Synthesis and characterization of polyphenylene vinylenes having <Emphasis Type="Italic">m</Emphasis>-terphenyl group: comparison of their optical properties

A series of alternate block copolymers of polyphenylene vinylenes that have 1,3-dioctyloxy phenylene in the center of kinked m-terphenyl group as one of the building blocks with either one of the aromatic groups, viz., 1,4-dioctyloxy benzene, 4,6-dioctyloxy benzene and 4,4′-dioctyloxy biphenyl, was synthesized through Heck polymerization. These alternate block copolymers, viz., poly(2,5-bis(octyloxy)phenylene vinylene alt 4′,6′-bis(octyloxy)-1,1′:3′,1″-terphenylene) (P1), poly(2,4-bis(octyloxy)phenylene vinylene alt 4′,6′-bis(octyloxy)-1,1′:3′,1″-terphenylene) (P2) and poly(4,4′-bis(octyloxy-3,3′-biphenylene vinylene alt 4′,6′-bis(octyloxy)-1,1′:3′,1″-terphenylene) (P3), were characterized for their thermal and optical properties. The synthesized polymers had good solubility in organic solvents and were stable up to 350 °C. The molecular weights of the synthesized polymers were in the range 4370–10,900 Da with polydispersity range 1.52–1.65, which were measured by the gel permeation chromatography technique. The optical properties of these polymers showed absorptions in solution at around 400, 329, and 345 nm for P1, P2, and P3 polymers, respectively. The photoluminescence emission maxima of the polymers were at around 461 nm with a shoulder 439 and 424 nm for P1, P2, and P3, respectively. Photoluminescence emission of films of these polymers showed minimum redshift (20 nm) when compared with spectra of their solutions. The optical and photoluminescence emission properties of these polymers were found to vary on the backbone structure.     

Carbon nanotube growth from alkali metal salt nanoparticles

We demonstrate that alkali metal salts, including KCl, NaCl, K₂SO₄, Na₂SO₄, K₂CO₃, and Na₂CO₃, can act as catalysts for carbon nanotube (CNT) growth in chemical vapor deposition (CVD). The solution of alkali metal salt, water and ethanol was nebulized and was introduced into the CVD reactor, producing CNT with a multi-walled structure. Individual CNT are terminated with an onion-shaped carbon tip even when different alkali metal salt catalysts are used. Through observation and analysis of the catalyst particles and the resulting product, we elucidate the mechanism by which the alkali metal salt nanoparticles are served as “seeds” and provide nucleation sites for CNT growth. The ethanol decomposes to release carbon atoms into the catalyst particles, and the carbon nucleates and then begins to assemble on the surface of the catalyst particles, resulting in the CNT growth. By altering growth conditions, branched CNT and single-walled CNT also can be grown on alkali metal salt nanoparticles.     

Ein effektives Verfahren zur Herstellung von 1α,25-Dihydroxy-cholecalciferol (Calcitriol) aus 1α3β,25-Trihydroxy-cholesta-5,7-dien (Procalcitriol)

An Effective Procedure for the Synthesis of 1α,25-Dihydroxy-cholecalciferol (Calcitriol) Starting with 1α,3β, 25-Trihydroxy-cholesta-5,7-diene (Pro-Calcitriol) In order to develop an effective synthesis of the important vitamin D metabolite 1α,25-(OH)₂-cholecalciferol (calcitriol) 5a starting with pro-calcitriol 1a the influence of reaction temperature and degree of turnover of 1a to the compositions of the photoproducts at irradiation in a 500 ml photoreactor were investigated. The combination of the highly photostable filter solution consisting of 2,7-dimethyl-3,6-diaza-cyclohepta-1,6-diene-tetrafluoroborate and biphenyl in ethanol realizes the double wavelength irradiation in the range of 290 to 300 nm and > 330 nm resulting in a highly amount of the desired pre-calcitriol 2a . The reversible photoisomers of pre-calcitriol 2a 1α,25-(OH)₂-lumisterol₃ 4a and 1α,25-(OH)₂-tachysterol₃ 3a were isolated from an irradiation mixture in pure form by means of an appropriate combination of flash-chromatography, MPLC and preparative HPLC, respectively. The isomers 2a, 3a and 4a were characterized chromatographically and spectroscopically. Photoisomerization of 1a at −45 °C using the filter solution mentioned above and recycling all reversible photoisomers resulted in highly pure 5a after thermally induced isomerization of 2a isolated from the irradiation mixture by means of flash-chromatography on Ag⁺- impregnated silica with a yield of 68%.     

