聚合物-溶剂-超临界CO2三元体系的相行为

研究了聚合物-超临界二氧化碳二元体系溶解性,并考查了添加共溶剂对溶解性的影响,结果表明,添加共溶剂会大大提高CO2的溶解度.此外,还研究了聚合物-溶剂-超临界二氧化碳三元体系在高压时的相行为, 探讨了组分性质、含量等对温度-压力相图的影响.随着CO2含量的增加,压力-温度相图L-LV（单一液相向液气两相共存）边界线的斜率会出现突变点,发生由L-LV边界线向L-LL（单一液相向液液两相共存）边界线的过渡, 而L-LV边界线对不同聚合物并不敏感.     

Structural Assignment of Side Chain Liquid Crystalline Monomer and Polymer by 1-D and 2-D Solution NMR Studies

In the present study, the synthesis and characterization of a methacrylic-based side chain liquid crystalline monomer and its polymer were investigated with the aid of both 1-D and 2-D nuclear magnetic resonance (NMR) techniques. The mesophase characteristics of the monomer and polymer were determined by hot-stage optical polarized microscopy (HOPM). The nematic and smectic phases were observed for the monomer and polymer. Furthermore, ¹³C spin-lattice relaxation time measurements were performed on the above systems in order to monitor molecular dynamics. The present study provides an opportunity to carry out a systematic comparison of the evolution of structural as well as dynamical changes of the monomer and the polymer.     

Magnesium and calcium surfactants Ternary phase diagrams of magnesium and calcium dodecylsulphate with decanol and water

The isothermal ternary phase diagrams for the systems magnesium dodecylsulphate-decanol-water at 40 °C and calcium dodecylsulphate-decanol-water at 50 °C are determined by water deuteron NMR and polarizing microscopic studies. In the magnesium system, three liquid crystalline phases (lamellar and normal and reverse hexagonal) and two isotropic (normal and reverse) solution phases are characterized and their ranges of existence are obtained. The calcium system yields the same liquid crystalline phases, but only the lamellar liquid crystalline phase is investigated in detail. The important observations made are: (i) The lamellar liquid crystalline phase for the magnesium and calcium systems can incorporate, respectively, a maximum of 22.5 and 14.3 mole water per mole surfactant ion against 139 mole water for the corresponding sodium system. (ii) The reverse hexagonal liquid crystalline phase is formed for both the magnesium and calcium systems while no such liquid crystalline phase exists for the corresponding sodium system. (iii) The²H NMR quadrupole splittings obtained in the liquid crystalline phases for C₈SO ₄ ^– and C₁₂SO ₄ ^– surfactant systems with different counterions (Ca²⁺,Mg²⁺,Be²⁺,Na⁺) reveal that surfactant hydration is almost independent of alkyl chain length and counterions.     

Effects of Cetylpyridinium Chloride on Phase and Rheological Behavior of the Diluted C(12)E(4)/Benzyl Alcohol/Water System

The influence of the pore size distribution of activated carbon on the adsorption of phenol from aqueous solutions was explored. Activated carbons with different porous structures were prepared by gasifying a bituminous coal char to different extents of burn-off. The results of adsorption experiments show that the phenol capacity of these carbons does not proportionally increase with their BET surface area. This reflects the heterogeneity of the carbon surface for adsorption. The pore size distributions of these carbons, determined according to the Dubinin-Stoeckli equation, were found to vary with the burn-off level. By incorporating the distribution with the Dubinin-Radushkevich equation using an inverse proportionality between the micropore size and the adsorption energy, the isotherms for the adsorption of phenol onto these carbons can be well predicted. The present study has demonstrated that the heterogeneity of carbon surface for the phenol adsorption can be attributed to the different energies required for adsorption in different-size micropores. Copyright 2000 Academic Press.     

