Nematic nanocomposites with enhanced optical birefringence

The proper performance of electro-optical devices utilising liquid crystals (LCs) requires materials with high diffraction efficiency, i.e. with high optical/dielectric anisotropy, low threshold voltage and fast switching. One can achieve increase of dielectric anisotropy by using chemical synthesis or mixing LC materials. However, in most cases, this causes an increase in the threshold voltage and switching times. Therefore obtaining materials with high dielectric anisotropy and keeping threshold voltage and switching times low is a challenging task. We achieved promising results by making binary mixtures of a polar nematic LC 4'-hexyl-4-biphenylcarbonitrile (HBPCN) with low percentage (1–10% by weight) gold nanoparticles. We report that for the mixtures with 1% and 2% gold the dielectric anisotropy increases by 100% and the birefringence by about 50% of their values for pure nematic. We also report that the increase of the dielectric anisotropy in the mixtures only slightly affects threshold voltage and switching times. We propose that this increase is caused by cluster formation in the mixtures.     

Development of an automated dual‐mode supercritical fluid chromatography and reversed‐phase liquid chromatography mass‐directed purification system for small‐molecule drug discovery

We report the development of a dual‐mode mass‐directed supercritical fluid chromatography and reversed‐phase liquid chromatography purification system. The addition of a third pump allows for flexible mobile phase control between the two techniques, and enables operation of either chromatography mode within minutes by activation of a set of switching valves on a single system. Software control, fluidic pathways, interface to the mass spectrometer, and fraction collection have been modified for compatibility between both separation methods. The conditioning solvent and tuning parameters for the mass spectrometer were adjusted to achieve an ideal signal trace in either mode with good linearity (r² > 0.970) over a range of concentrations and minimal noise for accurate peak detection and isolation. The registration success rate is 90% and overall sample recovery for either technique is 80?90%. Combining two orthogonal separation and purification modes in one single system has improved the purification throughput of complex mixtures and has been a valuable, cost‐saving tool in our laboratory.     

Automated preparative HPLC of prostanoids

Summary The separation of prostaglandins (PG) PGE₁, PGE₂, PGF_1α , PGF_2α and PGF_2β on Silasorb 600 columns with a water-containing mobile phases is described. A flexible, automated, preparative liquid-chromatographic (PLC) system has been used involving column switching, column temperature control, solvent selection and automated fraction collection.     

Multidimensional gas chromatographic separation of selected PCB atropisomers in technical formulations and sediments

A simple dual-column gas chromatographic system with a six-port switching valve has been used to separate the atropisomers of PCB congeners 84, 91, and 95 in technical PCB formulations and in extracts of soil and river sediment. A capillary column coated with a methylphenylsiloxane stationary phase (CP-Sil 8) was used as the first column, for retention window selection, and a permethylated β-cyclodextrin (ChirasilDex) capillary column as the main separation column. Because peak overlap could not be eliminated by optimization of column temperature, the enantiomeric ratios of PCB congeners could not be determined from the original chromatograms. The correct enantiomer ratio was determined from the peak areas obtained by deconvolution of the chromatograms. Whereas the PCB atropisomers considered were present in equal concentrations in the technical PCB formulations, analysis of a river sediment sample confirmed different residual concentrations of the atropisomers of congener 95.     

Polyamines and corresponding aminoacids measured together

Summary A two-column switching technique plus gradient elution have been developed to separate polyamines (putrescine, spermine and spermidine) and related aminoacids (aspartic, glutamic, glycine, taurine and gaba) as isoindole derivatives. The system uses two columns (CN and C18) arranged in series, via a valve which allows the effluent to be switched from the primary column to the secondary column or directly to the detector.     

无死体积蚀刻多孔膜接口的制作及其在二维毛细管电泳分离系统中的应用

介绍了一种在毛细管柱上原位腐蚀而成的多孔膜接口的制作方法,并用该接口构建了一类毛细管电泳二维分离技术平台。柱上原位腐蚀刻成的多孔膜接口具有零死体积、制作过程简易、成本低廉、耐用、柱间切换便捷等优点,特别适合作为基于毛细管柱的二维及多维电泳联用中的接口,是目前二维及多维毛细管柱联用中一类较为新型、实用、理想的接口。以鹿茸冻干粉可溶物样品为例,验证了该接口在二维毛细管电泳联用系统中的可行性和分离效能。实验结果表明：鹿茸冻干粉可溶物整个二维分离分析的时间在1 h内完成,二维分离系统的分辨率和总峰容量都比一维的高。     

毛细管等电聚焦-毛细管区带电泳二维蛋白质分离平台的构建及其性能

通常采用二维聚丙烯酰胺凝胶电泳 ( 2 D- PAGE)分析组织或细胞的全蛋白质 [1] ,但难与质谱 ( MS)直接联用 .用高效液相色谱 ( HPLC)和毛细管电泳 ( CE)分离分析蛋白质和多肽的一维分离模式的分辨率和峰容量有限 .多维柱联用技术比一维分离有更高的分辨率和峰容量 [2 ] ,便于和 MS直接联用 [3,4 ] ,易于实现自动化 .目前 ,有关 2 D- CE的报道相对较少 [5～ 7] ,我们初步实现了将 2 D- PAGE由平板转移到毛细管中[6 ,7] ,但凝胶柱的制作烦琐 ,存在交叉污染 ,不能与 MS直接联用 .本文用微透析中空纤维膜为接口构建了毛细管等电聚焦 ( …     

