Elasticity, Strength, and Other Related Properties of Some Refractory Castables

Young's modulus of elasticity, transverse strength, extensibility, and load resistance were determined at a series of test temperatures on six groups of laboratory-prepared refractory castables which had ( a ) no heat-treatment, ( b ) heat-treatment at 1050°C., and ( c ) heat-treatment at 1300°C. The data suggested that the alterations in composition that occur with a rise in temperature were related to corresponding changes in modulus of elasticity and strength. The effects of dehydration, conversion of amorphous alumina to γ-alumina, and silica inversions were evident. The cement content and temperature of operation as well as the heat-treatment of the castables affected all these mechanical properties to varying degrees.     

Direct Method of Preparation of Dodecanesulfonamide Derivatives and Some Surface Properties

Alkanesulfonamide compounds are known as surfactants because of the presence of –SO₂NH– function in their molecule. Thus, they are used in many formulations in the chemical and textile industries and also as inhibitors of corrosion. Generally, sulfonamide derivatives are prepared using sulfonyl chlorides as the raw material. The methods often described in the literature involve the use of ammonia gas and pressure. A simple and direct method to prepare pure alkanesulfonamide derivatives possessing good surface properties is presented in this work. Thus, n-dodecanesulfonyl chlorides obtained by photochemical sulfochlorination of n-dodecane under visible light using sulfuryl chloride were separated from the reaction mixture. These sulfonyl chlorides, a mixture of primary and secondary isomers, were transformed in one step into N-ethyldodecanesulfonamides, N-ethanoldodecanesulfonamides and the salts of dodecanesulfonamidoacetic acid. After purification on chromatographic column, the six position isomers of these sulphonamide derivatives were analysed and well separated by gas phase chromatography using a nonpolar column. Then, gas phase chromatography analysis coupled to mass spectrometry using electronic impact (GC/MS/IE) was performed to identify the different position isomers. The primary isomers of sulphonamide derivatives were identified by crossed injection of the compounds obtained by synthesis from the 1-chlorododecane using the Grignard reagent, and identified by IR, ¹H- and ¹³C-RMN, elementary analysis and GC/MS/IE. Some physico-chemical properties of these sulphonamide derivatives were examined. The variation of surface tension versus the concentration of both primary and secondary sulphonamide derivatives were studied, and the critical micellar concentration was determined for the compounds showing surface activity. The foaming power was also determined by the Bartsch method, and the results obtained were compared to those of a commercial surfactant, the linear alkylbenzenesulfonate. The stability of the foam formed was also evaluated.

Synthesis,Chiroptical, and Redox Properties of Ferrocene‐Containing Optically Active Polymers

The Sonogashira–Hagihara coupling polymerization of ferrocene‐containing l ‐phenylalanine‐derived optically active o‐, m‐, p‐substituted bis(iodophenylene) monomers 1o , 1m , 1p with 1,4‐diethynylbenzene ( 2 ) and 1,4‐diethynyl‐2,5‐bis[2‐(2‐methoxyethoxy)ethoxy]benzene ( 3 ) is carried out to obtain the corresponding polymers consisting of ferrocene, amino acid, and phenyleneethynylene moieties. In the solution state, poly( 1o ‐ 2 ), poly( 1o‐3 ), and poly( 1m ‐ 2 ) exhibit no circular dichroism (CD) signals in N,N‐dimethylformamide (DMF), while poly( 1m‐3 ), poly( 1p ‐ 2 ), and poly( 1p ‐ 3 ) exhibit CD signals assignable to the main chain chromophore, indicating the formation of certain chiral structures. In the solid state, poly( 1o ‐ 2 ), poly( 1o‐3 ), poly( 1m ‐ 2 ), and poly( 1m‐3 ) exhibit CD signals in the solid state, while poly( 1p ‐ 2 ), poly( 1p ‐ 3 ) does not, indicating the different aggregation manners of the polymers in the solution and solid states. The monomer and the polymers exhibit redox properties assignable to the ferrocene moieties. Thermal gravimetry analysis (TGA) measurements reveal that a 30% weight reduction occurs at 500 °C yielding black ferromagnetic solids.     