Thermodynamic and spectroscopic studies on cationic surfactant tetradecyltrimethylammonium bromide in aqueous solution of trisubstituted ionic liquid 1, 2-dimethyl-3-octylimidazolium chloride at different temperatures

In this work, the effects on micellar behavior of long chain cationic surfactant tetradecyltrimethylammonium bromide (TTAB) upon the addition of trisubstituted ionic liquid (IL), 1, 2-dimethyl-3-octylimidazolium chloride [odmim][Cl] at temperatures, 298.15–318.15 K has been studied. Different techniques such as conductance, surface tension, fluorescence and ¹H NMR have been employed to understand the interactional mechanisms. The values of critical micelle concentration (cmc) and various thermodynamic parameters have been calculated from conductivity measurements. The surface parameters like effectiveness of decrease in surface tension (Π_cmc), minimum surface area occupied per surfactant monomer (A_min), maximum surface excess concentration (Γ_max), and adsorption efficiency (pC₂₀) have been evaluated by surface tension measurements. Micellar aggregation number (N_agg) has been determined by quenching of pyrene. Further to understand interactions in post micellar region, ¹H NMR measurements have been performed. It has been observed that the lipophilicity of interacting ion modified the thermodynamic and aggregation properties of TTAB.     

Studies on the phase properties of lyotropic liquid crystals of Brij35/sodium oleate/oleic acid/water system: By means of polarizing microscope, SAXS, 2H-NMR and rheological methods

The pseudo-quaternary phase diagram of Brij35/sodium oleate/oleic acid/water systems has been investigated, and the liquid crystal area has been identified, which covers about two thirds of the whole phase diagram. The liquid crystal structure and behavior have been also studied by using polarizing texture, small angle X-ray scattering, ²H-NMR and rheometer etc. The result shows that when the composition of the system changes along the line of AA’ in this large liquid crystal region, the structural change is cubic→cubic/lamellar→lamellar→lamellar/hexagonal→hexagonal. Meanwhile, we made the first attempt of systematic study of the rheological properties of the above system. The lattice constants of cubic and hexagonal liquid crystals are 10.53 and 5.68 nm, respectively.     

The Additive Influence of Propane-1,2-Diol on SDS Micellar Structure and Properties

Micellar systems are colloids with significant properties for pharmaceutical and food applications. They can be used to formulate thermodynamically stable mixtures to solubilize hydrophobic food-related substances. Furthermore, micellar formation is a complex process in which a variety of intermolecular interactions determine the course of formation and most important are the hydrophobic and hydrophilic interactions between surfactant–solvent and solvent–solvent. Glycols are organic compounds that belong to the group of alcohols. Among them, propane-1,2-diol (PG) is a substance commonly used as a food additive or ingredient in many cosmetic and hygiene products. The nature of the additive influences the micellar structure and properties of sodium dodecyl sulfate (SDS). When increasing the mass fraction of propane-1,2-diol in binary mixtures, the c.m.c. values decrease because propane-1,2-diol is a polar solvent, which gives it the ability to form hydrogen bonds, decreasing the cohesivity of water and reducing the dielectric constant of the aqueous phase. The values of ΔGm0 are negative in all mixed solvents according to the reduction in solvophobic interactions and increase in electrostatic interaction. With the rising concentration of cosolvent, the equilibrium between cosolvent in bulk solution and in the formed micelles is on the side of micelles, leading to the formation of micelles at a lower concentration with a small change in micellar size. According to the ¹H NMR, with the addition of propylene glycol, there is a slight shift of SDS peaks towards lower ppm regions in comparison to the D₂O peak. The shift is more evident with the increase in the amount of added propane-1,2-diol in comparison to the NMR spectra of pure SDS. Addition of propane-1,2-diol causes the upfield shift of the protons associated with hydrophilic groups, causing the shielding effect. This signifies that the alcohol is linked with the polar head groups of SDS due to its proximity to the SDS molecules.     

Study on dynamic interfacial tension of 3-dodecyloxy-2-hydroxypropyl trimethyl ammonium bromide at liquid/liquid interface

