One-pot synthesis, optical property and self-assembly of monodisperse silver nanospheres

High-quality spherical silver (Ag) nanocrystals have been synthesized by using a one-pot approach, in which pre-synthesis of organometallic precursors is not required. This reaction involves the thermolysis of a mixed solution of silver acetate and n-dodecanethiol in a non-coordinating organic solvent. The size of the as-obtained Ag nanospheres can be controlled by adjusting the reaction time, reaction temperature and the amount of silver acetate added. The growth and nucleation process of the resultant Ag nanospheres have been studied by employing UV-vis absorption spectra and transmission electron microscopy (TEM) images. Furthermore, these Ag nanospheres have good self-assembly behaviors, and they are easily self-assembled into two- or three-dimensional superlattice structures due to the bundling and interdigitation of thiolate molecules adsorbed on Ag nanospheres. This one-pot synthetic procedure is simple and highly reproducible, which may be extended to prepare other noble-metal nanocrystals.     

One-pot synthesis of furocoumarins through cascade addition-cyclization-oxidation

A novel one-pot cascade addition-cyclization-oxidation for the regioselective synthesis of furo[3,2-c]coumarins has been developed; the reaction is mild and easily handled without the necessity for dry solvents and inert atmosphere.     

One-pot three-component synthesis of pyrazoles through a tandem coupling-cyclocondensation sequence

An efficient and general one-pot procedure for the synthesis of pyrazoles from acid chlorides, terminal alkynes and hydrazines was described via a coupling and cyclocondensation sequence. Acid chlorides coupled with terminal alkynes to give α,β-unsaturated ynones, and in situ converted into pyrazoles by the cycloaddition of hydrazines. The desired pyrazoles were obtained with 15-85% isolated yields.     

Novel bulk synthesis of magnesium oxide nanobelts networks by microwave hydrothermal route

Novel magnesium oxide (MgO) nanobelt structures were successfully synthesized on a large scale, low cost and catalyst free by a microwave hydrothermal route using the magnesium metal and potassium hydroxide precursors at 200 °C for 10 min. The synthesized MgO nanobelts were systemically characterized by power X-ray diffraction (XRD), scanning electron microscopy, energy dispersion spectroscopy and transmission-high resolution electron microscopy. The XRD results indicate that the MgO nanobelts have the well-crystalline cubic phase. The detailed morphological studies revealed that the synthesized products were nanobelts and were grown in large quantity. The optical energy gap of MgO nanobelts was found to be 3.1 eV. The photoluminescence spectra of the MgO nanobelts show a strong and broad green emission band, a weak ultraviolet emission band, and a weak red emission band. This novel method will open new dimensions for synthesized 1-D metal oxide and can be easily extended to the synthesis and assembly of other inorganic nanocrystals.     

Single-crystalline CuO nanobelts fabricated by a convenient route

A reverse micelle-assisted route for preparing CuO nanobelts from precursor Cu(OH)2- 4 is reported. The reverse micelles were used as microreactors, which led to anisotropic growth crystals during a simple solvothermal process. The formation conditions of the CuO nanobelts were also studied.     

One-pot synthesis and magnetic, electrical properties of single-crystalline α-MnS nanobelts

α-MnS single-crystalline nanobelts were synthesized for the first time on a large scale by solvothermal method in monosurfactant dodecylamine system. The investigation of magnetic properties shows antiferromagnetic transition temperature of as-synthesized α-MnS nanobelts is remarkably lower than that of bulk counterparts (152 K) and higher than that of corresponding nanoparticles (18 K). These single-crystalline α-MnS nanobelts exhibit higher coercivity (4013 Oe) than those of reported MnS nanowires (1020 Oe) and nanoparticles (330 Oe). The study on electrical transport shows that the conductivity of individual α-MnS nanobelt is as high as 3.2 × 10⁵ S/m.     

Shape-controlled synthesis of copper colloids with a simple chemical route

The new electrical and optical properties of nanomaterials depend sensitively on both size and shape, which are of both fundamental and technological interest. This paper introduces a simple chemical method to produce copper particles, which has the ability to shape the particle without using any capping agent or template. In our synthetic procedure, the reactant concentration and temperature exerted a strong influence on the shape of the copper particles. At low reactant concentrations, the particles were cubic; at high reactant concentrations, obtained particles were spherical. The number of hollow particles greatly increased when the synthesis was performed at low temperature. We also synthesized a copper cubic ring at lower temperature, and it has been rarely reported. The absorption spectrum of hollow particles showed obvious red shifts, which suggests the possible assembly of novel optical materials.     

