基于二茂铁的两个查尔酮衍生物的合成及超快三阶非线性光学响应

二茂铁是合成新颖有机功能材料的基本单元之一。 本文设计并合成了两个基于二茂铁的同分异构查尔酮衍生物:1-二茂铁基-3-(噻吩-2-基)丙烯酮(a)和1-二茂铁基-3-(噻吩-3-基)丙烯酮(b)。 采用超快激光Z-扫描技术(脉宽180 fs,波长532 nm)测定了化合物a和b的三阶非线性光学性质。 结果表明,化合物a吸收系数β=-2.1×10^-12 m/W,折射率n₂=1.9×10^-19 m²/W,分子超极化率γ=5.37×10^-32 esu;化合物b:β=-1.2×10^-13 m/W,n₂=2.0×10^-19 m²/W,γ=4.48×10^-32 esu。 说明在飞秒激光激发下,电荷转移能够在化合物a和b分子内部快速进行,二者均具有优异的超快三阶非线性光学响应。 在B3LYP/6-311+G(d,p)理论水平下,计算了化合物a和b分子轨道能量、极化率和各基团在前线分子轨道中的占有率。 理论计算结果显示,二茂铁基团在化合物a和b前线分子轨道中占有率分别为97%和98%,对两化合物的非线性光学性能起主导作用。     

芘基查尔酮的合成及三阶非线性光学性质

合成了一种新的具有潜在应用价值的非线性光学(NLO)有机材料1-(芘-1-基)-3-(4-二甲氨基苯基)丙烯酮(PMAK),并通过 NMR、IR、MS和元素分析等技术手段进行了表征。 采用溶液Nd:YAG激光技术测定了PMAK的三阶非线性光学性质并确定了相关参数。 纳秒实验结果:折射率n₂=-3.5×10^-17 m²/W,吸收系数β=7.0×10^-10 m/W,极化率χ⁽³⁾=2.54×10^-11 esu,分子超极化率γ=3.44×10^-30 esu;皮秒实验结果:n₂=-2.8×10^-18 m²/W,β=8.3×10^-11 m/W,χ⁽³⁾=2.49×10^-12 esu,γ=3.33×10^-31 esu。     

Molecular weights of polystyrenes in toluene solutions by light scattering. Comparison between classical values and values deduced from a new method

Light scattering measurements in toluene solutions are performed for a series of monodisperse polystyrenes with a molecular weight M_w range from 4×10³ to 8×10⁶. The scattered polarized intensities I_v and the natural depolarization ratios ρ_n are registered with different apparatus at λ=633 or 488 nm and the M_w values are deduced through different formulae. The complete Carr and Zimm formula (CL_a), from I_v and ρ_n, and the usual simplified formula (CL_b), from I_v, are considered for the classical method. An already demonstrated formula is considered for the new method (New). Values of M_w and related parameters do not depend on the experimental systems used but deviations appear when using different formulae. The deviations are generally low (about 10%) but often systematic: M_w(CL_a)<M_w(CL_b)<M_w(New). The most important difference concerns the effect of destructive interferences for M_w>5×10⁵: the new formula leads to a lower increase from θ=90° to θ→0 for M_w values (θ is the observation angle). For instance, in the 8×10⁶ sample, M_w(θ→0)/M_w(θ=90°)=3.6 instead of 6.1, which implies a revision of the usual determination of the radius of gyration, R_g.     

Ferroelectric liquid crystals with a thioester linking group positioned at the chiral tail

A homologous series of chiral thioesters, hexyl (2S)-2-[6-(4-alkanoyloxyphenyl)benzoyloxy-2'-naphthyl]thiopropionates, HnPBNTP (n=7-11) was synthesized, and the mesophases and electro-optical properties were studied. All the materials possess a ferroelectric SmC* phase, which was confirmed by the switching current behaviour. It was found that compounds with a shorter alkyl chain length (n=7-9) displayed SmA* and SmC* phases, while, compounds with a longer alkyl chain length (n=10 and 11), displayed the SmC* phase exclusively. Spontaneous polarization and apparent tilt angle were also measured. The maximum P_s values are in the range 15-26 nC cm^-2, and the maximum θ values are in the range 23°-28°.     

