Two 3D supramolecular polymers constructed from an amino acid and a high-nuclear Ln6Cu24 cluster node

The first successful attempt to construct 3D supramolecular frameworks with high-nuclear 3d-4f heterometallic clusters as a node is reported. The self-assembly of Ln3+, Cu2+ and amino acid in solution leads to the formation of two polymers, 35-nuclear complex [Sm6Cu29] 1 with a primitive cubic net-like structure and 36-nuclear complex [Nd6Cu30] 2 with a face-centred cubic network type structure. Glycine and L-proline, respectively, were used as ligands. It should be noted that 2 has a chiral framework. X-ray structure analyses show that 1 crystallizes in the triclinic P1 space group (a=19.6451(8), b=20.4682(8), c=20.7046(8) A, alpha=89.453(1), beta=66.290(1), gamma=68.572(1) degrees, V=7003.0(5) A3 and Z=1) and 2 belongs to the cubic P2(1)3 space group (a=b=c=32.4341(3) A, V=34 119.7(5) A3 and Z=4). Both complexes utilize Ln6Cu24 octahedral clusters as nodes and trans-Cu(amino acid)2 groups as bridges. Electrical conductivity measurements reveal that both polymers behave as semiconductors.     

Formation of α-Mn2O3 nanorods via a hydrothermal-assisted cleavage-decomposition mechanism

A hydrothermal cleavage-decomposition mechanism was used to synthesize single-crystal α-Mn₂O₃ nanorods at 160 °C for 16 h using KMnO₄ as manganese source and CTAB as reducing regent. The as-synthesized products were characterized by powder X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy and infrared spectrum. The results indicate that the reaction temperature is a crucial factor for the formation of α-Mn₂O₃ nanorods. These nanorods exhibit single-crystal nature, and have an average diameter of 36 nm and lengths of up to 1 μm. Based on our experimental results, a hydrothermal cleavage-decomposition mechanism has been proposed on the formation of α-Mn₂O₃ nanorods.     

Ternary surface complexes by theE(%)-pH curve method

A new method for the study of ternary surface complexes at liquid-solid interface, theE(%) -pH curve method, was proposed. Four types ofE(%)-pH curves, namely, phenomenon of left-right shifts of S-shaped curve, V-shaped curve, monodirection shift curve and X-shaped curve, were discovered. Correspondingly, apart from type (I) ternary surface complex and type (II) ternary surface complex , a new type of ternary surface complex was discovered. Project supported by the National Natural Science Foundation of China and the Fund of Doctoral Degree’s Spot.     

土壤微生物ATP、脱氢酶和尿素酶活性的ED50值评价外源镧的生物毒性

０IntroductionRareearthsarenowappliedwidelyinChina，whichcanimprovecropsyieldsandthetheirqualit－ies犤１犦．Thebeneficialeffectsmaybeduetothestimu－latoryeffectsoftheseelementsonthenutrientuptakebyplantsorontheincreasingofchlorophyllsynthesisintheplants犤２犦．Whilealotofresearcheshavebeendoneontheimprovednutritionofcropsafterapplica－tionofrareearths，muchlessattentionhasbeenpaidtothedeteriorationofsoilqualityduetotheapplicationofrareearthsforyears犤３犦．Scientistshavediscoveredthataccumula…     

Total synthesis of crotophorbolone

As a natural diterpenoid, crotophorbolone possesses a challenging trans,trans-5/7/6 framework decorated with six contiguous stereogenic centers and is structurally and biogenetically related to tigliane-type diterpenoids with intriguing bioactivities such as phorbol and prostratin. Based on the convergent strategy, we completed an eighteen-step total synthesis of crotophorbolone starting from (−)-carvone and (+)-dimethyl-2,3-O-isopropylidene-l-tartrate. The key elements of the synthesis involve expedient installation of the six-membered ring and the five-membered ring with multiple functional groups at an early stage, cyclization of the seven-membered ring through alkenylation of the ketone between the five-membered ring and the six-membered ring, functional group-sensitive ring-closing metathesis and final selective introduction of hydroxyls at C₂₀ and C₄.

