A solvothermal synthesis and the structure of K4Ag2Sn3S9 x 2KOH

A novel layered K(4)Ag(2)Sn(3)S(9) x 2KOH was synthesized solvothermally. A mixture of ethanol and HSCH(2)CH(SH)CH(2)OH was used for the synthesis. The HSCH(2)CH(SH)CH(2)OH plays an important role and appears to serve as a mineralizer for the solvothermal reaction. A layer comprises Sn(3)S(9)(6)(-) clusters linked by Ag(+) ions and possesses two types of 1D channels in which potassium ions are located. The compound crystallizes in the monoclinic P2(1)/m space group [a = 7.8071(2) A, b = 27.3508(1) A, c = 10.5008(2) A, alpha = 90 degrees, beta = 103.874(1) degrees, gamma = 90 degrees, Z = 4]. Its crystal structure, composition analysis, and IR are presented.     

Electrogenerated Chemiluminescence Based on Tris(2,2′-bipyridyl) Ruthenium(II) with Hydroxyl Carboxylic Acid

Upon the electrochemical oxidation of tris(2,2′-bipyridyl) ruthenium(II) [Ru(bpy)²⁺₃] and hydroxyl carboxylic acids, for instance, citric acid, tartaric acid, malic acid, and -gluconic acid, bright electrochemiluminescences (ECLs) were observed. Different luminescent reactions were presented depending on the applied potential. The light emission was mainly caused by the reaction between alkoxide radical ion and Ru(bpy)³⁺₃below the potential +1.80 V (vs Ag/AgCl). The luminescence intensity obviously increased because of the more complex reaction process. The luminescence wavelength of 608 nm, which could be found either at higher potential than +1.80 V or in the potential range from +1.30 to +1.80 V, confirmed that ECL was caused by Ru(bpy)²⁺₃*. The factors which affect the determination and HPLC separation of the four acids were also investigated.     

Immunosuppressive ent‐Kaurene Diterpenoids from Isodon serra

Three new enmein‐type ent‐kaurenoids, i.e., the two pairs 1 and 2 of 20‐epimers and the (20R)‐isomer 3 , besides the seven known diterpenoids 4 – 10 , were isolated from the aerial parts of Isodon serra. Their structures were elucidated by spectroscopic techniques and X‐ray diffraction. The immunosuppressive effect for T‐lymphocytes proliferation induced by Con A in BALB/c mouse was evaluated for the isolates 1 – 10 . They all displayed a remarkable inhibitory effect, with multi‐glycosides of Tripterygium wilfordii as positive reference substance (Table 3).     

Adsorption of NH3 onto activated carbon prepared from palm shells impregnated with H2SO4

Adsorption of ammonia (NH3) onto activated carbons prepared from palm shells impregnated with sulfuric acid (H2SO4) was investigated. The effects of activation temperature and acid concentration on pore surface area development were studied. The relatively large micropore surface areas of the palm-shell activated carbons prepared by H2SO4 activation suggest their potential applications in gas adsorption. Adsorption experiments at a fixed temperature showed that the amounts of NH3 adsorbed onto the chemically activated carbons, unlike those prepared by CO2 thermal activation, were not solely dependent on the specific pore surface areas of the adsorbents. Further adsorption tests for a wide range of temperatures suggested combined physisorption and chemisorption of NH3. Desorption tests at the same temperature as adsorption and at an elevated temperature were carried out to confirm the occurrence of chemisorption due to the interaction between NH3 and some oxygen functional groups via hydrogen bonding. The surface functional groups on the adsorbent surface were detected by Fourier transform infrared spectroscopy. The amounts of NH3 adsorbed by chemisorption were correlated with the contents of elemental oxygen present in the adsorbents. Mechanisms for chemical activation and adsorption processes are proposed based on the observed phenomena.     