1-二茂铁基-3-[(9-乙基)咔唑-3-基]丙烯酮的合成及三阶非线性光学性质

合成了一个新的非线性光学(NLO)有机材料1-二茂铁基-3-[(9-乙基)咔唑-3-基]丙烯酮(FCAK),并通过NMR、IR、MS和元素分析等技术手段进行了表征。 采用粉末Nd∶YAG激光技术测定了标题化合物的三阶非线性光学性质并确定了相关参数。 激光脉冲为4 ns时,非线性折射率n₂=-3.5×10^-18 m²/W,非线性吸收系数β=-2.7×10^-11 m/W,三阶非线性极化率χ⁽³⁾=2.04×10^-12 esu,三阶非线性分子超极化率γ=1.1×10^-30 esu。 激光脉冲为21 ps时,n₂=0.55×10^-18 m²/W,β=-0.6×10^-11 m/W,χ⁽³⁾=3.4×10^-13 esu,γ=0.13×10^-30 esu。     

七水合三氯化铈-碘化钠催化氨基苯硫酚与高位阻α, β-不饱和酮的迈克尔加成反应

对七水合三氯化铈-碘化钠(CeCl₃·7H₂O-NaI)化邻氨基苯硫酚、 对氯邻氨基苯硫酚、 间氨基苯硫酚、 对氨基苯硫酚和对甲基苯硫酚与α,β-不饱和酮(1a~1o)的迈克尔加成反应进行了系统研究. 结果表明, CeCl₃·7H₂O-NaI-SiO₂复合催化剂能有效催化邻氨基苯硫酚及对氯邻氨基苯硫酚与α,β-不饱和酮(1a~1o)的迈克尔加成反应. 在优化的反应条件下, 即n(CeCl₃·7H₂O):n(NaI):n(α,β-不饱和酮)=1:2:2, m(CeCl₃·7H₂O):m(SiO₂)=1:1.6, 三氯甲烷作溶剂, 反应温度为回流温度, 反应时间为2 h, 反应可达到中等产率(43.1%~58.8%). 催化剂重复使用4次基本稳定. 此外, 提出了可能的催化机理.     

Influence of temperature on surface tension of three liquid crystal polymers and polyethylene terephtalate

In this work Pressure Volume Temperature (PVT) data for three different liquid crystal polymers (LCPs), namely Vectra A950^® and two LCPs based on 4,4'-dihydroxybiphenyl (PB-n) (where n is the number of methylene units present in the polymer) and polyethylene terephtalate (PET), were obtained for temperatures ranging from 50 to 300°C and pressures ranging from 0.1 to 200 MPa. The experimental data were fitted to the Flory-Orwoll-Vrij equation of state and used to predict the influence of temperature on the surface tension of the four materials studied.

The surface tension of PET was shown to decrease linearly with increasing temperature. The surface tension of both PB-11 (γ_PB-11) and Vectra A950^® (γ_Vectra) decreased linearly with increasing temperature for temperatures corresponding to the nematic phases of the materials. Abnormal behaviour was observed for the surface tension of PB-8 (γ_PB-8): at temperatures just above T_b (the temperature at which the material became birefringent), γ levelled off and then decreased. A clear discontinuity was observed for both γ_PB-8 and γ_PB-11 near the mesophase to isotropic transition. For both PB-8 and PB-11, γ decreased linearly with increasing temperature for temperatures corresponding to the isotropic phases of the materials.     