Dynamic interfacial tension between aqueous solutions of 3-dodecyloxy-2-hydroxypropyl trimethyl ammonium bromide (R₁₂HTAB) and n-hexane were measured using the spinning drop method. The effects of the R₁₂HTAB concentration (the concentration below the CMC) and temperature on the dynamic interfacial tension have been investigated; the reason of the change of dynamic interfacial tension with time has been discussed. The effective diffusion coefficient, D_a, and the adsorption barrier, _a, have been obtained from the experimental data using the extended Word–Tordai equation. The results show that the dynamic interfacial tension becomes smaller while _a becomes higher with increasing R₁₂HTAB concentration in the bulk aqueous phase. D_a decreases from 5.56 × 10⁻¹² m⁻² s⁻¹ to 0.87 × 10⁻¹² m⁻² s⁻¹ while _a increases from 5.41 kJ mol⁻¹ to 7.74 kJ mol⁻¹ with the increase of concentration in the bulk solution of R₁₂HTAB from 0.5 × 10⁻³ mol dm⁻³ to 4 × 10⁻³ mol dm⁻³. Change of temperature affects the adsorption rate through altering D_a and _a. The value of D_a increases from 5.56 × 10⁻¹² m⁻² s⁻¹ to 13.98 × 10⁻¹² m⁻² s⁻¹ while that of _a decreases from 5.41 kJ mol⁻¹ to 5.07 kJ mol⁻¹ with temperature ascending from 303 K to 323 K. The adsorption of surfactant from the bulk phase into the interface follows a mixed diffusion–activation mechanism, which has been discussed in the light of interaction between surfactant molecules, diffusion and thermo-motion of molecules.     

Effect of L64 on the Phase Behavior of 1-Dodecyl-3-methylimidazolium Chloride/Water System

Phase behavior of ternary system involving surfactant‐like ionic liquid 1‐dodecyl‐3‐methylimidazolium chloride ([C₁₂mim]Cl), water, and nonionic surfactant PEO‐PPO‐PEO block copolymer (Pluronic L64) is investigated at 25°C. Hexagonal (H₁) and lamellar liquid crystal phase (Lα) are found in [C₁₂mim]Cl/H₂O/L64 system by using polarized optical microscopy (POM), small‐angle X‐ray scattering (SAXS) techniques and ²H NMR spectra. The phase structure (H₁ phase), which is formed in [C₁₂mim]Cl/H₂O binary system, is not changed when L64 with a low concentration is added. However, phase transitions will occur from hexagonal to multiphases of H₁ and cubic phases (C), then to Lα+C phases with constant [C₁₂mim]Cl/H₂O ratio and increasing L64 concentration. Moreover, at given L64 (5%, 20%) concentration, the lattice parameter of H₁ or Lα phase decreases with increasing [C₁₂mim]Cl/H₂O ratio. Fourier transform infrared (FTIR) spectra indicate that the H‐bonded network comprising an imidazolium ring, chloride ion and water formed in [C₁₂mim]Cl/H₂O binary system is disrupted upon addition of L64. This is helpful to the phase transition, due to the decreasing of interfacial curvature induced by dehydration of hydrated layer after the addition of PEO block of L64.     

Toward a Better Understanding on the Adsorption Behavior of Aromatics in 12R Window Zeolites

Benzene adsorption behavior in a large family of 12R window zeolites (X, Y, EMT, Beta and LTL) has been examined by means of in-situ FTIR spectroscopy and correlated with the zeolite structure, the type and number of counter-ions, and the negative charge on framework oxygen atoms of zeolites. The effect of coadsorption of HCl, NH₃ and CH₃NH₂ on the benzene location has also been studied. The present work illustrates that besides the benzene adsorption on counter ions of zeolites, the 12R windows could also be the adsorption sites for benzene. Upon adsorption of coadsorbates such as HCl, NH₃ and CH₃NH₂, the migration of preadsorbed benzene molecules from one type of adsorption sites towards another, i.e. from 12R windows towards the cations for HCl and opposite direction for NH₃ and CH₃NH₂, has been evidenced. The lack of adsorption of benzene on 12R windows of NaBeta even upon coadsorption of a series of basic molecules reveals that benzene adsorption on 12R windows is most likely governed by a molecular recognition effect where benzene molecule and 12R window should have the adapted chemical and structural properties like in enzyme-substrate system and zeolites can be referred to as solid enzymes or zeo-enzymes. This paper indicates also that the adsorption properties of zeolites can be modified and accommodated by introduction of a co-adsorbate.     

