THERMODYNAMIC STUDY OF ADSORPTION OF PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTION BY A WATER-COMPATIBLE HYPERCROSSLINKED POLYMERIC ADSORBENT

Equilibrium data for the adsorption of phenolic compounds, i.e., phenol, p-cresol, p-chlorophenol and p-nitrophenol from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent (NJ-8) within temperature range of 283-323 K were obtained and correlated with a Freundlich-type of isotherm equation, so that equilibrium constants KF and n were obtained. The capacities of equilibrium adsorption for all the four phenolic compounds on the NJ-8 from aqueous solutions are around 2 times as high as those of Amberlite XAD-4, which may be attributed to the unusual micropore structure and the partial polarity on the network. The values of the enthalpy (always negative) are indicative of an exothermic process, which manifests the adsorption of all the four phenolic compounds on the two polymeric adsorbents to be a process of physical adsorption. The negative values of free energy change show that the solute is more concentrated on the adsorbent than in the bulk solution. The absolute free energy values of adsorption for NJ-8 are always higher than those for Amberlite XAD-4, which indicates that phenolic compounds are preferentially adsorbed on NJ-8. The negative values of the adsorption entropy are consistent with the restricted mobilities of adsorbed molecules of phenolic compounds as compared with the molecules in solution. The adsorption entropy values of phenolic compounds for NJ-8 are lower than those for Amberlite XAD-4, which means the micropores of NJ-8 require more orderly arranged adsorbate.     

氰乙基纤维素溶致性液晶的研究

氰乙基纤维素在二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、乙腈以及丙酮等溶剂中可以形成溶致性液晶。随浓度增加,溶液从各向同性状态经两相共存态转变成为完全的液晶态。升高温度到T_c,液晶相消失;降低温度到T′_c,液晶相再生成。T_c总大于T′_c。而且,浓度越高,过冷温度△T=T_c—T′_c越小。在各向同性,两相共存或完全的液晶状态,溶液平均折射率和消光度均与浓度呈线性关系。但在两相间相互转变时,即在C_1~*和C_2~*处,n-C和 A-C 曲线上出现转折点。高聚物与溶剂的相互作用参数X_(12)愈小,临界浓度C_1~*愈小。把描述大分子链柔顺性的参数f与X_(12)联系起来,可用 1956年 Flory的理论定性地解释溶剂对高聚物溶致性液晶形成的影响。     

Extremal k *-Cycle Resonant Hexagonal Chains

Denote by ^* _n the set of all k ^*-cycle resonant hexagonal chains with n hexagons. For any B _n ^* _n , let m(B _n ) and i(B _n ) be the numbers of matchings (=the Hosoya index) and the number of independent sets (=the Merrifield–Simmons index) of B _n , respectively. In this paper, we give a characterization of the k ^*-cycle resonant hexagonal chains, and show that for any B _n ^* _n , m(H _n )m(B _n ) and i(H _n )i(B _n ), where H _n is the helicene chain. Moreover, equalities hold only if B _n =H _n .     

Analyzing Anisotropic Exchange in a Pentanuclear Os2Ni3 Complex

Spin Hamiltonian parameters of a pentanuclear Os Ni cyanometallate complex are derived from ab initio wave function based calculations, namely valence-type configuration interaction calculations with a complete active space including spin-orbit interaction (CASOCI) in a single-step procedure. While fits of experimental data performed so far could reproduce the data but the resulting parameters were not satisfactory, the parameters derived in the present work reproduce experimental data and at the same time have a reasonable size. The one-centre parameters (local matrices and single-ion zero field splitting tensors) are within an expected range, the anisotropic exchange parameters obtained in this work for an Os−Ni pair are not exceedingly large but determine the low-T part of the experimental χT curve. Exchange interactions (both isotropic and anisotropic) obtained from CASOCI have to be scaled by a factor of 2.5 to obtain agreement with experiment, a known deficiency of such types of calculation. After scaling the parameters, the isotropic Os−Ni exchange coupling constant is cm⁻¹ and the D parameter of the (nearly axial) anisotropic Os−Ni exchange is ⁻¹, so anisotropic exchange is larger in absolute size than isotropic exchange. The negative value of the isotropic J (indicating antiferromagnetic coupling) seemingly contradicts the large-temperature behaviour of the temperature dependent susceptibility curve, but this is caused by the negative g value of the Os centres. This negative g value is a universal feature of a pseudo-octahedral coordination with configuration and strong spin-orbit interaction. Knowing the size of these exchange interactions is important because Os(CN) is a versatile building block for the synthesis of / magnetic materials.     

