蒙脱土和高岭土对Pb2+的吸附

选择带结构负电荷的蒙脱土和带微量结构负电荷的高岭土,研究了其对Pb2+的吸附性能,并探讨了吸附机理。 研究表明,蒙脱土和高岭土吸附Pb2+的动力学曲线符合准二级动力学方程,吸附等温线符合Langmuir方程。 Pb2+同时以内层络合和外层配合形式吸附,其相对量与pH值有关。 在pH值小于4和大于8的范围内,以内层配合物为主;而pH值在4～8范围内外层配合物比例增大。 Pb2+能进入蒙脱土的层间,而不能进入高岭土的层间;部分Pb2+可进入黏土颗粒的微孔中被固定。 蒙脱土对Pb2+的吸附能力和饱和吸附量明显高于高岭土。     

Sorption and Preconcentration of the Herbicides Atrazine,Simazine, and Ametryne on Montmorillonite

This paper describes the treatment of montmorillonite (MT), with K⁺ (MT_K), Na⁺ (MT_Na), and Ca²⁺ (MT_Ca) to explore the use of these minerals for the extraction and preconcentration of the herbicides atrazine, simazine, and ametryne from aqueous medium. In the sorption process, the three materials exhibited good performance; ametryne was totally sorbed. For atrazine and simazine, MT_K showed a removal between 90% (atrazine) and higher than 99% (simazine). The recoveries employing solutions at initial concentrations of 100 µg L^?1 of each herbicide showed results of 90% (simazine) and 94% (atrazine), whereas for 10 µg L^?1, the results of 73% (simazine) and 81% (atrazine) were obtained. On the other hand, ametryne showed poor recovery values (25 to 40%), probably due to a stronger interaction with MT_K, lowering the recovery values. Based on the results for atrazine and simazine, MT_K presented good features to be used as sorbent phase and for preconcentration, being easily prepared with low cost, demanding low amounts to be used for this purpose, providing fast sorption of atrazine and simazine, and with appropriate recoveries.     

Sorption and permeation in elastic solids: applicability to gas transport in glassy polymeric materials

A thermodynamic analysis of sorption and transport in elastic solids is presented. The penetrant's chemical potential in the solid is calculated from the free energy changes that accompany deformation of the solid to accommodate the penetrant and mixing of the deformed solid and penetrant. Sorption isotherms are obtained by equating this chemical potential to that of that of the gas phase. The penetrant diffusivity is determined from a statistical mechanical analysis described in the literature. Both pure and mixed gas solubility, diffusivity and permeability are predicted. Mixed gas behavior is predicted using material parameters obtained from pure gas data only. The results suggest certain relationships between the dual mode model parameters that are found experimentally. Comparison with several experimental gas–polymer systems indicate the elastic solid analysis can reproduce pure gas data and predict mixed gas data well with physically realistic material parameters. The results provide a basis for investigating the relationships between the mechanical, volumetric, gravimetric and thermodynamic processes that give rise to transport.     

Diastereoselective and enantioselective chromatography of the pyrethroid insecticides allethrin and cypermethrin

Summary Liquid and gas chromatographic separations of the pyrethroid insecticides allethrin and cypermethrin have been investigated with various achiral and chiral stationary phases. Diastercomeric and enantiomeric selectivity was observed for cypermethrin on a Pirkle-type chiral LC stationary phase, but very strong interactions and therefore long retention times prevented the separation of allethrin on this phase. Trans-allethrin isomers were separated on a chiral -cyclodextrin RP-HPLC column while cypermethrin showed some difficulties on this phase due to isomerization. Diastereomeric but no enantiomeric selectivity by GC was achieved for cypermethrin with an apolar DB 5 capillary. GC separation of the diastereomers was used to study the selective photodegradation of cypermethrin isomers after forestry applications. Chiral -cyclodextrin-based GC phases showed some enantioselectivity for cis- and trans-allethrin isomers. A separation of the eight isomers into six partially resolved peaks was achieved by GC with a coupled column consisting of chiral permethylated -cyclodextrin and DB 1701 as stationary phases. This combination was used to characterize allethrin formulations intended for indoor use and to investigate allethrin products formed by ozonolysis of thin films of the insecticide.     