Phase behaviors of Gemini cationic surfactants/n-butanol/water systems

Phase diagrams for ternary system of the Gemini cationic surfactants, N,N-long chain alkyl-2-hydroxyl-N,N,N,N-tetramethyl diammonium dichloride (G_nCl₂) with butanol and water have been drawn based on experimental data at 25 °C. The phase diagrams show that L phase and different liquid crystalline phases are existent in the ternary system at different components. Electric conductivity of the L phase has been studied. Small-angle X-ray scattering (SAXS), ²H (deuterium) quadrupolar splitting (²H NMR) and the polarizing-light microscope were employed to confirm the characteristic texture structures and the microstructure of three different liquid crystalline phases.     

CCl2(A 1B 1,a3B1)自由基被烷烃类分子猝灭动力学

用放电 LIF实验装置,对CCl4/Ar混合气体放电产生CCl2自由基,再用541.52 nm激光将电子基态CCl2激励到激发态A 1B1(0,4,0)振动能级上,通过检测激发态CCl2时间分辨荧光信号,测得室温下CCl2(A 1B1)被烷烃类分子猝灭的实验结果,用我们提出的三能级模型分析处理实验数据,获得CCl2(A 1B1)态和CCl2(a 3B1)态的碰撞猝灭速率常数kA和ka值.     

CMPO/[Cnmim][NTf2]体系对Eu3+和UO22+的萃取行为

讨论了辛基(苯基)-N,N-二异丁基胺甲酰基甲基氧化膦(CMPO)/1-烷基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐([C_nmim][NTf₂],n=2,8,12)萃取体系分别对硝酸溶液中的铕离子(Eu³⁺)和铀酰根离子(UO₂²⁺)的萃取行为。主要研究了硝酸浓度、接触时间、温度、CMPO浓度对CMPO/[C_nmim][NTf₂]体系萃取性能的影响,并选取CMPO/[C2mim][NTf₂]体系对模拟高放废液中的镧锕元素进行了萃取分离。结果表明:随着离子液体侧链长度增长,萃取平衡时间逐渐延长;CMPO/[C2mim][NTf₂]体系对Eu³⁺的萃取是放热反应,萃取率随酸度增加而逐渐降低,对UO₂²⁺则是吸热反应,萃取率随酸度增加而逐渐升高;通过机理研究,推测出对Eu³⁺的萃取反应是离子交换,而对UO₂²⁺的萃取反应则是中性配位;CMPO/[C2mim][NTf₂]体系能有效的萃取模拟高放废液中的镧系、锕系元素,且在高酸下有一定的镧锕分离效果。     

Structural,spectroscopic and redox properties of transition metal complexes of dipyrido[3,2-f:2′,3′-h]-quinoxaline (dpq)

The chemistry of first row transition metal complexes obtained from the ligand dipyrido[3,2-f:2′,3′-h]-quinoxaline (dpq) have been reported. The reaction between Cu(ClO₄)₂ · 6H₂O with dpq under different reaction conditions led to the isolation of three polymorphic copper(II) complexes [Cu(dpq)₂(H₂O)](ClO₄)₂ · H₂O (2), [Cu(dpq)₂(ClO₄)](ClO₄) (3) and [{Cu(dpq)₂(H₂O)}{Cu(dpq)₂(ClO₄)}](ClO₄)₃ (4). The bluish-green compound 2, obtained by reacting Cu(ClO₄)₂ · 6H₂O with dpq in methanol, has a distorted trigonal bipyramidal structure with τ = 0.55. The reaction between Cu(ClO₄)₂ · 6H₂O and dpq in dry acetonitrile produced the blue compound 3 in which the copper(II) centre has a distorted square planar geometry. When the condensation reaction between 1,10-phenanthroline-5,6-dione and 1,2-diaminoethane was carried out in the presence of Cu(ClO₄)₂ · 6H₂O in methanol, the green copper(II) complex 4 was isolated along with 1. The structure determination of 4 has established the presence of two different complex cations in the asymmetric unit and they are considered as co-crystals. In the zinc(II) compound [Zn(dpq)₂(ClO₄)₂] (5), the two perchlorates are unidentately coordinated to the metal centre, providing a distorted octahedral geometry. The quinoxaline ring in 5 is involved in intermolecular π–π interactions, leading to the generation of a sinusoidal chain. The proton NMR spectra, especially those of the paramagnetic complexes [Ni(dpq)₃](ClO₄)₂ (6) and [Co(dpq)₃](ClO₄)₂ (7), have been studied in detail. The electronic absorption spectra and the redox behaviour of the copper(I), copper(II), cobalt(II) and cobalt(III) complexes have been studied. The three copper(II) compounds 2–4 show identical absorption spectra and redox properties when measured in acetonitrile, although in nitromethane they show small but definite differences in their spectral and redox features.     

