Synthesis, Crystal Structure and Theoretical Studies of (E)-1-((9-(2-(2-methoxyethoxy)ethyl)-9H-carbazol-3-yl)methylene)thiosemicarbazide

A novel thiosemicarbazide derivative, （E）-1-（9-（2-（2-methoxyethoxy）ethyl）-9H-carbazol-3-yl） methylene）-thiosemicarbazide （CMT）, was synthesized and structurally characterized by IR, 1H-NMR, EI-MS and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.769（5）, b = 8.279（5）, c = 17.166（5） , β = 114.391（5）°, V = 1911.6（14） 3, Z = 4, F（000） = 784, Dc = 1.287 g/m3, Mr = 370.47, μ = 0.190 mm-1, the final R = 0.0390 and wR = 0.1358 for 1446 observed reflections with Ⅰ 〉 2σ（Ⅰ）. The UV-vis absorption spectra of CMT were explained based on quantum chemical calculations, using time dependent density functional theory （TD-DFT） at the B3LYP/6-31G （d） level.

Synthesis, Crystal Structure, Theoretical Studies and Sensitive Response toward Fe^(3+) of a Novel Tripyrazole Derivative Ligand

A novel pyrazole derivative ligand, BTA（BTA = bis-（4-ethoxy-phenyl）-[4-（tripyrazol-1-yl-methyl）-phenyl]-amine）, was synthesized and fully characterized by 1H-NMR, MALDI-TOF-MS spectra and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1, with a = 11.827（1）, b = 16.000（2）, c = 16.527（2）A, α = 108.510（1）, β = 91.116（5）, γ = 101.734（1）°, V = 2894.5（6） A3, Z = 1, Dc = 1.262 g/m^3, F（000） = 1162, Μr = 545.63, μ = 0.083 mm-1, the final R = 0.0728 and w R = 0.2213 for 7541 observed reflections with I 〉 2（I）. The structural analysis revealed that three pyrazole units are attached to the same carbon atom connected with bis-（4-ethoxy-phenyl）-phenyl-amine group. UV-vis spectral features of the ligand in various solutions were explained by time dependent density functional theory（TD-DFT）. It was also found that the ligand（BTA） exhibits an exclusively selective and sensitive response toward Fe3＋ using UV-vis spectroscopic method.

Synthesis and Crystal Structure of a Novel 1D Mercury(II) Iodide Coordination Polymer Containing 40-Membered Macrocycle

A mercury coordination polymer [Hg3（TizT）216]n （Mr = 1921.72, TizT = 2,4,6- tri（imidazole- 1-yl）- 1,3,5-triazine） containing a 40-membered macrocycle which was constructed by four TizT ligands and four mercury（II） iodide molecules had been synthesized by the reaction of HgI2 with TizT. The complex was characterized by elemental analysis, FT-IR, ^1H NMR spectra and X-ray crystallography. The crystal of the complex belongs to the monoclinic system and C2/c space group with a = 35.840（5）, b = 8.169（5）, c = 14.980（5） A, β = 104.466（5）°, Z= 4, V= 4247（3） A^3, De = 3.006 g·cm^-3, μ= 15.223 mm^-1, F（000） = 3384, Rint = 0.0504, wR = 0.0833 and constructs a chair-like conformation of cyclohexane one by one, which forms a 1-D polymer through the fashion of fused ring aromatic hydrocarbon. The hydrogen bonds and π-π interactions shape the 2-D network structure. The two compounds excited weak fluorescence.

Studies on the Crystal Structure and Photoluminescence of a Mercury(Ⅱ)Complex Based on a Novel Pyridine Ligand

A novel mercury（H） complex HgL2Br2 was prepared from HgBr2 and the organic ligand 2-（N-methyl-N-（4-（（E）-2-（pyridine-4-yl）vinyl）phenyl）amino）ethanol （L）. The ligand was synthesized and then characterized by FT-IR spectroscopy, tH NMR, mass spectrum and elemental analysis, while the single-crystal diffraction data of the complex were collected on a Siemens Smart CCD diffractometer. The complex crystallizes in triclinic space group PI with a = 5.367（5）, b = 12.466（5）, c = 23.945（5） A, α = 90.812（5）, β = 96.318（4）, γ = 96.093（5）°, Z = 2, Dc = 1.817 g.cm3,μ = 7.395 mm^-1, S = 0.825, and the final R= 0.0396. The Hg（Ⅱ） ion in the distorted tetrahedral mercury（Ⅱ） complex C32H36HgBr2N4O2 is coordinated by two N atoms from the two ligands together with two bromide ions. Solid-state emission of the ligand and its complex has been investigated at room temperature.

