Studies on the Total Synthesis of Hainanolide (VII) - Analysis of the Relative Stereochemistry of key Intermediate 2

The natural product, hainanolide 1, also under the name harringtonolide2 demonstrated antitumor and antiviral activities in preliminary test. Its structure was determined by X-ray diffraction. The total synthesis of 1 was reported recently by Mander3. A different scheme of its synthesis has been studied in our laboratory4. Here the determination of the stereochemical structure of the key intermediate 2 in the synthesis was reported. HMBC and HMQC spectra identified the skeleton and H,…     

DiastereoselectiveandEnantioselectiveSynthesisof(1S,2S)-2-Ethyl-1-aminocyclopropaneCarboxylicAcid

During the last decade, 1-aminocyclopropanecarboxylic acid and its derivatives (ACCS) have attracted increasing attention of organic and bioorganic chemists due to their outstanding biological properties, ranging from antimicrobial, insecticidal, plant growth and fruit ripening controls, etc.1. Moreover, the three-membered carbocycle provides building blocks of unprecedented synthetic potential because it undergoes selective ring opening, ring enlargement or cycloaddition reactions2. The mo…     

Evaluation of Transient Absorption Spectra of N, N, N, N- Tetra - ( p -methylphenyl ) - 4, 4- diamino - 1, 1- diphenyl Ether ( TPDAE ) for Electron Transfer from TPDAE to Fullerenes ( C_(60) / C_(70) ) by Laser Flash Photolysis

Fullerenes C60 and C70 have high electron affinity ( 2.6 - 2.8 ev ) and readily form anions on electronchemical reduction1, which were famous as electron acceptor in photo-excitation because of symmetrical shape, large size, and properties of its p - electron system2. After observation of molecular ferromagnetism3 in the tetrakis (dimethylamino ) ethylene salt of C60 as well as the occurrence of ultra-fast photoinduced electron transfer within the dimethyl aniline - C60 complex4, prompted us…     

Synthesis and Crystal Structure of Triethyl 1,2,2-triphenylpyrrolidine-3,4,5-tricarboxylate,A Proline Derivative

１ＩＮＴＲＯＤＵＣＴＩＯＮＩｎｒｅｃｅｎｔｙｅａｒｓ，ｏｕｒｒｅｓｅａｒｃｈｇｒｏｕｐｈａｓｓｔｕｄｉｅｄｓｙｓｔｅｍａｔｉｃａｌｙｃｙｃｌｏａｄｄｉｔｉｏｎｒｅａｃ ｔｉｏｎｓｏｆｔｈｅＣ＝Ｎｄｏｕｂｌｅｂｏｎｄｓｉｎｔｈｅｂｅｎｚｏｈｅｔｅｒｏａ...     

α-Fe2O3/SiO2纳米颗粒混合体系表面的酸碱性质及其对重金属离子的吸附行为

以Fe(NO₃)₃·9H₂O和正硅酸乙酯(TEOS)为原料, 通过溶胶-凝胶法和辅助模板法分别制备了纳米α-Fe₂O₃和SiO₂, 并对所合成样品进行了粉末X射线衍射(XRD)和BET表征. 使用自动电位滴定仪测定了α-Fe₂O₃/SiO₂纳米颗粒混合体系的表面酸碱性质. 研究了在不同pH下α-Fe₂O₃/SiO₂混合体系对Cu²⁺、Pb²⁺、Zn²⁺离子的吸附行为. 基于上述实验数据, 用WinSGW软件计算了α-Fe₂O₃/SiO₂混合体系表面酸碱配位常数, 并得出结论: α-Fe₂O₃/SiO₂混合体系表面反应为单一脱质子反应≡XOH ⇔ ≡XO^-+ H⁺(lg K = -8.19±0.15), 明显区别于同时具有加质子和脱质子反应的α-Fe₂O₃/SiO₂/γ-Al₂O₃, α-Fe₂O₃/γ-Al₂O₃和SiO₂/γ-Al₂O₃等纳米颗粒混合体系. 在此基础上拟合得到α-Fe₂O₃/SiO₂混合体系吸附重金属离子Cu²⁺、Pb²⁺、Zn²⁺的表面络合反应平衡常数分别为:
≡XOH + M²⁺ ⇔ ≡XOM⁺+ H⁺ [lg K = -3.1, -3.6, -3.8 (M = Cu, Pb, Zn)].
≡XOH＋M²⁺＋H₂O ⇔≡XOMOH＋2H⁺[lg K = -8.8, -8.0, -10.5 (M = Cu, Pb, Zn)]     

