The isotopes259106,260106, and261106

In irradiations of²⁰⁷Pb and²⁰⁸Pb, respectively, with⁵⁴Cr theα-decay of the isotopes²⁵⁹106,²⁶⁰106, and²⁶¹106 could be observed for the first time. For²⁶⁰106 a spontaneous fission branch of (50 _?20 ⁺³⁰ )% was observed. The isotopes were identified by genetic relationships of α-decay after separation in-flight with the velocity filter SHIP and implantation into a position-sensitive silicon surface-barrier detector. The measured partial fission halflife of the doubly even isotope²⁶⁰106 of (7.2 _?2.7 ^+4.8 )ms exceeds the predicted values by at least a factor of 40. This result could be explained by the high shell corrections of the ground state mass, derived from the measured α-decay energies. The experimental results show evidence for an island of purely shell stabilized nuclei in the region of deformed isotopes beyond the actinides.     

Flow injection spectrofluorimetric determination of reserpine in tablets by on-line acetone sensitized photochemical reaction

On-line photochemical reaction of reserpine in the presence of acetone was investigated. Acetone was found to speed up the on-line photochemical conversion of reserpine into an intensively fluorescent compound. Not only reaction acidity but also the acetate buffer concentration affected the on-line photochemical induced fluorescence signal. Based on the observation an automated flow injection photochemical fluorimetric approach was developed. An injected sample zone was carried by a water stream to be merged with a acetate buffer (pH 3.4) solution containing 0.02% acetone in a knotted PTFE reactor (KR), which was freely coiled around a 6-W low pressure mercury lamp. While passing the KR, reserpine was transformed into an intensively fluorescent compound. It was on-line detected in a flow-through cell at the emission wavelength of 490 nm and excitation wavelength of 386 nm. At optimized conditions, a detection limit 0.45 mug l(-1) was achieved at a sampling rate of 90 h(-1). Eleven determinations of a 0.5 mg l(-1) reserpine standard solution gave a R.S.D. of 0.3%. The linear dynamic range of reserpine calibration curve was 0.01-0.75 mg l(-1). The proposed method was applied to assay the reserpine content in tablets and to monitor the dissolution profile of reserpine tablets. Satisfactory results were obtained for both the assays and dissolution studies.     

The thermal reaction of HNCO at moderate temperatures

The thermal reaction of HNCO has been studied in a static cell at temperatures between 873 and 1220 K and a constant pressure of 800 torr under highly diluted conditions. The reaction was measurable above 1000 K by FTIR spectrometry. The products detected include CO, CO₂, HCN, NH₃, and the unreacted HNCO. In this moderate temperature regime, the rates of product formation and HNCO decay cannot be accounted for by a previously established high-temperature mechanism, assuming HNCO → NH + CO (1) as the initiation process. Instead, a new bimolecular reaction, 2HNCO → CO₂ + HNCNH (2), has been invoked to interpret the disappearance of HNCO as well as the formation of various products, most importantly CO₂. The concentration profiles of all measured species can be quantitatively modeled, throughout the temperature range analyzed, by varying k₂ using a modified mechanism. The kinetically modeled values of k₂ can be effectively represented by This result agrees closely with that computed with the conventional transition-state theory using the TST parameters predicted by the BAC-MP4 method: The bimolecular reaction takes place via a stable 4-membered ring intermediate which is isoelectronic with diketene; viz.      

聚合物分子链的横截面积与分子链的运动

本文把单个分子链的横截面积与聚合物的玻璃化转变温度联系起来,发现对于所讨论的聚合物,考虑了分子链间的相互作用以后,上面二者之间有一一对应的关系。认为单个分子链的横截面积与聚合物分子链柔顺性有关。同时采用文献[17]的方法,得到了1,2-聚丁二烯的分子链的内旋转异构化能,比较所得结果,证实了上面的看法。     

Synthesis of a novel 18β-glycyrrhetinic acid derivative

A novel compound, biotinylated 18β-glycyrrhetinic acid (BGA), was synthesized. It is a compound of 18β-glycyrrhetinic acid linked with biotin. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 266–267, May–June, 2006. An erratum to this article is available at .     