Sintering Mechanism and Microwave Dielectric Properties of Bi12TiO20 Ceramics

A homogeneous Bi₁₂TiO₂₀ phase was developed in a specimen that was calcined at 700°C without the formation of a secondary phase. A small amount of the Bi₁₂TiO₂₀ phase melted during sintering and assisted the densification of the specimen. The Bi₂O₃ and Bi₈TiO₁₄ secondary phases were found in all specimens. All the specimens that were sintered at temperatures ≥775°C exhibited high relative densities above 98% of the theoretical density. The Q × f value of the Bi₁₂TiO₂₀ ceramics was influenced by the grain size. The Bi₁₂TiO₂₀ ceramics sintered at 800°C for 5 h showed promising microwave dielectric properties of ε_r = 41, Q × f = 10 400 GHz, and τ_f = ?10.8 ppm/°C.     

Bioinformatics of Differentially Expressed Genes in Phorbol 12-Myristate 13-Acetate-Induced Megakaryocytic Differentiation of K562 Cells by Microarray Analysis

Megakaryocytes are large hematopoietic cells present in the bone marrow cavity, comprising less than 0.1% of all bone marrow cells. Despite their small number, megakaryocytes play important roles in blood coagulation, inflammatory responses, and platelet production. However, little is known about changes in gene expression during megakaryocyte maturation. Here we identified the genes whose expression was changed during K562 leukemia cell differentiation into megakaryocytes using an Affymetrix GeneChip microarray to determine the multifunctionality of megakaryocytes. K562 cells were differentiated into mature megakaryocytes by treatment for 7 days with phorbol 12-myristate 13-acetate, and a microarray was performed using RNA obtained from both types of cells. The expression of 44,629 genes was compared between K562 cells and mature megakaryocytes, and 954 differentially expressed genes (DEGs) were selected based on a p-value < 0.05 and a fold change >2. The DEGs was further functionally classified using five major megakaryocyte function-associated clusters—inflammatory response, angiogenesis, cell migration, extracellular matrix, and secretion. Furthermore, interaction analysis based on the STRING database was used to generate interactions between the proteins translated from the DEGs. This study provides information on the bioinformatics of the DEGs in mature megakaryocytes after K562 cell differentiation.     

Microstructural and Microwave Dielectric Properties of Bi12GeO20 and Bi2O3‐Deficient Bi12GeO20 Ceramics

Bi₁₂GeO₂₀ ceramics sintered at 800°C had dense microstructures, with an average grain size of 1.5 μm, a relative permittivity (ε_r) of 36.97, temperature coefficient of resonance frequency (τ_f) of ?32.803 ppm/°C, and quality factor (Q × f) of 3137 GHz. The Bi_12‐xGeO_20‐1.5x ceramics were well sintered at both 800°C and 825°C, with average grain sizes exceeding 100 μm for x ≤ 1.0. However, the grain size decreased for x > 1.0 because of the Bi₄Ge₃O₁₂ secondary phase that formed at the grain boundaries. Bi_12‐xGeO_20‐1.5x (x ≤ 1.0) ceramics showed increased Q × f values of >10 000 GHz, although the ε_r and τ_f values were similar to those of Bi₁₂GeO₂₀ ceramics. The increased Q × f value resulted from the increased grain size. In particular, the Bi_11.6GeO_19.4 ceramic sintered at 825°C for 3 h showed good microwave dielectric properties of ε_r = 37.81, τ_f = ?33.839 ppm/°C, and Q × f = 14 455 GHz.     

Synthesis, Characterization, and Photovoltaic Properties of Soluble TiOPc Derivatives

We have synthesized soluble TiOPc derivatives containing alkoxy groups for use as additives in dye-sensitized solar cells (DSSCs). The DSSC devices containing these TiOPc derivatives exhibited short-circuit current densities of 8.49~10.04 mA/cm² and power conversion efficiencies of 2.73~3.62 % under AM 1.5 illumination and 100 mW/cm² irradiation.     

硼氟二吡咯亚甲基衍生物的合成、表征及光物理性质的研究

成功合成了中位为2-喹啉噻吩基硼氟二吡咯亚甲基和对葡萄糖四乙酸酯苯基的化合物4,4-二氟-8-[5'-(2-喹啉基)-2-噻吩基]-1,3,5,7-四甲基-4-硼-3a,4a-二氮杂-S-引达省和4,4-二氟-8-[4'-(2,3,4,6-O-四乙酰基-α-D-吡喃葡萄糖-1-氧基)苯基]-1,3,5,7-四甲基-4-硼-3a,4a-二氮杂-S-引达省,通过核磁进行表征。研究了这两个化合物在二氯甲烷中的紫外可见吸收光谱和荧光光谱,研究了化合物在薄膜和固体状态下的吸收光谱和荧光光谱,同时通过研究电化学性质得到化合物的HOMO和LUMO轨道。     

氟代四苯基联苯二胺衍生物的合成及其光谱和电化学性质

通过钯催化的Buchwald-Hartwig反应合成了三种新型的氟代四苯基联苯二胺衍生物N,N'-二苯基-N,N--二(2,4-二氟苯基)-[1,1’-联苯]-4,4’-二胺(TFTPB1),N,N’-二苯基-N,N’-二(3,4-二氟苯基)-[1,1’-联苯]-4,4’-二胺(TFTPB2)和N,N’-二苯基-N,N...     