Rationally construction of atomic-precise interfacial charge transfer channel and strong build-in electric field in nanocluster-based Zscheme heterojunctions with enhanced photocatalytic hydrogen production

The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-based heterojunction(Pt1Ag28-BTT/CoP,BTT=1,3,5-benzenetrithiol)with strong internal electric field is constructed via interfacial Co-S bond,which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h^(−1)·g−1 H_(2)production rate,25.77%apparent quantum yield at 420 nm,and~100%activity retention in stability,compared with Pt1Ag28-BDT/CoP(BDT=1,3-benzenedithiol),Ag29-BDT/CoP,and CoP.The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC,wherein,the center Pt single atom doping regulates the band structure of NC to match well with CoP,builds internal electric field,and then drives photogenerated electrons steering;the accurate surface S modification promotes the formation of Co-S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration.This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.

General synthesis of transition metal nitride arrays by ultrafast flash Joule heating within 500 ms

Transition metal nitrides(TMNs)are considered as viable alternatives to noble metal catalysts owing to their versatile electronic structure and favorable catalytic performance.However,the conventional synthetic processes for TMNs suffer from high energy consumption and low production yield.In this study,a range of TMNs and their hetero-composite arrays were successfully synthesized via an ultrafast flash Joule heating technology within 0.5 s.As a proof concept,the nitrides and hetero-composites were applied for the electrocatalytic hydrazine oxidation reaction(HzOR),in which the Co_(4)N/Mo_(16)N_(7)arrays shows the best performance with a geometric current density of 100 mA cm^(-2)at 23 mV(vs.reversible hydrogen electrode(RHE)).This work paves a new way for the ultrafast synthesis of TMNs which could meet the ever-increased energy crisis.

Metal complexes of a novel bis-β-diketone-type ligand and its copper(Ⅱ) complexes of two-photon biological imaging

A curcumin derivative ligand,1,7-bis(3-methoxyl-4-acetoxyl)phenyl-1,6-heptadiene-3,5-diketone (diacetylcurcumin,abbreviated as HL),and its Cu and Ni complexes have been synthesized and fully characterized by elemental analyses,IR,1 HNMR and molar conductivity.The resulting complexes exhibit two-photon excited fluorescence (TPEF) in DMF,and have been proven to be potentially useful for two-photon microscopy imaging in living cells.In addition,cytotoxicity tests showed that the low-micromolar concentrations of ML 2 did not cause significant reduction in cell viability over a period of at least 24 h and should be safe for further biological studies.

Rational design of a hollow porous structure for enhancing diffusion kinetics of K ions in edge-nitrogen doped carbon nanorods

The high electrical conductivity makes it possible for one-dimensional(1D)carbon materials to be used as the promising anodes for potassium ion batteries(PIBs),however,the sluggish diffusion kinetics caused by large-sized potassium ions(K^(+))limits their practical applications in energy storage systems.In this work,hollow carbon nanorods were rationally designed as a case to verify the superiority of 1D hollow structure to improve the diffusion kinetics of K^(+).Simultaneously,edge-N(pyridinic-N and pyrrolic-N)atoms were also introduced into 1D hollow carbon structure,which can provide ample active sites and defects in graphitic lattices to adsorb K^(+),providing extra capacitive storage capacity.As expected,the optimized edge-N doped hollow carbon nanorods(ENHCRs)exhibits a high reversible capacity of 544 mAh·g^(−1)at 0.1 A·g^(−1)after 200 cycles.Even at 5 A·g^(−1),it displays a long-term cycling stability with 255 mAh·g^(−1)over 10,000 cycles.The electrochemical measurements confirm that the hollow structure is favorable to improve the transfer kinetics of K^(+)during cycling.And the theoretical calculations demonstrate that edge-N doping can enhance the local electronegativity of graphitic lattices to adsorb much more K^(+),where edge-N doping synergizes with 1D hollow structure to achieve enhanced K^(+)-storage performances.