Gold Nano-size Effect in Au/SiO2 for Selective Ethanol Oxidation in Aqueous Solution

Narrowly sized colloidal Au particles of varying average sizes (3–30 nm) were immobilized on an inert support (SiO₂) to study the Au size effect on the aerobic oxidation of ethanol in aqueous solution. Au particles with an average diameter of 5 nm showed an areal activity that was about three times that of the smaller (3 nm), and 15 times that of larger (10–30 nm) Au particles. Investigation on the dependence of product yields on ethanol conversion over these differently sized Au particles clearly uncovered that the yield of acetic acid increased always with the ethanol conversion, while that of acetaldehyde passed a maximum at an ethanol conversion of 20–30%, therefore well demonstrating that acetaldehyde is the intermediate product in the oxidation of ethanol to acetic acid.     

Synthesis of 2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine-1-oxide and its hydrazones

An efficient method for preparation of earlier unknown S-oxide of 2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine by oxidation of 2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine hydrochloride with hydrogen peroxide in H₂O or EtOH/H₂O followed by the reaction mixture neutralization with Na₂CO₃ has been described. Interaction of the S-oxide with acetaldehyde, butanal, benzaldehyde, 4-methoxybenzaldehyde and 4-pyridinecarboxaldehyde in EtOH, C₆H₆, in the mixture of acetonitrile and ethanol or ethanol and benzene affords the unknown hydrazones, N-organylmethylidene-2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine-1-oxides.     

New photosensitive and optically active organo-soluble poly(amide–imide)s from N,N′-(bicyclo[2,2,2]oct-7-ene-tetracarboxylic)-bis-L-amino acids and 1,5-bis(4-aminophenyl)penta-1,4-dien-3-one: synthesis and characterization

A new series of N,N′-(bicyclo[2,2,2]oct-7-ene-tetracarboxylic)-bis-L-amino acids 3a–g were synthesized by the condensation reaction of bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride 1 with two equimolars of various amino acids such as L-alanine 2a, L-valine 2b, L-leucine 2c, L-isoleucine 2d, L-phenyl alanine 2e, L-2-aminobutyric acid 2f and L-histidine 2g in an acetic acid solution. Also 1,5-bis(4-aminophenyl)penta-1,4-dien-3-one 7 was synthesized by using a two-step reaction. At first 1,5-bis(4-nitrophenyl)penta-1,4-dien-3-one 6 was prepared from the reaction of two equimolars 4-nitrobenzaldehyde 5 and one equimolar acetone 4 in ethanol and NaHCO₃ and dinitro compound 6 was reduced by using Na₂S. Then seven new photosensitive and optically active organo-soluble poly(amide–imide)s (PAIs) 8a–g with good inherent viscosities were synthesized from the direct polycondensation reaction of new N,N′-(bicyclo[2,2,2]oct-7-ene-tetracarboxylic)-bis-L-amino acids 3a–g with 1,5-bis(4-aminophenyl)penta-1,4-dien-3-one 7 by two different methods such as direct polycondensation in a medium consisting of N-methyl-2-pyrrolidone (NMP)/triphenyl phosphite (TPP)/calcium chloride (CaCl₂)/pyridine (py) and direct polycondensation in a tosyl chloride (TsCl)/pyridine (py)/N,N-dimethylformamide (DMF) system. The polymerization reactions produced a series of photosensitive and optically active organo-soluble PAIs with high yield and good inherent viscosity. The resulted polymers were fully characterized by means of FTIR and ¹H-NMR spectroscopy, elemental analyses, inherent viscosity, specific rotation, solubility tests, UV-vis spectroscopy, differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), and derivative of thermaogravimetric (DTG). These macromolecules exhibited maximum UV-vis absorption at around 370 and 265 nm in a DMF solution.     