Synthesis,Characterization, and Antileukemic Properties of Naphthoquinone Derivatives of Lawsone

Naphthoquinones are considered privileged structures for anticancer drug molecules. The Heck reaction of 2‐hydroxy‐1,4‐naphthoquinone (lawsone) with 1‐bromo‐3‐methyl‐2‐butene offered easy access to lapachol. Several naturally occurring linear and angular heterocyclic quinoids (α‐lapachone, β‐lapachone, dunnione, and related analogues) were prepared from lapachol. Furthermore, we demonstrated that the synthetic naphthoquinones inhibit cell proliferation in human leukemia HL‐60 cells. In particular, angular‐type derivatives were found to possess moderate cytotoxicity and to elevate the levels of intracellular glutathione disulfide (GSSG). Our work highlights the significant potential of naturally occurring angular‐series naphthoquinones as antileukemic agents.     

Preparation and characterization of a series of polyamides with long alkylene segments: Nylons 12 20, 10 20,s 20,6 20, 4 20 and 2 20

Summary A series of nylons with long alkylene segments between amide groups were newly prepared by step-heating melt-polycondensation of 1,lS-octadecanedicarboxylic acid with various diamines. The prepared polyamides were characterized carefully. The results show that many properties of the prepared nylons change regularly with the length of methylene segments in diamines. In addition, nylon 2 20 has a relatively low molecular weight and much different melting and thermal decomposition behaviors in comparison with other nylons. Received: 21 June 2OO2/Revised version: 18 September 2002/ Accepted: 18 September 2002 Correspondence to Deyue Yan E-mail: dyyan@mail.sjtu.edu.cn Tel: 0086-21-54742863 Fax: 0086-21-54741297     

羧甲基壳聚糖的制备及应用

通过醚化途径，制备壳聚糖的衍生物，得出了以异丙醇为介质对壳聚糖进行改性研究的最佳反应条件。     

Synthesis and Properties of Amide Derivatives of 4-N,N-Dialkylaminoazobenzenes

Several disperse dyes, derivatives of 4-N, N-dialkylaminoazobenzene having acetylamino, carbamyl, phthalimide or naphthalimide substituents have been prepared. Their spectral properties and reaction to heat were determined, and their usefulness was evaluated in terms of the sublimation fastness. It was found that the dyes containing a benzamide system with an unsubstituted NH group, similar to that in phthalimide and naphthalimide derivatives, show a high sublimation fastness due to their ability to associate.     

Fluorene Derivatives with Multi-addressable Properties: Synthesis,Characterization, and Reactivity

A series of novel fluorene derivatives were synthesized from the target compound N-octadecyl-9-oxo-9H-fluorene-4-carboxamide (3), which led to new functionalized five- and six-membered heterocyclic derivatives via reaction with various reagents. The synthesized compounds were allowed to react with propylene oxide to afford unique surface-active properties. The chemical structures of the newly synthesized compounds were elucidated and confirmed by spectroscopic and analytical tools. The synthesized compounds have good surface activity and the biological degradation of these fluorene-based surfactants was greater than 96% after 7 days.     

Ceramic Properties of Samarium Oxide and Gadolinium Oxide; X-Ray Studies of Other Rare-Earth Oxides and Some Compounds

Samarium oxide forms a ceramic of medium strength and density (6.0) when it is fired at 1300°C. When it is fired at 1500°C., its density is increased to 7.4 but it loses its stability toward boiling water. X-ray data are given concerning the structure of the oxide as received and at 1300°C. and of the reaction product of Sm203 with water. Gadolinium oxide forms a ceramic of somewhat higher density (7.0) at 1300° than does Sm₂O₃; at 1500°C. its density is slightly higher (7.6) whereas its stability toward water is unchanged. Data concerning both oxides include density, shrinkage, moduli of elasticity and of rupture, linear thermal expansion, differential thermal analysis, and specific heat as well as X-ray data. Results are given of a brief survey of the reaction products obtained when Sm₂O₃ and Gd₂O₃ are heated at 1500°C. in equimolecular quantities with Al₂O₃, BaO, CaO, CdO, Fe₂O₃, HfO₂, MgO, SO₂, SrO, ThO₂, and ZrO₂. X-ray data for the following rare-earth oxides as received and after calcination at 1400°C. are given: ceria, praseodymia, neodymia, europia, dysprosia, holmia, erbia, thulia, and ytterbia.     