Binding of acrylic and sulphonic polyanions by open-chain polyammonium cations

The interactions between some acrylic and sulphonic polyanions and some protonated amines (diamines NH₂-(CH₂)_x-NH₂, x=2,…,10; linear tri-, tetra-, penta- and hexa-amines) were studied potentiometrically in aqueous solution, at 25°C. For both types of polyanions AL₂H_i (L⁻, monomer of polyanion, A, amine) species are formed, with i=1,…,n (n=number of amino groups in the amine). The stability of these species is strictly dependent on the polyammonium cation charge, and fairly independent of the type of amine (in diamine species maximum stability is observed for x=4, 5). Acrylic and sulphonic polyanion complexes are considerably stronger than analogous species formed by low molecular weight anions. Mean stability can be expressed as log K=2.87ζ^2/3, for polyacrylic anions and log K=2.42ζ^2/3 for polysulphonic anions (ζ=absolute value for charge product of reactants).     

Small angle X-ray scattering from lamellar phase for β-3,7-dimethyloctylglucoside/water system: comparison with β-n-alkylglucosides

Small angle X-ray scattering (SAXS) is measured for the lamellar phase in aqueous systems of 1-o-β-3,7-dimethyoctyl-D-glucopyranoside (β-Glc(Ger)), which has recently been prepared by us, 1-o-β-decyl-D-glucopyranoside (β-GlcC₁₀), and 1-o-β-octyl-D-glucopyranoside (β-GlcC₈). The repeat distance d obtained from the position of the diffraction peak does not follow the swelling law d = 2δ_hc/_hc, where δ_hc and _hc are the thickness and the volume fraction of the hydrophobic layer, respectively. This may result from the fact that δ_hc increases and, equivalently, the surface area per surfactant molecule (a_s) decreases with increasing concentration. So we calculate δ_hc and a_s from the observed d value at each concentration using the above swelling law. The half-thickness δ_hc increases in the order β-GlcC₈ < β-Glc(Ger) < β-GlcC₁₀ at a fixed concentration. On the other hand, the data on a_s for β-GlcC₁₀ and β-GlcC₈ lie on the same line and the data for β-Glc(Ger) lies above this line. These results suggest that the cross-sectional area of the geranyl chain is larger than that of the glucose headgroup. Existence of water filled defects in bilayer sheets is also discussed based on the SAXS pattern and the concentration dependence of d.     

Kinetic analysis of thermogravimetric data obtained under linear temperature programming—a method based on calculations of the temperature integral by interpolation

A new technique, called interpolation method, with general application in the kinetic analysis of processes studied by thermogravimetry (TG) under linear temperature programming is developed. It is based on the linear relationship, with slope 1, between log g() and log I(γ, θ) for the appropriate kinetic function, where I(γ, θ) is the normalized temperature integral, θ the normalized temperature (θ=T/T₀) and γ a dimensionless activation energy (γ=E/RT₀). Values of log I(γ, θ) are calculated by linear interpolations in a pre-built table. This method can easily be programmed and implemented in a personal computer, where the results (kinetic parameters and quality of regressions for the kinetic functions considered) are typically obtained in a very short time. The method is validated by analyzing different simulated thermogravimetric curves and comparing the results with those determined with some classic methods taken from the literature. In addition, the results are compared with the values obtained by a similar method, also developed and explained in this paper, which involves the evaluation of all the values of the temperature integral by numerical integration, therefore, demanding a much larger calculation time. The interpolation method is found to be more accurate than other published methods, particularly in the case of thermogravimetric curves corresponding to processes with low activation energies. The results obtained are always similar to those determined by the integration method, which is taken as reference. Application of the technique to experimental data for various types of reactions shows that the results are in agreement with the published parameters and kinetic laws.     