Sorption of dissolved galactoglucomannans and galactomannans to bleached kraft pulp

Sorption of mannans onto bleached kraft pulp (BKP) was investigated withreference to other interactions of mannans in mechanical pulping andpapermaking. O-Acetyl galactoglucomannans (GGM) isolated from thermomechanicalpulp (TMP), as well as enzymatically modified guar gum galactomannans (GM) wereused in the study. The results showed that deacetylation of TMP GGMs, alsooccurring during peroxide bleaching of TMP, dramatically increased thesorption.A higher sorption was also achieved after salt addition, while temperature hadno effect. Sorption of guar gum GMs onto BKP fibres was, on the other hand,quite unaffected by external conditions such as temperature, pH and saltaddition. The degree to which the pulp was beaten did not notablyinfluence the sorption either – only unbeaten pulp gave a clearly lower mannansorption. A lower number of galactose side groups, however, strongly affectedsorption – the lower the number of side groups, the higher the sorption.The molar mass did not seem to affect the rate of sorption to any higher extentat ambient temperature. At higher temperatures the rate of sorption of smallerGM polymers was, nevertheless, slightly increased. Low-molar-mass GMs alsosorbed at a higher rate onto unbeaten pulp compared to high-molar-mass mannans.GM sorption appeared to be virtually irreversible.     

Kinetics of Sorption,Desorption, and Diffusion in Zeolites

Sorption and desorption in zeolites (molecular sieves) have to be considered as complex processes, involving simultaneous diffusion in zeolite crystals, mass transfer in the intercrystalline void of a pellet, and heat transfer between the zeolitic sorbent and its surroundings. The kinetics of sorption and desorption, respectively, of n-C₄H₁₀ in zeolite X and of CO₂ in zeolite A have been investigated: only the initial rates of uptake or release of the sorbet are controlled by mass transfer alone whereas ultimately they also depend on the rate of heat transfer from the sorbent to its surroundings or vice versa. Diffusivities of the sorbate in the zeolite crystals can be obtained from the kinetics of mass transfer, provided the resistance due to viscous or Knudsen flow between the crystals of the zeolitic sorbent can be eliminated. A sample consisting of a monolayer of single crystals had to be used for this purpose in the n-butane/zeolite X system; the intracrystalline diffusivity obtained in this way is not in conflict with data obtained by NMR spectroscopy. The intracrystalline diffusivities obtained in this way—taking into account the coupling of several processes during sorption — are higher than values reported in the literature.     

An Effective Method to Construct Cluster‐based Frameworks with Multifarious Structures,Luminescence, and Sorption Properties

An effective method was developed for the synthesis of three cluster‐based frameworks with multifarious secondary building units (SBUs) and various structures, which were formulated as [Me₂NH₂]₂[Zn₁₀(BTC)₆(μ₃‐O)(μ₄‐O)(H₂O)₅] · 3DMA · 9H₂O ( FJI ‐ 3 ), [Me₂NH₂]₂[Zn₉(μ₃‐OH)₂(BTC)₆(H₂O)₃] · 5DMA · 6H₂O ( FJI ‐ 4 ) and [Me₂NH₂][Zn₃(μ₃‐OH)(BTC)₂DMF] · H₂O ( FJI ‐ 5 ) (H₃BTC = 1,3,5‐benzenetricarboxylic acid, DMA = N,N′‐dimethyl acetamide and DMF = N,N′‐dimethyl formamide), respectively. X‐ray structural analysis reveals that FJI ‐ 3 displays 3D highly porous metal‐organic framework with four kinds of microporous cages constructed by two paddle‐wheel Zn₂(CO₂)₄, trimeric Zn₃O(CO₂)₆, and tetrameric Zn₄O(CO₂)₆ SBUs. FJI ‐ 4 exhibits 3D microporous MOFs with a dodecahedral cavities built by paddle‐wheel Zn₂(CO₂)₄ and trimeric Zn₃O(CO₂)₆. FJI ‐ 5 shows 3D microporous MOFs with an 1D channel assembled by the Zn₃O(CO₂)₆ SBUs. In addition, the fluorescence and sorption properties in these cluster‐based frameworks were also investigated. Furthermore, the method employed in this work may provide an useful approach to the design and synthesis of novel cluster‐based frameworks.     

