A Ditopic Catechol Phosphane as Building Block for Selective Construction of Heterometallic Complexes with Early and Late Transition Metal Centers

Base‐assisted reaction of catechol phosphane 2 (H₂L) with [M′Cl₂(cod)] (cod = 1, 5‐cyclooctadiene, M′ = Pd, Pt) yielded chelate complexes [M′(HL)₂] ( 7a, b ). Spectroscopic and single‐crystal X‐ray diffraction studies revealed that both complexes feature cis‐configuration of the P‐ and O‐donor atoms in solution and in the solid state. Reaction of 7a, b with acetylacetonato or alkoxide complexes [MO₂(acac)₂] (M = Mo, W), [VO(acac)₂], [{Ti(μ‐O)(acac)₂}₂], or Ti(OiPr)₄ gave good to excellent yields of early‐late heterometallic complexes [MO_n(μ‐L)₂M′] (MO_n = MoO₂, WO₂, VO; 8a, b – 10a, b ) or [Ti(RO‐1κO)₂(μ‐L ‐1κ²O, O'‐2κ²P, O)₂Pd] (R = Me, iPr; 11a, b ), which were inaccessible via other synthetic routes. Spectroscopic and single‐crystal X‐ray diffraction studies revealed that the early metal centres in 8a, b, 9b and in 11b feature distorted octahedral coordination spheres with rigid transoid alignment of the catechol ring planes. Vanadium complexes 10a, b exhibit a square‐pyramidal coordination sphere with cisoid alignment of the catechol ring planes and evidence for intermolecular pairing via weak VO ··· Pd contacts in the solid state; complexes 8 , 9 do not undergo conformational inversion on the NMR time‐scale. The molecular structure of Ti complex 11a is characterized by a different orientation of the catechol moieties, which can be envisaged to picture an intermediate state during a configuration inversion process, and a strong hydrogen bridge between a terminally coordinated catecholato‐oxygen atom and a solvent molecule (MeOH). Solution NMR studies indicate that the (MeO)₂Ti(μ‐L)₂M' framework is in this case conformationally labile and that the MeO ligands undergo intermolecular dynamic exchange with the solvent.     

锚定基团对HKUST-1/TEMPO共催化体系催化性能的影响

用异烟酸(Iso-NTA)为桥接分子,将有机小分子自由基4-氨基-2,2,6,6-四甲基哌啶-1-氧自由基(4-NH₂-TEMPO)与异烟酸缩合,合成出含吡啶官能团的TEMPO自由基(Iso-NTA-TEMPO).与TEMPO相比,Iso-NTA-TEMPO具有较高的氧化电位,在无Cu (Ⅱ)辅助时,Iso-NTA-TEMPO对苯甲醇的氧化效率高于TEMPO.在与HKUST-1组成的复合催化体系中,Iso-NTA-TEMPO可通过吡啶基团与HKUST-1孔道中的Cu(Ⅱ)相互作用,从而在催化过程中(部分)锚定在HKUST-1孔道内部.与TEMPO/HKUST-1体系相比,Iso-NTA-TEMPO/HKUST-1体系表现出对芳香醇更加高效的催化活性.采用模板辅助溶剂诱导结晶法合成的HKUST-1晶体表面具有较多缺陷,更有利于Iso-NTA-TEMPO自由基分子扩散进入HKUST-1孔道内部,也有助于提高Iso-NTA-TEMPO/HKUST-1体系的催化效率.Iso-NTA-TEMPO/HKUST-1体系可将各种取代基(苄醇、杂环醇以及二级脂肪醇)高效、高选择性地...     

Sacrificial template growth of CdS nanotubes from Cd(OH)2 nanowires

A diffusion-controlled process was proposed for the preparation of inorganic nanotubes from nanowires. The preformed Cd(OH)₂ nanowires were used as the sacrificial templates to generate CdS nanotubes with different wall thickness. The axle-sleeve transition state found in-between the precursor and the formation of products proves the diffusion-controlled mechanism. CdS nanotubes can be prepared via this method at different temperature and with various sulfide sources. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) results showed that all obtained CdS nanotubes consist conglomerated crystallites, and the crystallinity can be altered by changing the temperature of the growth process. The wall thickness of the produced CdS nanotubes can be controlled by changing the concentration of the sulfide source and stopping the reaction at different stages.     