Studies on photocrosslinkable copolymers of 4-methacryloyloxyphenyl-3′,4′-dimethoxystyryl ketone and methyl methacrylate

Copolymers with various contents of 4-methacryloyloxyphenyl-3′,4′-dimethoxystyryl ketone (MPDSK) and methyl methacrylate (MMA) were prepared in methyl ethyl ketone solution using benzoyl peroxide as a free radical initiator at 70 °C. Characterization of the resulting polymers was done by UV, FT-IR, ¹H NMR and ¹³C NMR spectroscopic techniques. The copolymer compositions were determined by ¹H NMR analysis. The monomer reactivity ratios were calculated using linearisation methods such as Finemann-Ross (r₁ = 0.4283 and r₂ = 0.3050), Kelen-Tudos (r₁ = 0.4264 and r₂ = 0.2606), and extended Kelen-Tudos (r₁ = 0.4022 and r₂ = 0.2704) methods as well as by a non-linear error-in-variables model (EVM) method using the computer program RREVM (r₁ = 0.4066 and r₂ = 0.2802). The molecular weights ( and ) and the polydispersity index of the copolymers were determined by gel permeation chromatography. The thermal stability of the copolymers increases with increase in concentration of MPDSK. Glass transition temperatures were determined by differential scanning calorimeter under nitrogen atmosphere. The photoreactivity of the copolymers having pendant chalcone moieties was studied in chloroform solution.     

Li and Li MAS NMR Studies on Fast Ionic Conducting Spinel-Type Li2MgCl4, Li2-xCuxMgCl4, Li2-xNaxMgCl4, and Li2ZnCl4

⁶Li and ⁷Li MAS NMR spectra including 1D-EXSY (exchange spectroscopy) and inversion recovery experiments of fast ionic conducting Li₂MgCl₄, Li_2-xCu_xMgCl₄, Li_2-xNa_xMgCl₄, and Li₂ZnCl₄ have been recorded and discussed with respect to the dynamics and local structure of the lithium ions. The chemical shifts, intensities, and half-widths of the Li MAS NMR signals of the inverse spinel-type solid solutions Li_2-xM^I_xMgCl₄ (M^I=Cu, Na) with the copper ions solely at tetrahedral sites and sodium ions at octahedral sites and the normal spinel-type zinc compound, respectively, confirm the assignment of the low-field signal to Li^tet of inverse spinel-type Li₂MgCl₄ and the high-field signal to Lioct as proposed by Nagel et al. (2000). In contrast to spinel-type Li_2-2xMg_1+xCl₄ solid solutions with clustering of the vacancies and Mg²⁺ ions, the Cu⁺ and Na⁺ ions are randomly distributed on the tetrahedral and octahedral sites, respectively. The activation energies due to the various dynamic processes of the lithium ions in inverse spinel-type chlorides obtained by the NMR experiments are E_a=6.6-6.9 and ΔG^*>79 KJ mol⁻¹ (in addition to 23, 29, and 75 kJmol-1 obtained by other techniques), respectively. The largest activation energy of >79 KJ mol⁻¹ corresponds to hopping exchange processes of Li ions between the tetrahedral 8a sites and the octahedral 16d sites. The smallest value of 6.6-6.9 KJ mol⁻¹, which was derived from the temperature dependence of both the spin-lattice relaxation times T₁ and the correlation times τ_C of Li^tet, reveals a dynamic process for the Li^tet ions inside the tetrahedral voids of the structure, probably between fourfold 32e split sites around the tetrahedral 8a site.     