Analysis of carboxylic acids by gas chromatography of acetonyl esters. Application to aromatic,dicarboxylic and higher fatty acids

Summary The gas chromatographic analysis of the acetonyl esters of aromatic, dicarboxylic and higher fatty acids is reported and discussed together with their electron impact and chemical ionisation mass spectra. An improved method for the preparation of acetonyl esters is discussed.     

Gas chromatographic determination of the configuration of isovaline in antiamoebin,samarosporin (emerimicin IV), stilbellin,suzukacillins and trichotoxins

Summary The D-(resp. R) configuration of isovaline (=2-ethylalanine) was proved for the peptide antibiotics antiamoebin, Tü 165 (CBS 382.62), stilbellin, samarosporin (=emerimicin IV), suzukacillin B (A), trichotoxin A-40 and A-50. This contradicts the previously reported L-configuration for isovaline in antiamoebin and emerimicin IV. The configuration was determined by GC of the N-trifluoroacetyl-isovaline n-propyl ester on glass capillary columns coated with the chiral stationary phase N-propionyl-L-valine tert.-butylamide polysiloxane (Chirasil Val). The D-configuration of the isovaline from trichotoxin A-40 was also established independently using GC of N-pentafluoro-propionyl-isovaline (+)-3-methyl-2-butyl esters on glass capillary columns coated with OV 17.     

Sorption and diffusion of ethanol vapor in polybutadiene/acrylonitrile, polybutadiene/styrene and polybutadiene based polyurethanes

The sorption and diffusion behavior of ethanol vapor in series of polyolefine based polyurethanes (PU) made from hydroxyl-terminated polybutadiene/acrylonitrile (HTBN), hydroxyl-terminated polybutadiene/styrene (HTBS) and hydroxyl-terminated polybutadiene (HTPB) were investigated by using the quartz-spring, DSC, FTIR and AFM. The equilibrium absorption reduced with increasing content of hard segments for all the three types of PUs. The values of the maximum absorption were in the order of HTBN > HTBS > HTPB based PU and related to their composition. The non-Fickian diffusion was confirmed and the sorption was discovered mainly in the hard segments. The HTBN based PU revealed different sorption and diffusion behavior from the other two, which was resulted from its hydrogen bonding not only between ethanol and hard segments but also soft segments. The morphologies of PUs before and after ethanol absorption were also compared. The HTBN based PU showed the most evident phase re-congregation after ethanol absorption.     

中药材中拟除虫菊酯类农药残留量的毛细管气相色谱测定方法

首次建立了中药材中氯氰菊酯、氰戊菊酯和溴氰菊酯的提取、净化及其毛细管气相色谱测定法。运用混合溶剂提取,填有Ｆｌｏｒｉｓｉｌ和氧化铝的层析柱净化。样品中氯氰菊酯、氰戊菊酯和溴氰菊酯的添加回收率分别为９４．３０％～９９．３４％,９５．１７％～１０１．５５％和８９．１２％～１００．９７％;ＲＳＤ分别为４．０２％～８．２２％,１．９０％～８．０４％和３．７５％～５．０９％。结果表明,被测样品中除白芍外均含有氰戊菊酯,个别样品中含溴氰菊酯。实验表明,该法具有灵敏度高、选择性强、操作简便、净化效果好、适用性广等特点     