铂/石墨烯氧还原电催化剂的共还原法制备及表征

使用硼氢化钠共还原法制备40% (w)铂/石墨烯电催化剂用于氧还原反应. 通过循环伏安测试发现, 这种方法制备所得铂/石墨烯催化剂对氧还原反应活性较铂/碳催化剂差, 但稳定性有所提高. 在稳定性测试中,铂/石墨烯电催化性能衰减为50%, 较铂/碳(79%)好. X射线衍射(XRD)和透射电子显微镜(TEM)表征发现在铂/石墨烯催化剂中两者存在明显交互作用, 这可能是阻止石墨烯再堆垛和防止铂颗粒团聚的主要原因. 通过对单电池性能测试也发现铂/石墨烯催化剂更有利于电池长期稳定.     

Structural Study of Inclusion Complex of Andrographolide with β-Cyclodextrin Prepared under Microwave Irradiation

Andrographolide (Andro) (Figure 1) is a diterpene lactone isolated from Andrographis paniculate Nees1. It has showed several biological activities including analgesic, antipyretic and anti-inflammatory effects2. However, its poor water solubility and unstability towards oxygen restrained its application. In pharmaceutics, b-CD is used to increase solubility and stability3. We have prepared the inclusion compound of Andro/b-CD (Figure 2) under microwave irradiation4. It has been found…     

A New Approach to Inducing Silicon Tethered Ring-closing Metathesis Reactions

IntroductionGrubbs catalyst bis(tricyclohexylphosphine)benzylidene ruthenium( ) dichloride1 can be usedin a variety of ring- closing metathesis (RCM )reactions,cross metathesis(CM) reactions andring- opening metathesis polymerization(ROMP) [1— 4 ] .It remains metathetically active inthe presence of a variety of functional groups,suchas carbonyls,alcohols,and amides[1] .The use ofcatalyst1 in the synthesis has drawn more andmore attention[5— 13] . However,this catalyst is veryexpensive,an…     

Synthesis and gelation behaviors of five new dimeric cholesteryl derivatives

Five new diacid amides of di-cholesteryl L-glycinates were designed and prepared.The compounds with linkers containing 0,1, 2,3,or 4 methylene units are denoted as 1,2,3,4,and 5,respectively.Their gelation behaviors in 25 solvents were tested as novel low-molecular-mass organic gelators(LMOGs).It was shown that the length of the linker connecting the two-cholesteryl residues in a gelator plays a crucial role in the gelation behavior of the compound.1 gels 11 of the 25 solvents tested at a concentration lowe...     

Determination and Temperature Dependence of Plateau Modulus for Polymerization of Propylene to Isotactic Polypropylene with Ultra-high Molecular Weight under Catalysis of Ziegler-Natta Catalyst

The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight (UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means of oscillatory rheometry at 180 and 200 ℃, whose loss modulus(G") plots at 180 and 200 ℃versus the natural logarithm of angular frequency(ω) present a pronounced maximum at 34.35 and 69.21 rad/s, respectively, and do not show a maximum peak at 0. 01-100 rad/s for Ziegler-Natta catalyzing ethylenepropylene random copolymerization (PPR) with a conventional molecular weight and broad MWD. The fact indicates that the high molecular weight is responsible for a maximum peak of G"(ω) vs. lnω curves for UHPPH. This makes it possible to determine the plateau modulus (G0N) of UHPPH from a certain experimental temperature G"(ω) curve directly. For UHPPH, the G0N determined to be 4. 28×105 and 3. 62×105 Pa at 180and 200 ℃, respectively, decreases with the increase of temperature and is independent of the molecular weight, which directly confirms reputation theoretical prediction that the G0N has no relation to the molecular weight.