One-pot conditional self-assembly of multicopper metallacycles

The self-assembly of supramolecular metallacycles via the coordination-driven directional bonding approach can be modified to produce some unexpected structural variations. The combination of a flexible ligand-capped dinuclear transition-metal acceptor like [Cu(2)(dppm)(2)(NCMe)(2)]X(2) (1X(2); dppm = Ph(2)PCH(2)PPh(2); X(-) = BF(4)(-), PF(6)(-), or BPh(4)(-)) with monodentate-bidentate donors like 2-, 3-, and 4-pyridylcarboxylates produced oligomeric compounds [{Cu(2)(dppm)(2)}(μ-(2-PyCO(2)))](2)X(2) (2X(2)), [{Cu(2)(dppm)(2)}(μ-(3-PyCO(2)))](2)X(2) (3X(2)), and [{Cu(2)(dppm)(2)}(μ-(4-PyCO(2)))](4)X(4) (4X(4)), respectively, as the thermodynamically stable products in one-pot reactions. However, the modified self-assembly is still subject to steric hindrance. The reaction of complex 1(BF(4))(2) with 6-Me-3-PyCO(2)H did not produce a polygonal dimeric metallacycle but a simple dinuclear complex, [Cu(2)(dppm)(2)(6-Me-3-PyCO(2))](BF(4)) (5(BF(4))). The crystal structures of complexes 2(PF(6))(2), 3(PF(6))(2), 4(BF(4))(4), and 5(BF(4)) were determined using X-ray diffraction.     

微波合成铜酞菁及荧光猝灭测定痕量亚硝酸根离子的研究

自1986年Gedye[1]和G iguere[2]等报道利用微波辐射促进有机反应的研究之后,微波技术在合成化学中的应用已成为人们关注的热点,采用微波固相法合成酞菁化合物已有报道[3,4]。本研究小组以邻苯二腈和氯化铜为原料,采用微波固相法合成铜酞菁,其特点为反应速度快,收率高,污染少,且节约能源[5]。将合成的铜酞菁进行磺化,发现其磺化液有很强的荧光特性[6]。进一步研究得出,NO2-能使磺酸基铜酞菁溶液发生荧光猝灭,荧光强度和NO2-浓度呈现出良好的线性关系,线性范围为4×10-7mol·L-1~1×10-5mol·L-1,检测下限3.01×10-7mol·L-1,且常见共存离…     

One-pot synthesis, photoluminescence, and electrocatalytic properties of subnanometer-sized copper clusters

Subnanometer-sized copper nanoclusters were prepared by a one-pot procedure based on wet chemical reduction. The structural characteristics of the 2-mercapto-5-n-propylpyrimidine-protected nanoclusters, Cu(n) (n ≤ 8), were determined by mass spectrometry. The Cu nanoclusters displayed apparent luminescence, with dual emissions at 425 and 593 nm, with quantum yields of 3.5 and 0.9%, respectively, and high electrocatalytic activity in the electoreduction of oxygen.     

One-pot copper(I)-catalyzed synthesis of 3,5-disubstituted isoxazoles

[reaction: see text] 3,5-Disubstituted isoxazoles are obtained in good yields by a convenient one-pot, three-step procedure utilizing a regioselective copper(I)-catalyzed cycloaddition reaction between in situ generated nitrile oxides and terminal acetylenes. Most functional groups do not interfere with the reaction, which can be performed in aqueous solvents without protection from oxygen. Since all reagents are used in stoichiometric amounts, formation of byproducts is minimized.     

酞菁和酞菁铜的三阶非线性光学性质

用INDO/SDCI方法研究了酞菁和酞菁铜的电子结构, 紫外-可见光谱, 三阶非线性光学系数及其色散效应, 发现酞菁铜中Cu^2+对γ的贡献很小, 故酞菁与酞菁铜的γ几乎相等, 我们的计算结果对此进行了合理的解释。     

Rapid self-assembly of oligo(o-phenylenediamine) into one-dimensional structures through a facile reprecipitation route

The self-assembly of oligo(o-phenylenediamine) (OPD) into 1-D nanostructures on a macroscopic length scale was found when they were transferred from N-methyl pyrrolidone to deionized water. Field emission scanning electron microscopy and confocal fluorescence microscopy were used to investigate the morphology of the precipitates. Results showed that large amounts of OPD 1-D supertructures could be obtained through the simple reprecipitation route, and the length of the fibers could be tuned from microscale to macroscale by adjusting the ratio of two solvents. X-ray diffraction patterns and UV-vis spectra revealed that pi-pi interactions between OPD molecules that facilitated the formation of 1-D structures became predominant when they were transferred from a good solvent to a bad one. Accordingly, a possible formation mechanism was proposed.     