自然水体生物膜、悬浮颗粒物和表层沉积物的轻、重组分对有机氯农药的吸附特征

利用重液分离方法对自然水体中的生物膜、悬浮颗粒物和表层沉积物中的轻、重组分进行了分离,采用批量平衡法研究了各固相样品及其轻、重组分对六六六(HCHs)和滴滴涕(DDTs)的吸附特征,通过比较各组分对吸附的贡献,分析了固相样品吸附HCHs和DDTs的机制.结果表明,表层沉积物对HCHs和DDTs的吸附过程是沉积物中矿物表面和无定型有机质中的分配机制起主要作用,而对于结构更为复杂、非均质性程度更高的生物膜和悬浮颗粒物对HCHs和DDTs的吸附过程同时发生线性的分配作用和非线性的孔隙填充作用.     

Synthesis,isolation, and chromatography of perdeuterated α-1,2,3,4,5,6-hexachlorocyclohexane

Perdeuterated α-1,2,3,4,5,6-hexachlorocyclohexane (α-PDHCH) was synthesized and isolated in pure form. α-PDHCH was baseline separated from unlabeled α-HCH by high resolution gas chromatography on different stationary phases. α-PDHCH was also resolved into its enantiomeric forms by application of a chiral GC phase. Furthermore, chiral chromatography of a mixture of labeled α-PDHDH and unlabeled α-HCH resulted in four peaks. Standard solutions of α-PDHCH are recommended both as recovery standard for sample clean-up and as internal standard for the quantitation of chlorinated hydrocarbons with GC/MS or GC/ECD in environmental samples.     

Sorption of As(V) from waters using chitosan and chitosan-immobilized sodium silicate prior to atomic spectrometric determination

A natural biosorbent containing amine functional groups, chitosan, and a novel sorbent, chitosan-immobilized sodium silicate, were prepared and utilized for the selective sorption of As(V) from waters prior to its determination by atomic spectrometric techniques, namely, hydride generation atomic absorption spectrometry (HGAAS) and inductively coupled plasma mass spectrometry (ICP-MS). Chitosan was synthesized from chitin and sodium silicate was used as the immobilization matrix due to its straightforward synthesis. Through sequential sorption studies, it was shown that chitosan-immobilized sodium silicate has exhibited a better chemical stability than the chitosan itself which demonstrates the advantage of immobilization method. Both chitosan and chitosan-immobilized sodium silicate were shown to selectively adsorb As(V), arsenate, from waters at pH 3.0 at which neither chitin nor sodium silicate displayed any sorption towards As(V). The sorption of arsenate by chitosan is supposed to have electrostatic nature since pH of 3.0 is both the point at which the amino groups in chitosan are protonated and also the predominant form of As(V) is H₂AsO₄⁻. A pre-oxidation step is required if both As(III) and As(V) are to be determined. Desorption from the sorbents was realized with 1.0% (w/v) l-cysteine prepared in a pH 3.0 solution adjusted with HCl. Among the possible interfering species tested, only Te(IV) and Sb(III) were shown to cause a decrease in the sorption capacity especially at high interferant concentrations. High concentrations of Sb(III) also resulted in gas phase interference during hydride generation.The validity of the method was checked both via spike recovery experiments and also through the analysis of a standard reference material. Spike recovery tests were carried out with four different types of water; namely, ultra-pure, bottled drinking, tap, and sea water; and percent recovery values were found to be 114 (±4), 112 (±2), 43 (±4), and 0 (±1), respectively. It was concluded that the proposed methodology can be applied efficiently to low-to-medium ionic strength solutions, such as most drinking waters. The accuracy of the method was additionally investigated through the analysis of a standard reference material and a good correlation was found between the determined (26.6 ± 2.4 μg L⁻¹) and the certified (26.67 μg L⁻¹) value.     