Theory of profiles of hydrogen stretching infrared bands of hydrogen-bonded solids. Multi-Fermi resonance effects and strong coupling between the high-frequency hydrogen stretching vibration and low-frequency phonons

A theory is developed to describe the profiles of hydrogen stretching infrared bands of hydrogen-bonded solids taking into account the anharmonic coupling between the high-frequency stretching vibration, ν(XH), and low-frequency lattice phonons, Ω_i, as well as multi-Fermi resonances between states involving the ν(XH) stretching and overtones or combinations of some internal modes. The theory has been constructed in the framework of the extended molecular exciton Davydov approach. Model calculations show that the strong couplings between the high frequency ν(XH) and low-lattice vibration frequencies, Ω_i, generate the broadness of the ν(XH) band but the multi-Fermi resonances between the ν(XH) state and overtones or combinations of internal modes generate the complicated substructure band which is observed experimentally.     

白山毛桃根抗脑胶质瘤活性成分及其纳米胶束的制备

采用溶剂提取和萃取方法得到白山毛桃根乙酸乙酯、 正丁醇和水层萃取物. 通过噻唑蓝(MTT)比色法考察了各萃取物对脑胶质瘤细胞U87MG活性的抑制作用. 采用高效液相色谱(HPLC)指纹图谱法比对确认活性部位的主要化学成分为2α,3α,24-三羟基-12-烯-28-乌苏酸. 采用溶剂挥发法制备了2α,3α,24-三羟基-12-烯-28-乌苏酸纳米胶束, 对其包封率、 粒径及ζ电位等进行了表征, 并考察了其抗肿瘤活性. 体外细胞实验结果表明, 白山毛桃根乙酸乙酯萃取物对脑胶质瘤细胞U87MG具有抑制作用, 通过与标准品比对确认2α,3α,24-三羟基-12-烯-28-乌苏酸为乙酸乙酯部位的主要成分, 且该成分对脑胶质瘤细胞活性具有较强抑制作用. 通过溶剂挥发法制备的2α,3α,4-三羟基-12-烯-28-乌苏酸纳米胶束包封率为64.7%, 粒径为20 nm, 粒径分布宽度(PDI)为0.246, ζ电位为-5.7 mV. 细胞实验结果进一步证明, 与单体化合物相比, 2α,3α,24-三羟基-12-烯-28-乌苏酸纳米胶束对脑胶质瘤细胞活性具有更强的抑制作用, 为白山毛桃根在脑胶质瘤治疗中的应用提供了实验依据.     

Polarised vibrational spectra of KH2PO3 single crystal

Polarised IR and Raman spectra for KH₂PO₃ single crystal samples were measured at room temperature. Additionally, the IR spectra for the Xb(Z) sample were also measured at low temperatures (300–14 K). The spectra are discussed on the basis of oriented gas model and group theory. The stretching νOH vibrations of the hydrogen bonds with the OO distances of 2.547 and 2.529 Å give characteristic broad ABC-type bands in the IR (polarised parallel to the X and to the b(Z) directions) and Raman (xx, xz and yx) spectra. The Davydov-type (correlation field or factor group) splitting is not observed for the νOH modes. The presence of two independent hydrogen bonds in the crystal is manifested by splitting of the C band into two (C′, C″) components and by the different frequencies of the out-of-plane bending γOH vibrations. The in-plane bending modes δOH are strongly mixed/coupled with the stretching vibrations of the PO₃ groups.

The C bands (C′ and C″) change into quite sharp bands on lowering of the temperature. Various simplified models for internal vibrations of the phosphite anions are applied for finding a correlation between the crystal structure and polarised vibrational spectra. The stretching vibrations of the νPH groups manifest their unequivalence in two symmetry-independent hydrogenphosphite anions.     

Surface properties of ω-perfluorooctyl-alkyl polyacrylates: odd–even effect

A series of ω-perfluorooctyl-alkyl polyacrylates has been prepared and analysed. The odd–even effect, already observed in the case of liquid crystalline polymers has been exhibited for perfluorinated ones. Values of the contact angles to advanced (θ_a), with withdrawal (θ_r), as well as the contact angle hysteresis (Δθ) of various ω-perfluorooctyl-alkyl polyacrylates in water at 20 °C are described. Contrary to the advancing contact angle which is almost independent of spacer length, the receding one varies strongly with it.     