高比表面积二氧化钛的合成-制备条件的探讨

利用中性胺作为模板剂，由钛酸四丁酯水解合成了一系列二氧化钛。考察了加料顺序、陈化及模板剂的去除条件对其比表面积的影响。结果表明，采用反加料顺序、在酸性条件下短时间陈化，以及用稀硝酸洗涤或环己烷萃取除去模板剂的办法，都有助于比表面积的提高。沉淀时加入1％的异丙醇铝共沉淀，可大大提高高比表面积二氧化钛的耐热性；同时发现，酸洗可使二氧化钛在350℃低温下由锐钛矿向金红石转变。     

Molecular assemblies based on the template-directing effect of anionic polyoxometalate clusters and organic cationic flexibility

Molecular assembly processes by utilizing the template-directing effect of anionic polyoxometalate clusters and the flexible organic cation have achieved three hybrids: (H₂bpp)(Hbpp)[PMo₁₂O₄₀]·3DMF (1), (H₂bpp)(Hbpp)(bpp)₂ [PMo₉V₃O₄₀(VO)₂]₂ (2), and (H₂bpp)₂[β-Mo₈O₂₆] (3) (bpp = 1,3-bis(4-pyridyl)propane). Three compounds were characterized using single crystal X-ray crystallography, elemental analysis, IR, XPS, EPR, voltammetric behavior and TGA. Crystal structural analyses revealed that compounds 1–3 were all constructed from protonated organic bpp cations with different POM clusters: isolated α-Keggin P–Mo cluster in 1; dimer of bi-capped α-Keggin P–Mo–V anions linked through a {V₂O₂} unit in 2; β-octamolybdate isopolyanion in 3, respectively. All three assemblies demonstrated a higher thermal stability. The protonated bpp cations lost at temperature higher than 300 °C that the strong intermolecular interactions may account for the high initial temperature of weight loss. The electrochemistry property of compound 2 modified carbon paste electrode was also studied in 1 M H₂SO₄ aqueous.     

Template tailoring: Accurate determination of heterozygous alleles using peptide nucleic acid and dideoxyNTP

Measurement of the length of DNA fragments plays a pivotal role in genetic mapping, disease diagnostics, human identification and forensic applications. PCR followed by electrophoresis is used for DNA length measurement of STRs, a process that requires labeled primers and allelic ladders as standards to avoid machine error. Sequencing‐based approaches can be used for STR analysis to eliminate the requirement of labeled primers and allelic ladder. However, the limiting factor with this approach is unsynchronized polymerization in heterozygous sample analysis, in which alleles with different lengths can lead to imbalanced heterozygote peak height ratios. We have developed a rapid DNA length measurement method using peptide nucleic acid and dideoxy dNTPs to “tailor” DNA templates for accurate sequencing to overcome this hurdle. We also devised an accelerated “dyad” pyrosequencing strategy, such that the combined approach can be used as a faster, more accurate alternative to de novo sequencing. Dyad sequencing interrogates two bases at a time by allowing the polymerase to incorporate two nucleotides to DNA template, cutting the analysis time in half. In addition, for the first time, we show the effect of peptide nucleic acid as a blocking probe to stop polymerization, which is essential to analyze the heterozygous samples by sequencing. This approach provides a new platform for rapid and cost‐effective DNA length measurement for STRs and resequencing of small DNA fragments.     

大肠杆菌为模板制备Au@TiO_2催化剂及其CO氧化反应活性

许多微生物对金属离子有较强的吸附还原能力.本文利用大肠杆菌(DH5α)对金属离子较强的吸附与还原能力制备了Au@DH5α,再利用大肠杆菌的水分来水解钛酸四丁酯,得到Au@DH5α-Ti(OH)4样品,焙烧去除大肠杆菌后得到氧化钛包裹的纳米金粒子催化剂Au@TiO2.以N2吸附,X射线衍射(XRD),紫外-可见漫反射光谱(UV-VisDRS),热重-差热分析(TG-DTA),透射电镜(TEM)对所得材料进行表征.结果表明:该催化剂具有与大肠杆菌类似的杆状结构,以大肠杆菌为生物模板生成的氧化钛孔道结构在一定程度上抑制了金粒子的聚集长大.随菌体用量的增加,金粒子减小,等离子共振吸收发生紫移,催化剂有较大的比表面积,但催化剂中积炭量也会增加.将该催化剂用于CO氧化反应,发现当菌体用量为100或150mL时,制得的金催化剂可在80℃下将CO完全氧化为CO2.     