掺氮TiO_2的制备与光谱分析

用硫酸钛与氨水反应得到TiO2前体,煅烧后制得掺氮TiO2粉体,研究了不同温度和加热时间下掺氮TiO2的XPS、FTIR和紫外可见光谱,结果表明,掺氮TiO2在400℃下加热1 h,所得粉体是锐钛矿相结构,与未掺杂TiO2相比,吸收边红移22 nm,对400~510 nm的可见光有一定的吸收率。氮的掺杂不仅使TiO2带隙变小,而且有助于氧空位的形成。     

Synthesis and properties of various PPV derivatives with phenyl substituents

New electroluminescent polymers with various phenyl groups, poly[2-dimethyl(octyl)silyl-5-(4-(dimethyl(octyl)silyl)phenyl)-1,4-phenylenevinylene] (P1), poly[2,5-bis(4-(dimethyl(octyl)silyl)phenyl)-1,4-phenylenevinylene] (P2), poly[2,5-bis(9,9-dihexylfluorenyl)-1,4-phenylenevinylene] (P3), and poly[2,5-bis(4-(4-(2-etylhexyloxy)phenyl)phenyl)-1,4-phenylenevinylene] (P4), have been synthesized by the Gilch polymerization. The maximum absorption peaks of P1-P4 appeared at 388-423 nm in THF solution, and are red-shifted to 404-425 nm in solid thin film. The photoluminescence (PL) emission spectra of P1-P4 show a maximum peak at 482-503 nm in THF solution and at 521-549 nm as the solid film state. The emission spectra in the solid film state are more red-shifted over 40 nm, and the full width at half maximum (fwhm) was 30 nm greater than the solution conditions. The polymer light-emitting diodes (PLEDs) with the configuration of ITO/PEDOT/polymer/Al emitted light with maximum peaks at around 517-546 nm. The various phenyl substituents, with intermolecular interactions in the solid film state, can introduce the color tuning and device performance enhancement of the conjugated polymer as an emissive layer in PLED.     

The highly active saddle-like Ag3PO4 photocatalyst under visible light irradiation

Saddle-like Ag₃PO₄ particles of tetrahedron structure were successfully synthesized using a co-precipitation method by mixing H₃PO₄ ethanol solution and AgNO₃ ethanol aqueous solution, where the percentage of ethanol in AgNO₃ ethanol aqueous solution was varied at 0, 50, 80, 90 and 100% (v/v). The photocatalytic performance of the synthesized samples was evaluated by photodegradation of Rhodamine B (RhB) under blue light irradiation (λ = 455 nm). The results showed that the morphology of the Ag₃PO₄ particles greatly changed depending on the ethanol content in the reaction solution. Excellent photocatalytic activity was observed at 80% (v/v) of ethanol, where the Ag₃PO₄ showed saddle-like morphology derived from the tetrahedron structure.     

Synthesis and Characterization of ZnO Nano-rods via Thermal Decomposition of Zinc(II) Coordination Polymers and Their Photocatalytic Properties

Two Zinc(II) coordination polymers [Zn(NO₂)₂(3-bapp)]_n·nH₂O (1) and [Zn(NO₂)₂(4-bapp)]_n·nH₂O (2) have been synthesized by using zinc acetate, sodium nitrite, {3-bapp: 2,6-bis (3-amidopyridyl) pyridine} and {4-bapp: 2,6-bis (4-amidopyridyl) pyridine} as precursor. Pure phase ZnO nano-rods were obtained by thermolyses of compound 1 and 2 in 600 °C for 3 h under air atmosphere. The ZnO nano-rods were characterized by X-ray diffraction and scanning electron microscopy. The average crystallite size of ZnO nano-rods (1), (2) were determined 30 and 40 nm respectively. The particle size of hexagonal nano-rods of (1) and (2) are in the range of 20–70 and 30–80 nm respectively. The photo-catalytic performance of degradation of Congo red solution was increased when the particles size were decreased.     

三嗪类光生酸剂的产酸性能研究

采用UV-vis光谱分析的方法,选用罗丹明B为酸示踪剂,对4种新合成的三嗪类光生酸剂(PAG1 -PAG4),分别在405nm和365nm下乙腈中的分解及产酸性能进行了研究,推导计算得到了其分解及产酸量子产率,并对这4种化合物的产酸量子产率进行了比较。实验结果表明405nm光源下4种三嗪光生酸剂中2-(9-葸乙烯基)-4,6-双(三氯甲基)-1,3,5-三嗪(PAG4)的分解和产酸量子产率达到分别为10%,9%,为四者中最高的;2-(4-羟基-1-苯乙烯基)-4,6-双(三氯甲基)-1,3,5-三嗪(PAG2)几乎不分解也不产酸;而在365nm光源下4种光生酸剂的分解及产酸量子产率均很低。     