Synthesis of two carbazole-based dyes and application of two-photon initiating polymerization

Two carbazole-based polymerization initiators possessing blue fluorescence emission have been synthesized via Wittig reaction in the solid phase at room temperature.Two-photon excited fluorescence(TPEF) spectra for them were investigated under 800 nm fs laser pulse and two-photon absorption cross sections were determined by the Z-scan technique.Then two-photon initiating polymerization(TPIP) microfabrication experiments were successfully carried out.Three-dimensional lattice and artificial defects were gained,indicating that they were viable candidates for the two-photon polymerization initiator in practical application of microfabrication.

Crystal structures,two-photon absorption and theoretical calculation of a series of bis-vinylpyridine compounds synthesized by one-step solid state reaction

Three bis-vinylpyridine compounds (4,4′-bis(2-vinylpyridine)biphenyl L1,4,4′-bis(3-vinylpyridine) biphenyl L2,and 4,4′-bis (4-vinylpyridine)biphenyl L3) were synthesized by one-step solid-state reactions at room temperature,giving nearly quantitative yields. The compounds obtained were fully characterized by IR,MS and NMR spectroscopies. The structures of L2 and L3 were determined by single crystal X-ray diffraction analysis. No noticeable solvatochromism was observed in either one-photon absorption or one-photon excited fluorescence spectra. All of the compounds have high fluorescence quantum yields and long fluorescence lifetime. The linear and nonlinear optical properties of the compounds were investigated both experimentally and theoretically. Interestingly,the position of the nitrogen atom from pyridine influences their two-photon absorption across-sections.

A new series of two-photon polymerization initiators:Synthesis and nonlinear optical properties

Four photopolymerization initiators with D-π-D (D,donor; π,conjugation system) structure have been synthesized by solvent-free reaction and characterized by 1H NMR spectroscopy,IR and elemental analysis. The one-photon and two-photon excited fluorescence have been investigated in different solvents. Experimental results of the one-photon and two-photon absorption cross sections show different trends in OPA and TPA ability with different substitution groups in donor units.

反钙钛矿结构氮化铜纳米片实现高效电催化甲醇氧化转化为甲酸盐

钙钛矿氧化物具有灵活的组成和电子结构,在电催化水氧化反应中具有很大的应用潜力.然而,钙钛矿氧化物在电催化有机小分子转化中的应用研究较少,这可能是由于其导电性差,表面重构产生活性物种所需的能垒高.在本文中,我们报道了具有典型反钙钛矿结构的氮化铜纳米片作为甲醇选择性转化为甲酸盐的电催化剂,其形成甲酸盐的法拉第效率超过90%.原位电化学质谱和原位红外反射吸收光谱进一步证实了制备的氮化铜样品在较宽的电位范围内具有较高的甲酸盐选择性.此外,高分辨率透射电镜、X射线吸收光谱和原位拉曼光谱表明,该催化剂在电催化过程中发生表面重构形成了氧化态铜物种壳,从而提升了其整体甲醇氧化性能,而原始的氮化铜核则利于在催化剂内部的电子传递.本研究不仅为甲醇的高选择性转化提供了一种有意义的方案,而且为有机小分子的电化学转化提供了一种新型的非氧化物钙钛矿材料模型.

简单的蛋白质组装激活三光子活性:由烷基链“奇-偶”效应调控其“之”字形提升

设计具有高阶多光子活性、无重原子的纳米光敏剂,用于近红外(NIR-Ⅱ,1000-1700 nm)二区光诱导的深层肿瘤的光动力学治疗是一个棘手的挑战.本文利用牛血清白蛋白(BSA)与一系列无重原子光敏剂TPA-nCs(n=2-7)进行超分子组装.通过一种简单的方式,成功激活了TPA-nCs多光子荧光,并展现了“奇-偶”效应的趋势,揭示了一个有趣的构效关系.具体来说,奇、偶数烷基取代TPA-nCs偶极矩的差异,导致制备的蛋白质纳米组装体TPA-nCs@BSA呈现了“之”字型增强的三光子荧光性能.其中,TPA-7C@BSA具有最大的三光子吸收截面(可达到4.81×10^(-81)cm~6 s~2 photon^(-2)),其在1250 nm近红外光照射下产生的活性氧物种可实现H22肿瘤高效光动力学治疗.本文报道的烷基链“奇-偶”调控为开发和改进多光子无重原子光敏材料在生物医学中的应用提供了新的思路.