Synthesis,Structural Characterization,Spectroscopic Properties,and Theoretical Investigations of Aminoacridine Derivatives

Synthesis of four N-(heterocyclic)-9-aminoacridine derivatives was investigated. The synthesized compounds, N-thiazolyl-9-aminoacridine (AC1), N-(1,3,4-thiadiazolyl)-9-aminoacridine (AC2), N-(5-methyl-1,3,4-thiadiazolyl)-9-aminoacridine (AC3), and N-(5-phenyl-1,3,4-thiadiazolyl)-9-aminoacridine (AC4) were characterized by FT-IR, ¹H NMR, mass-spectral, and elemental analysis. Amine-imine tautomerism was suggested by density functional theory (DFT) calculations. The optimized structures were obtained using B3LYP/6–311++G(d,p) level of theory. The UV–Vis absorption spectra were measured in various organic solvents. The synthesized compounds AC1–AC4 exhibit absorption spectra characteristic of typical donor–acceptor compounds. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) analysis have been used to explain the internal charge transfer (ICT) phenomena within the molecules. Also, simulated UV spectra were calculated using TD-DFT (B3LYP/6–311++G(d,p) and the results were compared with the experimental values.     

喹唑啉酮类化合物的合成及光电性能

以5-溴靛红和2,5-二溴吡啶为原料,合成了2,8-二溴-11H-吡啶并[2,1-b]喹唑-11-酮(Ⅱ),再通过Suzuki偶联反应在分子两侧用三芳胺等供电子基团进行了修饰,合成了3个喹唑啉酮衍生物,收率在68%～85%,其结构经1HNMR、13CNMR和MS确证。通过UV-Vis、FL测试考察了其光学性能,用循环伏安法和理论计算考察了其电化学性质。结果表明:在喹唑啉酮母体分子两侧接入供电子基团延长了分子的π共轭体系,增加了喹唑啉酮母体两侧的空间位阻,减少了分子间的π-π堆积,两侧的供电子基团与喹唑啉酮母体形成了推挽结构,有利于分子内的电子转移,减少电子由基态到激发态的跃迁能,其中接入三芳胺基团的2,8-双(4-(二苯基氨基)苯基)-11H-吡啶并[2,1-b]喹唑-11-酮(Ⅲa)的能带隙(Egap)最小,为2.2533 eV,而未修饰的喹唑啉酮母环(Ⅰ)的能带隙Egap为2.7231 eV。喹唑啉酮化合物的能带隙具有明显优势,该类化合物是一类潜在的三阶非线性光学功能材料。     

Environmental Effects on the Fluorescence of Tryptophan and Other Indole Derivatives

The fluorescence quantum yields of tryptophan, 3-methylindole and 3-β-hydroxyethylindole were investigated as a function of temperature in a variety of polar and non polar solvents. Similar quantum yields and “activation energies” were found for the different systems. It was concluded that the same collisional solvent deactivation is responsible for the decrease in quantum yield with temperature irrespective of solvent system used. A notable exception is water where a different mechanism is indicated. The quenching of the indole chromophore fluorescence by a variety of specific agents both attached to the ring by an ethylene bridge and in homogeneous solution was also studied. It was found that potential proton donating groups were good quenching agents, the effect being much greater for groups carrying a positive charge. Polarization by a neighboring group also enhanced the quenching ability of any specific group. It was concluded that an excited state charge transfer complex is probably involved as a first step in the quenching process.     

二苯乙烯腈衍生物的合成及其光学性质研究

通过Suzuki偶联反应和Knoevenagel反应设计合成一种新型的二苯丙烯腈类化合物CNS-OMe,不同比例四氢呋喃与水的混合溶液中化合物的荧光测试结果表明目标化合物具有聚集荧光增强现象。通过紫外-可见光吸收光谱、荧光光谱和SEM分析,推测聚集诱导的分子平面化和J型聚集的协同作用是荧光分子具有荧光增强效应的原因。此外,研磨前后荧光颜色由蓝绿色变为绿色表明目标化合物具有压致变色的性质。分子空间结构的平面化,引起分子共轭加强,是产生压致变色的原因。