０．５，０．６的样品为菱方相；伴随相结构从正交向菱方结构的转变，ＩＲ谱上Ｆｅ（Ｎｉ）－Ｏ键伸振动谱带向高频移动近２０ｃｍ＾－１，Ｍｏｓｓｂａｕｅｒ谱测试表明Ｆｅ均处于＋３自旋态，Ｎｉ离子以＋３价进入晶格。     

Synthesis and properties of an ω,ω′-appended eighteen carbon chains hypericin derivative

Summary An ,-appended eighteen carbon chains hypercin derivative (2) was synthesized starting from emodin. The overall yield of the seven step synthesis was 12%. The¹H and¹³C NMR, absorption, and emission spectroscopic properties were measured;2 can be dissolved even in apolar solvents and polyethylene.

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Synthese und Eigenschaften eines mit C₁₈-Ketten ,-substituierten Hypericinderivats

Zusammenfassung Ein in den Positionen , mit zwei C₁₈-Ketten substituiertes Derivat des Hypericins (2) wurde ausgehend von Emodin synthetisiert. Die Gesamtausbeute der siebenstufigen Synthese betrug 12%. Die¹H- und¹³C-NMR, absorptions- und emissionsspektroskopischen Eigenschaften wurden gemessen;2 kann sogar in apolaren Lösungsmitteln und Polyethylen gelöst werden.

     

Research on 1-azabicyclic compounds

1-(2-Furyl)-3-amino-4,4-dimethylpentane was used to obtain 3-tert-butyl-1,2-dihydropyrrolizine, the catalytic hydrogenation of which over Rh/Al₂O₃ at room temperature gives a mixture of cis- and trans-3,8-H-3-ter-butylpyrrolizidines with predominance of the cis isomer, whereas hydrogenation at 90–100 °C gives a mixture containing the trans isomer as the principal component. The three-dimensional structures of the isomers follow from data on the catalytic hydrogenation and isomerization and the IR, Raman, and PME spectra. A considerable percentage of the trans-fused form is characteristic for cis-3,8-H-3-tert-butylpyrrolizidine.     

Diffusion of additives and plasticizers in poly(vinyl chloride)—II: The self-diffusion of the stabilizers dibutyltin dilaurate and dibutyltin bismonobutylmaleate in plasticized poly(vinyl chloride)

The self-diffusion coefficient, D, of dibutyltin dilaurate and dibutyltin bismonobutylmaleate have been obtained at 35, 45 and 55° in samples of poly(vinyl chloride) plasticized with 34, 60 and 100 phr of di(2-ethylhexyl)phthalate. D at 2 phr of the laurate is 3–5 times larger than for the smaller maleate molecule. In all cases, D increases with increasing plasticizer concentration, an effect interpreted in terms of the free volume theory of diffusion. D for the laurate increases by a factor of about 2.7 when the laurate diffusant concentration is increased from 0 to 4 phr. The activation energies for diffusion, E_D, lie between 50 and 90 kJ mol^?1. They increase with increasing plasticizer concentration but become constant at higher plasticizer concentrations (60–100 phr). It is impossible to correlate all the known data on diffusion in plasticized PVC with an equation of the form log D₀ = C₁ + C₂ E_D/RT