Direct determination of estriol 3- and 16-glucuronides in pregnancy urine by column-switching liquid chromatography with electrospray tandem mass spectrometry

Using column-switching liquid chromatography/tandem mass spectrometry (LC-MS/MS), we developed an improved analytical method of urinary estriol glucuronides. This new method is derived predominantly from maternal and fetal precursors in pregnancy. We used in the following procedure: first, we filtered urine samples with a membrane filter. Next, we directly injected the 50 microL aliquot of urine samples onto a pre-column. Then, after activating the column-switching valve, we backflushed the loaded samples onto the C(18) analytical column. Urine samples can be assayed within 20 min without any sample preparation steps. We monitored separated estriol glucuronides by negative electrospray ionization (ESI) and selected-reaction monitoring (SRM). The calibration range of estriol-3-glucuronide (E3-3G) and estriol-16-glucuronide (E3-16G) was 0.1-20 microg/mL and the linearity of the method was 0.9984 for E3-3G and 0.9987 for E3-16G. The limits of detection at a signal-to-noise (S/N) ratio of 3 were 10 ng/mL (E3-3G) and 5 ng/mL (E3-16G). The analytical recovery was over 85% and, in general, inter-day and intra-day variability for precision and accuracy were less than 10%. When applied to a pregnancy urine sample to biomedical monitoring of the function of the maternal/fetal unit, the proposed method allowed rapid and sensitive screening for the detection of E3-3G and E3-16G.     

Fast spatially localised electrooptical mode in vertically aligned nematic LCs with negative dielectric anisotropy

ABSTRACT

Electro-optical switching and the liquid crystal (LC) director distribution are studied in spatially periodic electric field for vertically aligned LC with negative dielectric anisotropy. Two electro-optical switching modes characterised by different switching times are observed. These modes are well distinguished optically by choosing proper geometry for the polarisers axes orientation. One of these modes is significantly faster as compared to the other. The fast switching is explained in terms of localised near-to-surface director reorientation. The 3D-numerical simulation shows very good agreement with the experiment: it points out the existence of the disclination lines and field-stabilised walls responsible for the localised director field switching and its relaxation. Possibilities of enhancing the fast mode for high-speed light modulators are discussed.     

Classification of oxide glasses: A polarizability approach

A classification of binary oxide glasses has been proposed taking into account the values obtained on their refractive index-based oxide ion polarizability α_O2−(n₀), optical basicity Λ(n₀), metallization criterion M(n₀), interaction parameter A(n₀), and ion's effective charges as well as O1s and metal binding energies determined by XPS. Four groups of oxide glasses have been established: glasses formed by two glass-forming acidic oxides; glasses formed by glass-forming acidic oxide and modifier's basic oxide; glasses formed by glass-forming acidic and conditional glass-forming basic oxide; glasses formed by two basic oxides. The role of electronic ion polarizability in chemical bonding of oxide glasses has been also estimated. Good agreement has been found with the previous results concerning classification of simple oxides. The results obtained probably provide good basis for prediction of type of bonding in oxide glasses on the basis of refractive index as well as for prediction of new nonlinear optical materials.     

CO吸附在过渡金属铂表面的微观动力学研究

建立了处理双原子分子-表面相互作用的推广的LEPS势.借助推广的LEPS势,系统研究了一氧化碳分子在铂低指数表面吸附的动力学特性,重现了低指数表面的分子吸附热、吸附几何及本征振动等实验数据；鉴定了某些不合理的文献信息,预测了实验尚未探测到的重要信息:预测到Pt(100)表面四重洞位的C－O伸缩振动频率为1 962.60 cm－1;预测到Pt(110)表面吸附态的C－O及C－Pt键长分别为115.1、147 pm.     

New stationary phase polarity parameters considering the electric intermolecular interactions in gas chromatographic column

Summary The possibility of evaluation of the parameters representing the dispersive solute-solvent interactions is presented. B_N and B_s values can be used to describe the liquid phase polarity and to predict the retention indices of alcohols when the model polyxyethylene glycol dialkyl ethers and their sulphur analogs are used as stationary phases. The possibility of the first ionization potentials estimation is also presented.     

Kubische Berechnung der Retentionsindices ohne Kenntnis der Totzeit tm

Zusammenfassung In der vorliegenden Arbeit wird eine Methode zur Retentionsindex-Bestimmung beschrieben, die von einem kubischen Zusammenhang zwischen Bruttoretentionszeit-Differenzen der Referenzhomologen und der Kohlenstoffzahl ausgeht. Hieraus ergeben sich direkt die Nettoretentionszeiten. Der Fehler der Totzeitbestimmung entfällt bei dieser Methode. Mit den so gewonnenen Nettoretentionszeiten erhält man über einen kubischen Zusammenhang zwischen 1g t_s=f(C) die Retentionsindices. Extrapolationen und Interpolationen sind über 300 Retentionsindexeinheiten mit einem mittleren Fehler von ±0,02 Retentionsindexeinheiten möglich. Das Verfahren bietet sich für eine automatische Berechnung der I-Werte mittels on-line-Datenverarbeitung an.

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Cubic calculation of retention indices without determining the dead-time t_m

Summary The method for the calculation of retention indices described here is based on a third order relationship between the logarithm of differences of unadjusted retention times of homologues and the carbon number. From this adjusted retention times are directly calculated. A determination of the dead-time is not necessary thus avoiding the errors connected with this factor. A cubic equation for the logarithm of the adjusted retention time lg t_s as a function of carbon number C_n is used for the retention index calculation. Extrapolations and interpolations can be done over a range of 300 index units with an average deviation of ±0.02 i.u.. The method offers the possibility of an automated on-line calculation of retention indices by computer merely on the basis of unadjusted retention times.