CMPO/[Cnmim][NTf2]体系对Eu3+和UO22+的萃取行为

讨论了辛基(苯基)-N,N-二异丁基胺甲酰基甲基氧化膦(CMPO)/1-烷基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐([C_nmim][NTf_2],n=2,8,12)萃取体系分别对硝酸溶液中的铕离子(Eu~(3+))和铀酰根离子(UO_2~(2+))的萃取行为。主要研究了硝酸浓度、接触时间、温度、CMPO浓度对CMPO/[C_nmim][NTf_2]体系萃取性能的影响,并选取CMPO/[C_2mim][NTf_2]体系对模拟高放废液中的镧锕元素进行了萃取分离。结果表明:随着离子液体侧链长度增长,萃取平衡时间逐渐延长;CMPO/[C3+2mim][NTf_2]体系对Eu的萃取是放热反应,萃取率随酸度增加而逐渐降低,对UO_2~(2+)则是吸热反应,萃取率随酸度增加而逐渐升高;通过机理研究,推测出对Eu~(3+)的萃取反应是离子交换,而对UO_2~(2+)的萃取反应则是中性配位;CMPO/[C_2mim][NTf_2]体系能有效的萃取模拟高放废液中的镧系、锕系元素,且在高酸下有一定的镧锕分离效果。     

Raman spectra and O NMR study effects of CaCl2 and MgCl2 on water structure

With various concentrations of CaCl₂ and MgCl₂ aqueous solution below 1.0 mol/l, Raman spectra of water in the OH stretch region of 2500-4000 cm⁻¹ and ¹⁷O NMR chemical shift of water are measured and the Raman spectra are deconvoluted. Both Raman spectra and ¹⁷O NMR of water show that the effect of Ca²⁺ on water structure is stronger than that of Mg²⁺. CaCl₂ and MgCl₂ destroy four hydrogen bonded water structure, but promote median water cluster size.     

Chiral “P-N-P” ligands, (C20H12O2)PN(R)PY2 [R = CHMe2, Y = C6H5, OC6H5, OC6H4-4-Me, OC6H4-4-OMe or OC6H4-4-Bu] and their allyl palladium complexes

Chiral “P-N-P” ligands, (C₂₀H₁₂O₂)PN(R)PY₂ [R = CHMe₂, Y = C₆H₅ (1), OC₆H₅ (2), OC₆H₄-4-Me (3), OC₆H₄-4-OMe (4) or OC₆H₄-4-^tBu (5)] bearing the axially chiral 1,1′-binaphthyl-2,2′-dioxy moiety have been synthesised. Palladium allyl chemistry of two of these chiral ligands (1 and 2) has been investigated. The structures of isomeric η³-allyl palladium complexes, (R′ = Me or Ph; Y = C₆H₅ or OC₆H₅) have been elucidated by high field two-dimensional NMR spectroscopy. The solid state structure of [Pd(η³-1,3-Ph₂-C₃H₃){κ²-(racemic)-(C₂₀H₁₂O₂)PN(CHMe₂)PPh₂}](PF₆) has been determined by X-ray crystallography. Preliminary investigations show that the diphosphazanes, 1 and 2 function as efficient auxiliary ligands for catalytic allylic alkylation but give rise to only moderate levels of enantiomeric excess.     

双帽Keggin型杂多阴离子[H4As3Mo12O40]-和Keggin型杂多酸H3PM12O40 (M＝Mo, W)质子化的DFT研究

选用B3LYP方法在LanL2MB水平下, 对双帽α-Keggin型杂多阴离子[H₄As₃Mo₁₂O₄₀]^-的电子结构和质子的定位进行了密度泛函理论(DFT)研究. 结果表明, 双帽的形成大大影响了杂多阴离子[As₃Mo₁₂O₄₀]^5－的电子结构和性质, NBO分析显示参与成帽的三桥氧上的电子密度比双桥氧上的要大, 简单地从电荷密度来看, 质子将首先在三桥氧上定域成键, 但通过比较质子定域在几种桥氧上质子化稳定化能的大小, 发现[H₄As₃Mo₁₂O₄₀]^-中的四个质子将在八个双桥氧中的其中四个氧原子上定位, 而不是如文献中报道的在四个三桥氧上定域成键. 对杂多酸H₃PM₁₂O₄₀ (M＝Mo, W)中质子的定位也进行了理论计算并与文献进行了比较, 结果显示, H₃PMo₁₂O₄₀中质子是定位在双桥氧上; 而H₃PW₁₂O₄₀中质子将优先在双桥氧上定位, 但也可在端氧上定位; 这一结果与文献报道的相一致.