Convergent total synthesis of crotophorbolone was accomplished in 18 longest linear steps. Observation of unexpected thermodynamic stability of a cis,trans-5/7/6 tricycle would benefit synthetic design of tigliane- and daphnane-related diterpenoids.     

Ab initio studies on the thermolysis of azetidine

The reaction mechanism of the thermolysis of azetidine to form ethylene and methylen-imine has been studied by ab initio SCF MO method at STO--3G and 3-21G levels. Two possible step-wise pathways are explored. One is the breaking of C--C bond as the first step, while the other is thebreaking of C--N bond. All the stationary points on the potential energy surface (PES) are fully optimiz-ed. MP2 / 3-21G single point calculations on all stationary points and MCSCF / STO-3G computationsfor some stationary points are also carried out. The calculations indicate that azetidine decomposesvia biradicaloid intermediates and the cleavage of C--N bond is preferable to that of C--C bond.     

Formation and photoluminescence of silver nanoparticles stabilized by a two-armed polymer with a crown ether core

Silver nanoparticles were synthesized by the use of a two-armed polymer with a crown ether core [poly(styrene)]-dibenzo-18-crown-6-[poly(styrene)] based on the flexibility of the polymer chains and the complex effect of crown ether with Ag(+) and Ag. The size of silver nanoparticles could be tailored by controlling the initial concentrations of the polymer and Ag(+), and the molecular weight of the polymer. The emission of silver nanoparticles was blue-shifted, and the intensity of the photoluminescence of silver nanoparticles stabilized by the polymer was significantly increased due to the complex effect between the crown ether embedded in the polymer and the silver nanoparticles.     

DSC study of cold and heat denaturation processes of β-lactoglobulin A with guanidine hydrochloride

The cold and heat denaturations of bovine P-lactoglobulin A ((β-lg A) has been studied in solutions of guanidine hydrochloride (GuHCI) by differential scanning calorimetry (DSC). The experimental results are presented and discussed. It is shown that the number of protons bound by the monomeric molecules of β-lg A was unchanged before and after its heat denaturation below pH 3, and that the activation energy of the heat denaturation was depressed owing to the presence of GuHCI. In the solutions with 2.50 and 3.06 mol/L of GuHCI, both the cold and heat denaturations of P-lg A were observed. In comparison with the heat denaturation, the activation energy of cold denaturation was far lower and the number of GuHCl molecules bound by the unfolded polypeptide chains after culd denaturation increased a lot. The absolute value of the enthalpy of cold denaturation was larger than that of heat denaturation. It was found by the analysis that the contribution to the total denaturational enthalpy of conformational change itself of the monomeric molecules of β-lg A was the lowest among the globulins, according to the average of the number of heavy atoms. Project supported by the National Natural Science Foundation of China, and by the fund for excellent items under Director of the Institute of Chemistry.     

三苄基氯化锡及其衍生物的合成

三苄基氯化锡最初用格氏法制得。Keiti等曾报道由锡和苄基氯直接制备,这时溶剂对反应的影响很大:用水作溶剂时得到三苄基锡;用甲苯作溶剂时得到二苄基二氯化锡;用正丁醇作溶剂时三苄基氯化锡的产率只有61％。在反应体系中加入KI、KBr或H_3PO_4等催化剂,三苄基氯化锡的产率也只有60％。本文用DMF作溶剂,AlCl_3-I_2作催化剂,并首次在反应体系中加入镁、锌、铝和钠等使副产物氯化亚锡还原成活性很高的金属锡,后者再与等基氯反应,可使三苄基氯化锡的产率提高到91.3％。文中还报导三种尚     

Promoting effect of sol-gel method and pre-treatment on the activity of SnO2/Al2O3 catalyst for NO reduction by propene

SnO₂/Al₂O₃ catalyst prepared by sol-gel method showed higher activity than those prepared by impregnation method, and their activity was significantly improved by pre-treatment in the reaction gas. The increased activity is closely related to the agglomeration of SnO₂ species and the re-exposure of Al₂O₃, which was previously covered by dispersed SnO₂ species. This revised version was published online in June 2006 with corrections to the Cover Date.