Analysis of calcium blocker drugs in plasma,HRGC and HPLC analytical conditions for pharmacokinetic studies

Calcium blocker drugs are of increasing therapeutic relevance. Verapamil, nifedipine, diltiazem, and flunarizine are the most widely applied drugs of this type. New dihydropyridines (felodipine, nitrendipine) and related agents are presently undergoing intense investigation. HRGC and HPLC were used to determine eight of these drugs in spiked plasma samples. Both methods allow separation of most of the compounds in a single run and are specific, sensitive, and reproducible both for therapeutic monitoring and for pharmacokinetic studies in man and animals.     

Direct enantiomer resolution of primary,secondary, and tertiary alcohols by gas chromatography on Chirasil-Val

Summary Many enantiomeric pairs of alcohols (primary, secondary or tertiary) are resolved directly on persilylated glass capillary columns, coated with the chiral stationary phase L- or D-Chirasil-Val. Dependent on the chemical structure of the substrate, considerable resolution factors can be obtained, even with simple aliphatic alcohols. Thus, one strong attraction may be sufficient to produce significant chiral recognition. Enantiomeric purities of these alcohols can be determined with high accuracy and great ease.     

Characterization of complex hydrocarbon mixtures using on-line coupling of size-exclusion chromatography and normal-phase liquid chromatography to high-resolution gas chromatography

An on-line coupling of size-exclusion Chromatography (SEC), normal-phase liquid Chromatography (NPLC), and gas Chromatography (GC) for the characterization of complex hydrocarbon mixtures is described. The hyphenated system separates according to size, polarity, and boiling point. The use of size exclusion as the first separation step allows for the direct injection of complex (“dirty”) samples withont prior clean-up. SEC-NPLC coupling was realized using an on-line solvent evaporator based on fully concurrent solvent evaporation (FCSE) using a modified loop-type interface, vapor exit and co-solvent trapping. Complete reconcentration of the analytes was realized by the introduction of a cryogenic cold trap. For the subsequent hydrocarbon group-type separation an ammo-silica column with n-heptane as eluent was used. The NPLC-GC coupling was based on an on-column interface using partially concurrent solvent evaporation (PCSE) and an early vapor exit. Initial results obtained on the analysis of a residue from the atmospheric crude-oil distillation (a so-called long residue) are presented as an example of the enormous separation power of the SEC-NPLC-GC system. The application of the system for quantitative analysis has not yet been studied.     

Enantiomeric separation of 5-alkyl-5methylhydantion derivatives by capillary gas chromatography on permethylated β-cyclodextrin and molecular modeling

Permethylated β-cyclodextrin (hereafter designated perMe-β-CD), dililuted or not in polysiloxane, is an efficient chiral discriminant for native, 3-methylated, and 1,3-dimethylated series of 5-methyl-5-(C_nH_{2n + 1})hydantoins. From thermodynamic data obtained with pure perMe-β-CD and with the aid of molecular modeling, it is concluded that: (i) For native hydantoin derivatives having a carbon chain at the 5-position varying from ethyl to nonyl (2?n?9), the retention time is related to their H-bonding capability. The resolution is poor for derivatives with n?4. For n?5, the resolution is considerably improved and this increase in resolution is attributed to the long alkyl chain being capable of being buried inside the cyclodextrin cavity. (ii) For 1,3-dimethylhydantion derivatives having a carbon chain at the 5-position varying from ethyl to hexyl(2?n?6), the retention time is mainly determined by a steric fit between the solute and the inner volume of the macrocyclic cavity. For n = 2, a particular behavior is observed, consistent with a total inclusion of the solutes inside the cavity. By contrast with the native hydantoins, the selectively is high for light derivatives. Thus, the selectivity does not correlate with a strong docking energy (such as the presence of H-bonds postulated with native derivatives). (iii) For 3-methylhydantoin derivatives having a carbon chain at the 5-position varying from ethyl to octyl (2?n?8), as expected, retension time and selectivity are intermediate between that of native hydantoins and 1,3-dimethylhydantoins. For all three series, where n?5, the increase in chain length (n) does not bring about substantial changes in the chromatographic results. Therefore, for these long alkyl chain derivatives, similar dominant interactions with perMe-β-CD are postulated.