Palladium(II) complexes of bowls, pinwheels, cages, and N,C,N-pincers of starburst ligands 1,3,5-Tris(di-2-pyridylamino)benzene and 2,4,6-Tris(di-2-pyridylamino)-1,3,5-triazene

The reactions of Pd(II) ions with starburst ligands 1,3,5-tris(di-2-pyridylamino)benzene (tdab) and 2,4,6-tris(di-2-pyridylamino)-1,3,5-triazene (tdat) have been investigated. Complexes with the Pd:tdab (or tdat) ratio being 1:1 and 3:1 have been isolated and characterized. The structures of five new Pd(II) complexes containing the starburst ligands have been determined by X-ray diffraction analyses, which include chelate compounds [PdCl(2)(tdab)], 1, [(PdCl(2))(3)(tdab)], 2, [(Pd(OAc)(2))(3)(tdab)], 4, and [(Pd(OAc)(2))(3)(tdat)], 5, and a cyclometalated compound [Pd(OAc)(NCN-tdab)], 3. The Pd(II) ion in the 1:1 compound 1 is chelated by two pyridyl groups. Similarly, each Pd(II) center in the 3:1 compounds 2, 4, and 5 is chelated by two pyridyl groups. However, these three compounds display distinct structural features: 2 adopts a "bowl-shaped" structure, 4 has a "pinwheel"-like structure, and 5 has a "up-and-down" structure. Compounds 4 and 5 were examined in solution by variable-temperature (1)H NMR, which revealed that both compounds retain the "pinwheel" and the "up-and-down" structure, respectively. The observed structural preference by 4 and 5 is attributed to both electronic and steric factors.     

新型Zhuo酚酮类糖苷化合物的合成

根据Zhuo酮的结构特点，对Zhuo酚酮类化合物与半乳糖的Kenigs-Knorr反应进 行了研究。探索出一种具有较高立体选择性的合成方法，从而制得四种具有β－构 型的单一端基异构体的Zhuo酚酮半乳糖苷新化合物。生成的新化合物不但保持了原 有的生理活性，而且降低了毒性、提高了药效，为人工合成Zhuo酚酮类增添新化合 物的同时，也扩展了此类化合物的应用领域。应用元素分析、核磁共振、红外光谱 表征了它们的结构。     

Thermodynamics and dynamics of metallic glass formers: their correlation for the investigation on potential energy landscape

Great progress has been made in basic features of the potential energy landscape (PEL) theoretically. The present work, however, attempts to cast new light on it from experimental aspects. By a survey of experimental data related to thermodynamics or dynamics of metallic glass-forming liquids, it is found that the increased rate of excitation of vibrational entropy at glass transition tends to increase the rate of generation of configurational part. Although for the type of metallic materials a generally positive relationship exists between the density of the energy minima at glass transition and the liquid fragility strength, just as expected, our main attention is paid to the phenomenon of the scattering of the slopes. Analysis shows that the phenomenon results from the different average height of energy barriers between minima near glass transition. Investigation on the PdNiP metallic system indicates that the mismatch entropy is a dominant factor in the barrier height: a large value of it results in low energy barriers. Our previous work on the AlNiCe system gives the support to this finding.     

The glass transition time scale and configurational entropy in polymers: an experimental molecular view

We report direct experimental observation of local conformational dynamics in a polymer chain at the calorimetric glass transition temperature Tg. Variable-temperature two-dimensional (2D) solid-state exchange NMR, at natural abundance, reveals segmental dynamics in pure polyisobutylene (PIB) occurring on a time scale of several seconds over the Tg range observed by DSC (203-208 K). To our knowledge, this is the first direct observation of molecular-level conformer interchange (trans-trans/trans-gauche/gauche-gauche) at the caloric glass transition temperature. Our results provide a chronologically accurate and pedagogically advantageous demonstration of molecular processes during a polymer phase transition, relative to traditional bulk mechanical and calorimetric techniques. More importantly, we use a miscible blend to demonstrate a general strategy for quantitative evaluation of configurational entropy changes via combination of temperature-dependent 2D exchange NMR and Adams-Gibbs theory. Our results on the Tg time scale are directly relevant to fundamental understanding of the Tg length scale, i.e., the dimension of cooperatively rearranging regions.     

Recent Advances of Catalytic Enantioselective Heck Reactions and Reductive-Heck Reactions

Heck reaction is one of the most important carbon-carbon bond forming reactions with wide applications in organic synthesis.Considerable advances of enantiosele...