A method for correcting the contact angle from the θ/2 method

The θ/2 method, a widely used technique on measuring the contact angle of a sessile drop, assumes that the drop profile is part of a sphere. However, the shape profile of a sessile drop is governed by the Young–Laplace equation and is different from a sphere, especially for drops with a large bound number (e.g. large volume or small surface tension). The spherical assumption, therefore, causes errors on evaluating the contact angles. The deviation of contact angle from the θ/2 method is evaluated from a theoretical calculation in this work. A simple means is given for correcting the measurement error. The corrected angle results from the drop volume, surface tension, liquid density and the contact angle from θ/2 method. An algorithm for finding the correct contact angle without knowing the density and surface tension is also given. At the end, two examples of pendant drops are given for the illustration.     

尿素改性β-分子筛催化苯与煤制油烷基化制重烷基苯

对β-分子筛(n(Si)：n(Al)=15：1)分别进行酸洗、碱洗改性,制备出孔结构、酸性等性质不同的分子筛催化剂。 通过扫描电子显微镜(SEM)、X射线衍射(XRD)、N₂吸附-脱附、NH₃-TPD和Py-FTIR等表征手段对分子筛催化剂的结构、性能及其在苯的烷基化反应中的应用进行了研究。 结果表明,盐酸浸洗对β-分子筛的孔径、比表面积及孔容均有扩大作用,但在酸性上有所减弱;NaOH溶液浸洗造成了分子筛骨架的崩塌,对其酸性与孔结构均造成了破坏;尿素改性不仅改善了分子筛的孔结构性质,而且对分子筛酸性影响较小,是一种温和、有效的改性方式。 尿素改性β-分子筛催化剂催化苯与煤基冷阱油的烷基化反应活性最好,烯烃转化率达91.2%,且重烷基苯2位异构体(2-HAB)和3位异构体(3-HAB)在产物中含量最高,选择性分别为50.1%和33.5%,占整个烷基化产物的84%。     

Characterization and decomposition mechanism of an unusual nickel, thiocyanate and 4-methylpyridine polymeric complex

The synthesis, characterization, and thermal decomposition of the [Ni(SCN)₂(H⁺SCN)₂(4-mepy)₂] compound with an octahedral structure in polymeric chain were reported, in which SCN groups form bridges among Ni(II) ions. The compound decomposes in water resulting in a pH<4 solution. The FT-IR spectrum presented doublet bands at 2117; 2128 cm⁻¹, 788; 773 cm⁻¹ assigned to ν(C---N) and ν(C---S) stretching modes, respectively, and δ(SCN) deformation modes at 468; 476 cm⁻¹. The Raman spectrum of the compound presented the ν(C---N) stretching as a strong doublet at 2122; 2128 cm⁻¹, ν(C---S) at 783; 770 cm⁻¹, and δ(SCN) at 468; 477 cm⁻¹. No significant changes were observed in the 4-mepy ligand bands compared with the vibrational frequencies of the pure compound or the compound in aqueous solution 0.2 mol l⁻¹. The crystal UV–vis reflectance spectrum presented two bands centered in 626 and 424 nm tentatively assigned to the d→d type transitions, ³A_2g→³T_1g and ³A_2g→³T_1g, for a symmetry close to O_h. The TG curve showed a mass loss between 120 and 200 °C assigned to the loss of the two 4-mepy molecules; from 200 to 265 °C, the loss of the two H⁺SCN groups; and from 265 to 450 °C, the loss of the two SCN groups that formed the bridges among the nickel atoms. Based on these mass loss data, a mechanism of thermal decomposition for the compound was proposed.     