Chemistry on the decay of the phenoxy radical from butylated hydroxytoluene

Decay of unstable 2,6-di-tert-butyl-4-methylphenoxy radical (2) was investigated in various solvents. Radical 2 was conveniently generated by dissociation of bis(methylcyclohexadienone) (1a), unstable dimer of 2, in solution. The products were butylated hydroxytoluene (3), 1,2-bis(4-hydroxyphenyl)ethane (7), 4,4′-stilbenequinone (8), and 4-(4-hydroxybenzyl)cyclohexadienone (5). Unidentified products also were formed. The formation of 5 was favored in polar solvents, but was not subject to catalysis with Et₃N or HCl. In contrast, the rates of formation of 7 and 8 appeared to be independent of solvent polarity. The mechanism of formation of the dimeric productsvia reactive intermediate quinone methide 4, generated from 2 by disproportionation, is discussed. Gradual disintegration of 5 in solution into 3 and 4 was investigated.     

Effect of cations and anions on properties of zinc oxide particles synthesized in supercritical water

Hydrothermal synthesis of zinc oxide fine particles from zinc salt (Zn(CH₃COO)₂, ZnSO₄, Zn(NO₃)₂) and alkali metal hydroxide (LiOH, KOH) aqueous solution was carried out with a Ti alloy batch reactor in supercritical water. Particle size synthesized in LiOH solution was relatively smaller than that in KOH. Emission spectra of the particle produced from ZnSO₄ and LiOH aqueous solution shows the highest intensity among these systems. Hydrothermal synthesis of zinc oxide fine particles from Zn(NO₃)₂ and LiOH solution was also carried out with a flow-through apparatus for continuous production and rapid heating of the starting solution to supercritical states. Nanoparticles having an average particle diameter of 16 nm was produced at 659 K and 30 MPa.     

二芳基乙烯类光致变色化合物的合成及其光电性质研究

在氮气及-78℃条件下,合成了两种二芳基乙烯类光致变色化合物1,2-双(2-甲基-5-(4-N,N-二甲氨基苯基)噻吩-3-基)全氟环戊烯(Ⅰa)和1,2-双(2-甲基-5-萘基噻吩-3-基)全氟环戊烯(Ⅱa),通过紫外-可见吸收光谱、荧光光谱、循环伏安法对其光谱特性和电化学性质进行了初步研究。在254nm紫外光照射下,Ⅰa和Ⅱa的氯仿溶液均由无色变为蓝色,最大吸收峰分别为620和570nm,在适当波长可见光照射下,均从有色态返回到无色态。通过UV-Vis光谱考察了这两种二芳基乙烯类化合物在溶液中的光致变色反应的动力学特征,实验结果表明,二芳基乙烯类光致变色化合物的闭环反应属于零级反应,开环反应为一级。电化学研究表明,在溶液中,Ⅰa和Ⅱa可发生不可逆的阳极氧化反应。     

N-Arylsulfonyl-N′-(pyrimidin-4-yl)ureas-synthesis and reaction with dimethyl sulfoxide

The N-arylsulfonyl-N′-(pyrimidin-4-yl)ureas ( 3a – 1 ) were synthesized by reaction of arylsulfonyl isocyanates ( 1 ) with 4-amino-2,6-dialkylpyrimidines ( 2 ). Treatment of 3 with alkali or of 1 with an excess of 4-amino-2,6-dimethylpyrimidine ( 2a ) gave the salts 4a – e . Reaction of the ureas 3a – c with dimethyl sulfoxide at 90 to 120°C afforded N,N′-bis(2,6-dimethylpyrimidin-4-yl) ureas 8a – c . The reaction is assumed to involve a four-centre mechanism with 5 as intermediate.     

咪唑苦味酸盐C3N2H5＋C6N3O7H2^-的合成、晶体结构和量子化学

利用咪唑的醇溶液与苦味酸的醇溶液合成了咪唑的苦味酸盐C_3N_2H_5~+C_6N_3O_7H_2~-,并培养出单晶,通过X射线单晶结构分析法测定了其晶体结构.结果表明,晶体属于正交晶系,空间群为Pbca,晶胞参数为:a=0.895 0 nm,b=1.347 4(3)nm,c=2.016 4 nm,α=β=γ=90°,V=2.431 7(3) nm~3,D_c=1.624 g/cm~3,Z=8,F(000)=1 216.运用Gaussian 03程序,在6-311+G(d)的基组上,用HF和B3LYP两种方法对标题化合物进行了理论研究,并对原子净电荷及原子间布局进行了分析.     