Photoinduced deformation of amphiphilic azo polymer colloidal spheres

Photoinduced shape deformation of colloidal spheres made of an amphiphilic azo polymer has been demonstrated in this work. The polymer contains the donor-and-acceptor-type azobenzene chromophores and can form uniform colloidal spheres by dropwise adding water into its THF solution. When the colloidal spheres obtained were exposed to the interfering p-polarized Ar+ laser beams (150 mW/cm2), the colloidal spheres changed to prolates (i.e., "rugby-balls"), "spindles", and finally "rods", depending on the irradiation times. The elongated direction of the spheres was observed to be the same as the polarization direction of the laser beam. The average major-to-minor ratio of the ellipsoids could be easily adjusted by controlling the irradiation time. The deformation effect observed in this work can offer a new way to prepare nonspherical colloids from colloidal spheres and will shed new light on the correlation between the photodriven shape deformation and photoinduced surface relief gratings for the same type of polymers.     

Cyclization reactions of N-acryloyl-2-aminobenzaldehyde derivatives: formal total synthesis of martinellic acid

N-Alkyl acryloylamides derived from o-aminobenzaldehyde derivatives react with N-alkyl glycine derivatives to provide cis-fused pyrrole[3,2-c]quinolones in moderate yield and high diastereoselectivity. These same substrates engage in a tandem Michael-Mannich pathway on treatment with a secondary amine, providing corresponding quinolone derivatives. The elaboration of a pyrroloquinolone derivative via addition of an in situ generated functionalized copper acetylide to an in situ generated iminium ion provided the C2-substituted derivative. Global deprotection and reduction of the alkyne afford the tricyclic triamine core (as the HCl salt) found in martinellic acid.     

Ion flotation of rhodium(III) and palladium(II) with anionic surfactants

The ion flotation of rhodium(III) and palladium(II) with some anionic surfactants has been investigated. Two flotation procedures are proposed for the separation of some platinum metals, based on differences in the kinetic properties of the chloro-complexes of rhodium(III), palladium(II) and platinum(IV). The first involves the selective flotation of Rh(H(2)O)(3+)(6) from PdCl(2-)(4) and PtCl(2-)(6) in dilute hydrochloric acid with sodium dodecylbenzenesulfonate (SDBS). After precipitation of the hydroxide and redissolution in dilute acid, the Rh(III) is converted into Rh(H(2)O)(3+)(6), Pd(II) and Pt(IV) remaining as PdCl(2-)(4) and PtCl(2-)(6) respectively, and separation is achieved by floating the Rh(H(2)O)(3+)(6) with SDBS. The second is for separation of Pd(II). Prior to flotation, the solution of PdCl(2-)(4) and PtCl(2-)(6) is heated with ammonium acetate to convert PdCl(2-)(4) into Pd(NH(3))(2+)(4). The chloro-complex of Pt(IV) is unaffected. The complex cation, Pd(NH(3))(2+)(4), is then selectively floated with SDBS. The procedures are fast, simple and do not require expensive reagents and apparatus.     

Synthesis of nonracemic allylic hydroxy phosphonates via alkene cross metathesis

Allylic hydroxy phosphonates and their derivatives can be interconverted by using cross metathesis with second generation Grubbs catalyst. The absolute stereochemistry of the starting phosphonate is conserved in the product. Cross metathesis reaction of the acrolein-derived phosphonate 2a yields a series of functionalized allylic hydroxy phosphonates. However, the cross metathesis reaction is often accompanied by competing dimerization and alkene migration reactions leading to a reduction in yield. The cinnamaldehyde- and crotonaldehyde-derived phosphonates 2b and 2c were also examined. In general, the metathesis reactions of phosphonates 2b and 2c are considerably slower than those for phosphonate 2a leading to mixtures. Several hydroxyl-protected derivatives of the phosphonate 2a (methyl carbonate 3a, acetate 4a, N-tosyl carbamate 5a, TBDMS 6a, and acetoacetate 7a) undergo metathesis without competing side reactions to give substituted allylic phosphonates in good to excellent yield.