用于硝基苯选择性加氢催化的钯镍合金/氮化镍界面构筑

金属负载型催化剂的界面结构设计一直是实现高效、高选择性催化反应的核心研究.本文表明,异质结结构PdNi&Ni_(3)N的界面电荷重新分布可以催化硝基苯选择性加氢成为偶氮类化合物.相比之下,独立的PdNi合金催化硝基苯转化为苯胺,而Ni_(3)N载体在相同条件下对硝基苯加氢的催化几乎没有效果. X射线光电子能谱和理论计算表明,PdNi&Ni_(3)N界面电荷重新分布导致有机反应中间体的吸附能发生变化,从而改变加氢反应途径,实现偶氮化合物的高选择性生成.本研究进一步表明了界面结构设计在有机催化加氢反应中的重要性,而且可能会引起研究者对于异质结构金属(合金)/过渡金属氮化物更多的科学兴趣,以应用于催化领域的不断发展.

Covalence bridge atomically precise metal nanocluster and metalorganic frameworks for enhanced photostability and photocatalysis

Metal nanoclusters(NCs)with precise structure and ultrasmall size have attracted great interests in catalysis.However,the poor stability has limited its large-scale use.Herein,we proposed the“covalence bridge”strategy to effectively connect atomically precise metal NCs and metal-organic frameworks.Benefiting from the covalent linkage,the synthesized UiO-66-NH2-Au25(LCys)18 showed outstanding stability after 16 h photocatalysis.Moreover,the covalence bridge created a strong metal-support interaction between the two components and provided an effective charge transport channel and thereby enhanced photocatalytic activity.UiO-66-NH2-Au25(L-Cys)18 displayed an exceptional photocatalytic H2 production rate,which is 21 and 90 times higher than that of UiO-66-NH2/Au25(PET)18(made by physically combination)and bare UiO-66-NH2,respectively.Thermodynamic and kinetic studies demonstrated that UiO-66-NH2-Au25(L-Cys)18 exhibited higher charge transfer efficiency,lower overpotential of water reduction and activation energy barrier compared with its counterparts.

Two novel terpyridine-based chromophores with donor-acceptor structural model containing modified triphenylamine moiety: Synthesis, crystal structures and two-photon absorption properties

Two novel terpyridine-based chromophores with D-A (D = donor, A = acceptor) structural model containing modified triphenylamine moiety (L1 and L2 ) have been conveniently synthesized via formylation and reduction in satisfactory yields, and fully characterized. The single crystals of them were obtained and determined by X-ray diffraction analysis. The relationships between structure and photophysical properties of the two chromophores were investigated both experimentally and theoretically. The measured maximum TPA cross-sections per molecular weight (δmax /MW) of the chromophores are 0.63 GM/(g mol) (L1) and 0.72 GM/(g mol) (L2), respectively, in DMF as a high polar solvent. The results indicate that the value of δmax/MW could be well tuned by the intramolecular charge transfer (ICT), which could be realized by introducing additional elecron-donor/acceptor groups.

Recovering rare earth elements via immobilized red algae from ammonium-rich wastewater

Biotreatment of acidic rare earth mining wastewater via acidophilic living organisms is a promising approach owing to their high tolerance to high concentrations of rare earth elements(REEs);however,simultaneous removal of both REEs and ammonium is generally hindered since most acidophilic organisms are positively charged.Accordingly,immobilization of acidophilic Galdieria sulphuraria(G.sulphuraria)by calcium alginate to improve its affinity to positively charged REEs has been used for simultaneous bioremoval of REEs and ammonium.The results indicate that 97.19%,96.19%,and 98.87%of La,Y,and Sm,respectively,are removed by G.sulphuraria beads(GS-BDs).The adsorption of REEs by calcium alginate beads(BDs)and GS-BDs is well fitted by both pseudo first-order(PFO)and pseudo second-order(PSO)kinetic models,implying that adsorption of REEs involves both physical adsorption caused by affinity of functional groups such as-COO-and -OH and chemical adsorption based on ion exchange of Ca^(2+) with REEs.Notably,GS-BDs exhibit high tolerance to La,Y,and Sm with maximum removal efficiencies of 97.9%,96.6%,and 99.1%,respectively.Furthermore,the ammonium removal efficiency of GS-BDs is higher than that of free G.sulphuraria cells at an initial ammonium concentration of 100 mg L^(-1),while the efficiency decreases when initial concentration of ammonium is higher than 150 mg L^(-1).Last,small size of GS-BDs favors ammonium removal because of their lower mass transfer resistance.This study achieves simultaneous removal of REEs and ammonium from acidic mining drainage,providing a potential strategy for biotreatment of REE tailing wastewater.