Mechanochemistry of Syringylglycerol-β-Guaiacyl Ether and Its Similarity to the Conventional Bleaching of Mechanical Pulps

Syringylalcohol (1), α-methyl syringylalcohol (2), 3, 4, 5-trime-thoxyphenyl methylcarbinol (3) were dispersed onto filter paper pulp or linter pulp, and treated, respectively, with a ceramic ball mill (CBM) or a vibration ball mill (VBM-1 or -2) under air for 1h. Mechanical treatment of VBM-2, having the more rigid surface of linter pulp, furnished the p-carbonylphenols (5), (6), and 3, 5-dimethoxy-p-benzoquinone (7). Mechanical treatments of syringylgl-ycerol-β-guaiacyl ether (4) with CBM, VBM, and a laboratory refiner provided α-(2-methoxyphenoxy)-β-hydroxypropiosyringone (8) in the highest yield and a less yield of p-quinone derivative (7) and others as shown in TABLE 2 and FIGURE 3. When treated the resultant mixture with alkaline H₂0₂, the chromophore (III) can be decomposed, but remarkable amounts of the leucochromophre (IV) are produced as shown in FIGURE 4.     

Molten salt synthesis of in-situ TiC coating on graphite flakes

TiC coating was synthesized on graphite flakes (G_f) by molten salt synthesis (MSS) using metal Ti powder and alkali salts. Three different alkali chloride salts of KCl, NaCl, and NH₄Cl were selected as the molten salt media substrate. Two mass ratios of 1:3 and 1:5 were chosen for Ti: G_f ratio, and the mass ratio of the powder (Ti + G_f) to the salt was 1:1. The synthesis was carried out at a temperature of 1100°? for 4 h. XRD was used to study the effect of alkali chloride salts and the Ti: G_f mass ratio on the synthesized coating. FE-SEM and AFM were accomplished to investigate the carbide formation and microstructure of the samples. Results showed that TiC coating was formed at 1100 °C for 4 h with both mass ratios in all three alkali chloride salts, but KCl was found to be the optimum alkali chloride salt or reaction medium. FE-SEM results displayed the formation of uniform coatings, and results from AFM indicated that the surface roughness increased from 0.72 for G_f to 4.94 nm for TiC coated G_f.     

Surface-diffusion mechanism for synthesis of substrate-free and catalyst-free boron nitride nanosheets

This study presents an innovative surface-diffusion mechanism for the growth of substrate-free and catalyst-free boron nitride nanosheets (BNNSs) by annealing an ammonium borate hydroxide hydrate precursor in a NH₃ chemical vapor deposition system. At elevated temperatures, part of NH₄B₅O₈ slowly decomposes and forms B₂O₃, and flowing NH₃ gradually diffuses to the B₂O₃ surface to form vertically aligned BNNSs. The lateral dimension and crystallinity of the BNNSs increase, while their thickness decreases with the continuous surface-diffusion reaction. The residual NH₄B₅O₈ and B₂O₃ absorbs moisture in the air to constitute NH₄B₅O₈·4H₂O and H₃BO₃ substrates. With increasing annealing temperature and soaking time (at 1400 °C for 7 h), all NH₄B₅O₈ decomposes and the surface-diffusion reaction between B₂O₃ and NH₃ completely occurs, forming substrate-free BNNSs with a lateral dimension of 1 μm and a thickness of 10 nm. This reliable approach for synthesizing BNNSs paves the way for future applications in advanced ceramic composites.     

TiO2 thin films synthesized by the spray pyrolysis deposition (SPD) technique

Anatase-type TiO₂ thin films with high transmittance (>70%) in the visible region were successfully synthesized on glass substrates by the spray pyrolysis deposition (SPD) technique. Two kinds of starting solutions; TiCl₄ ethanol solution and Ti(i-OC₃H₇)₄ 2-propanol solution with TiCl₄ as an additive were prepared separately. The TiO₂ thin film obtained from the former solution showed the preferred orientation along the [101] direction. However, a 1·5 μm thick film from the latter solution revealed almost the same transmittance as a 200 nm thick film from the former. The result indicates that the complexes produced by adding TiCl₄ in Ti(i-OC₃H₇)₄ 2-propanol solution plays an important role in the mechanism of the crystallization of TiO₂.