Ab initio structural trends and torsional sensitivity in n-hexane and comparisons with crystallographic structural results

The molecular structures of n-hexane were determined by RHF/4-21G ab initio geometry optimization at 30° grid points in its three-dimensional τ₁(C11–C8–C5–C1), τ₂(C14–C11–C8–C5), τ₃(C17–C14–C11–C8) conformational space. Of the resulting 12×12×12=1728 grid structures, 468 are symmetrically non-equivalent and were optimized constraining the torsions τ₁, τ₂, and τ₃ to the respective grid points, while all other structural parameters were relaxed without any constraints. From the results, complete parameter surfaces were constructed using natural cubic spline functions, which make it possible to calculate parameter gradients, |P|=[(∂P/∂τ_i)²+(∂P/∂τ_j)²]^1/2, where P is a C–C bond length or C–C–C angle. The parameter gradients provide an effective measure of the torsional sensitivity of the system and indicate that dynamic activities in one part of the molecule can significantly affect the density of states, and thus the contributions to vibrational entropy, in another part. This opens the possibility of dynamic entropic conformational steering in complex molecules; i.e. the generation of free energy contributions from dynamic effects of one part of a molecule on another. When the conformational trends in the calculated C–C bond lengths and C–C–C angles are compared with average parameters taken from some 900 crystallographic structures containing n-hexyl fragments or longer C–C bond sequences, some correlation between calculated and experimental trends in angles is found, in contrast to the bond lengths for which the two sets of data are in complete disagreement. The results confirm experiences often made in crystallography. That is, effects of temperature, crystal structure and packing, and molecular volume effects are manifested more clearly in bond lengths than bond angles which depend mainly on intramolecular properties. Frequency analyses of the τ₁, τ₂ and τ₃ torsional angles in the crystal structures show conformational steering in the sense that, if τ₁ is trans peri-planar (170°≤τ₁≤180°; −180°≤τ₁≤−170°), the values of τ₂ and τ₃ are clustered closely around the ideal gauche (±60°) and trans (±180°) positions. In contrast, when τ₁ is in the region (50°≤τ₁≤70°), there is a definite increase in the populations of τ₂ and τ₃ at −90 and −150°.     

Length dependence of coherent electron transportation in metal–alkanedithiol–metal and metal–alkanemonothiol–metal junctions

We have applied the elastic-scattering Green’s function theory to study the coherent electron transportation processes in both metal–alkanedithiol–metal (gold–[S(CH₂)_nS]–gold, n = 8–14) and metal–alkanemonothiol–metal (gold–[H(CH₂)_nS]–gold, n = 8–14) at the hybrid density functional theory level. It is shown that the current decreases exponentially with the molecular length. At the low temperature limit the electron decay rate, β, for alkanedithiol junction is found to be around 0.30/CH₂ at 1.0 V bias, much smaller than the calculated value of 0.60/CH₂ for alkanemonothiol junction. The decay rate for alkanedithiol junction at the room temperature is neither sensitive to the activation of the Au–S stretching vibrational mode nor to the external bias. The calculated current–voltage characteristics and decay rates for both junctions are in excellent agreement with the corresponding experimental results.     

Density and refractive index measurements in hexaheptyloxytriphenylene, a discotic liquid crystal

Density and refractive index measurements in the discotic liquid crystal hexaheptyloxytriphenylene were performed in the hexagonal columnar Col_ho and isotropic I phases. The temperature dependence of the density ρ(T) for this compound was obtained by combining small angle X-ray data and capillary methods. The ordinary n_o extraordinary n_e and isotropic liquid n_i refractive indices were measured using a modified Abbe refractometer to an accuracy of about 10^-3. To check the consistency of the density and the refractometry experiments we used the Lorentz-Lorenz relation. An anomaly in the empirical relationship at the Col_ho-I phase transition, which holds for many uniaxial liquid crystals, was detected. A discrepancy between low birefringence Δn∼0.109 and a relatively high local electric field anisotropy for hexaheptyloxytriphenylene is discussed.