One-pot biomimetic synthesis of monolithic titania through mineralization of polysaccharide

To obviate the common precipitation of titania after a precursor addition into aqueous or water-containing solutions, here we are using ethylene glycol as the reaction media with dissolved polysaccharide xanthan. The water is introduced in a restricted amount to provide only the hydration of polysaccharide macromolecules. An introduced precursor is involved into instant hydrolysis and following condensation reactions where contacting with the hydrating water. This resulted in titania formation on carbohydrate macromolecules like the biomineralization in living organisms. The gelling of solution proceeded without the precipitation even when the precursor was taken in concentration of ca. 3 wt.%. Polysaccharide in these syntheses served as a template. By varying the concentrations of precursor, xanthan and water, it was possible to manipulate the metal oxide morphology. Fibrillar, particulate and plate-like structures presented that depended on the synthesizing conditions. Titania prepared at ambient conditions was amorphous. When it was calcined at temperatures between 300 and 900 °C, crystalline anatase and rutile were found at 300 and 700 °C, respectively.     

The synthesis of a fluorinated phthalocyanine

The reaction of perfluoroalkylcopper with 4-iodophthalonitrile provides a convenient route to fluorinated phthalonitriles which readily form phthalocyanines in the presence of stannous chloride dihydrate.During the course of preparing 4-perfluoroheptylphthalonitrile $\text{1}$, a secondary reaction was observed when the reaction time was extended beyond two hours. This reaction involves the interaction of the orthodinitrile with copper and/or cuprous iodide to afford the phthalocyanine nucleus. This coaction is portrayed by the appearance of a green color in the reaction media.     

One-pot synthesis of block copolymers in supercritical carbon dioxide: a simple versatile route to nanostructured microparticles

We present a one-pot synthesis for well-defined nanostructured polymeric microparticles formed from block copolymers that could easily be adapted to commercial scale. We have utilized reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare block copolymers in a dispersion polymerization in supercritical carbon dioxide, an efficient process which uses no additional solvents and hence is environmentally acceptable. We demonstrate that a wide range of monomer types, including methacrylates, acrylamides, and styrenics, can be utilized leading to block copolymer materials that are amphiphilic (e.g., poly(methyl methacrylate)-b-poly(N,N-dimethylacrylamide)) and/or mechanically diverse (e.g., poly(methyl methacrylate)-b-poly(N,N-dimethylaminoethylmethacrylate)). Interrogation of the internal structure of the microparticles reveals an array of nanoscale morphologies, including multilayered, curved cylindrical, and spherical domains. Surprisingly, control can also be exerted by changing the chemical nature of the constituent blocks and it is clear that selective CO(2) sorption must strongly influence the block copolymer phase behavior, resulting in kinetically trapped morphologies that are different from those conventionally observed for block copolymer thin films formed in absence of CO(2).     

Controlled synthesis of tetragonal terbium orthophosphate nanostructures through a solvothermal route

The tetragonal TbPO₄ was controlled synthesized via a simple solvothermal route by using glycol as solvent. The structures and micromorphologies of the as-synthesized TbPO₄ have been investigated by means of X-ray powder diffraction (XRD) and field-emission scanning electronic microscopy (FE-SEM). The results showed that the tetragonal TbPO₄ are composed of square-like particles about 200 nm in diameter. The photoluminescence spectra exhibited that the emission spectra of the sample could be divided into two parts, representing the ⁵D₄ ?? ⁷F_J (J = 6, 5, 4, 3) transitions and ⁵D₃ ?? ⁷F_J (J = 6, 5, 4, 3) transitions of Tb³⁺.     

One-pot synthesis and characterization of a chromophore--donor--acceptor assembly

The acid-functionalized tris-heteroleptic chromophore--donor--acceptor assembly [RuII(bpyCOOH)(bpyCH2PTZ)(bpyCH2MV2+)](PF6)4]4+ (1) (bpyCOOH = 4'-methyl-2,2'-bipyridine-4-carboxylic acid; bpyCH2PTZ = 10-((4'-methyl-2,2'-bipyridin-4-yl)methyl)phenothiazine; bpyCH2MV2+ = 1-((4'-methyl-2,2'-bipyridin-4-yl)methyl)-1'-methyl- 4,4'-bipyridinediium) was synthesized in a one-pot reaction by careful selection of the order of ligand addition to RuCl2(DMSO)4 (DMSO = dimethyl sulfoxide). The success of this method was based upon separation and isolation of 1 from mixtures containing ligand-scrambled products by cation exchange chromatography. Metal-to-ligand charge-transfer (MLCT) excitation in acetonitrile at 464 nm was followed by intramolecular electron transfer to give a redox-separated state [RuII(bpyCOOH)(bpyCH2PTZ.+)(bpyCH2MV.+)]4+ with an efficiency of eta RS = 0.35 +/- 0.05.