Template self-assembly of cyano-bridged supramolecular complexes {[Cu(en)2][KM(CN)6]} n (M = CrIII,FeIII, CoIII)

Reaction of K₃[M(CN)₆] (M?=?Cr^III, Fe^III, Co^III ) with [Cu(en)₂](ClO₄)₂ in water gives three cyanide-bridged supramolecular complexes, {[Cu(en)₂][KM(CN)₆]} _n [M?=?Cr^III (1), Fe^III (2), Co^III (3); en?=?ethylenediamine], which have been characterized by elemental analysis, ICP analysis, IR spectra, TGA-DTA analysis and X-ray diffraction. Complex 1 crystallizes in the monoclinic, space group C2/c with cell dimensions a?=?0.85237(12), b?=?1.7014(3), c?=?1.2103(2)?nm, β =?98.70(2)° and Z?=?4, and 2 crystallizes in the same space group with a?=?0.8401(2), b?=?1.6844(5) Å, c?=?1.1859(2)?nm, β =?98.98(2)° and Z?=?4. The crystal structures of 1 and 2 reveal a novel three-dimensional porous framework in which [Cu(en)₂]²⁺ acts as a template, [M(CN)₆]^3? as a building block and K⁺ as a connecting unit.     

Self-assembly of supramolecular Ni(II) and Cu(II) metalmacrocyclic compounds with tetraazamacrocyclic ligand into a gelatin-immobilized matrix

Self-assembly in M(II)-ethanedithioamide [H₂N–C(=S)–C(=S)–NH₂]-propanone triple systems (M=Ni, Cu) into corresponding metal(II) hexacyanoferrate(II) gelatin-immobilized matrix systems under contact with aqueous-alkaline (pH?～?12) solutions containing ethanedithioamide and propanone have been studied. Formation of supramolecular macrotetracyclic compounds of Ni(II) and Cu(II) with 2,7,7,9,14,14-hexamethyl-3,6,10,13-tetraazacyclotetradecadien-2,9-tetrathione-4,5,11,12 containing original “kernel” (metal complex) and “shell” surrounding this “kernel”, of polypeptide chains of the gelatin molecules, occurs under such specific conditions.     

Template-directed synthesis of macrocyclic copper(II) complexes of diazacyclam, 1,3,6,10,12,15-hexaazatricyclo[13.3.1.16,10]eicosane

Template reaction of copper(II) nitrate with N-(2-aminoethyl)-1,3-diaminopropane and formaldehyde yields a macrocyclic copper(II) complex of 1,3,6,10,12,15-hexaazatricyclo[13.3.1.1^6,10]eicosane (L), [CuL(NO₃)₂] (1). Replacement of nitrate with perchlorate gives [CuL(ClO₄)₂] (2). These complexes have been characterized by FT-IR and Raman spectroscopies, electronic absorption, cyclic voltammetry, and X-ray crystallography. The crystal structure of 1 shows that copper has distorted octahedral geometry with two secondary and two tertiary amines of the macrocycle and two oxygen atoms from nitrate coordinating the axial positions. The copper in 2 has the same geometry with axial positions occupied by one oxygen atom of perchlorate. Copper lies on the plane of four coordinated nitrogen atoms and there is no rms deviation from this plane. Cyclic voltammetry of 1 and 2 gives two one-electron waves corresponding to Cu^II/Cu^III (?0.75,??0.72) and Cu^II/Cu^I (0.48, 0.24) processes. For understanding of geometry parameters in diazacyclam-based copper(II) complexes, a survey on complexes from CSD structures is presented. In this study the macrocycle hole size was estimated by ionic radii of metal ions located inside of it.