含双T切换接口的胶束电动色谱-毛细管区带电泳二维电泳芯片上混合氨基酸的分离富集

基于时间顺序设计提出了含双T切换接口的胶束电动色谱(MEKC)和毛细管区带电泳(CZE)的二维芯片,构建了相应的芯片分析测试系统.基于FITC标记的氨基酸样品的一维MEKC和CZE实验结果,对二维进样时间、二维分离启动时间等二维芯片电泳关键操作参数进行了优化.采用所构建的MEKC-CZE二维芯片电泳分析系统对精氨酸、赖氨酸、组氨酸、苯丙氨酸和酪氨酸的混合样品进行了二维芯片电泳分离分析,计算得到两种分离模式的正交性为56.0%.     

Recent Advances in The Polymer Dispersed Liquid Crystal Composite and Its Applications

Polymer dispersed liquid crystals (PDLCs) have kindled a spark of interest because of their unique characteristic of electrically controlled switching. However, some issues including high operating voltage, low contrast ratio and poor mechanical properties are hindering their practical applications. To overcome these drawbacks, some measures were taken such as molecular structure optimization of the monomers and liquid crystals, modification of PDLC and doping of nanoparticles and dyes. This review aims at detailing the recent advances in the process, preparations and applications of PDLCs over the past six years.     

Tunable separation of anions and cations by column switching in ion chromatography

A convenient ion chromatography method has been proposed for the routine and simple determination of anions (Cl⁻, SO₄²⁻ and NO₃⁻) and/or cations (Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺) using a single pump, a single eluent and a single detector. The present system used cation-exchange and anion-exchange columns connected in series via two 6-port switching valves or a single 10-port valve. The connection order of the ion-exchange columns could be varied by switching the valve(s). The present system therefore allowed the separation of either cations or anions in a single chromatographic run. While one ion-exchange column is being operated, the other ion-exchange column is being conditioned, i.e., the columns are always ready for analysis at any time. When 2.4 mM 5-sulfosalicylic acid was used as the eluent, the three anions and the five cations could be separated on the anion-exchange column and cation-exchange column, respectively. In order to obtain the separations of the target ions, the injection valve was placed between the two columns. Complete separations of the above anions or cations were demonstrated within 10 min each. The detection limits at S/N = 3 were 19-50 ppb (μg/l) for cations and 10-14 ppb for anions. The relative standard deviations of the analyte ions were less than 1.1, 2.9 and 2.8% for retention time, peak area and peak height, respectively. This proposed technique was applied to the determination of common anions and cations in river water samples.     

Two-dimensional liquid chromatography–ion trap mass spectrometry for the simultaneous determination of ketorolac enantiomers and paracetamol in human plasma: Application to a pharmacokinetic study

A bioanalytical method was developed for the simultaneous determination of paracetamol and ketorolac enantiomers in human plasma using two-dimensional liquid chromatography–mass spectrometry. Separation was first achieved in a reversed-phase C18 column by using a gradient solvent system consisting of 0.1% aqueous formic acid and acetonitrile (ACN). The effluent between 8.9 and 9.9 min, corresponding to phenacetin and racemic ketorolac peaks, was transferred to a polysaccharide-based chiral column (ChiralPak AD-RH) by using a six-port switching valve. Ketorolac enantiomers were subsequently separated on the chiral column using an isocratic mobile phase composed of ACN/0.1% formic acid 50:50 (v/v). The total run-time was less than 18 min. This innovative strategy prolongs the lifetime of chiral columns by avoiding damages due to the sample matrix. The detection was carried out with an ion trap mass spectrometer equipped with an electrospray ionisation source. The tested ranges were 0.05–20 μg/ml for paracetamol and 0.005–2 μg/ml for each ketorolac enantiomer. This method was fully validated and showed good performances in terms of trueness (80–110%) and precision (6.7–13.2%). The mean extraction recoveries were 60%, 72% and 76% for paracetamol, R-ketorolac and S-ketorolac, respectively. Finally, this procedure was successfully applied to a pharmacokinetic study.     

自粘结低硅铝X型沸石的结构、吸附和N_2/O_2分离比

用原位合成方法直接将高岭土转化为所需形状的低硅X型沸石(PLSX),经X衍射,~(29)Si,~(27)AI MAS NMR谱证实PLSX的结构硅铝比接近1,它含LSX的组成为40.40%,含4A的组成为17.92%,其余为无定形硅、铝氧化物.LSX的骨架硅铝比接近1,是骨架负电荷分配最均匀的X型沸石,293K时静态法测定和推算ISX的饱和吸附水达39.80wt%,LSX的组成为Na(96-x)K_x(Al_(96)S_i(96)O_(384))·310H_2O,是吸附量高、价廉的吸水剂.PLSX对空气中氮氧的分离系数为α(N_2/O_2)=3.15,高于用于PSA的商品5A的α(N_2/O_2)=2.33和已报道的13X的α(N_2/O_2)=2.36.PLSX也是一种极好的吸附分离剂.     

A Metalloregulated Four‐State Nanoswitch Controls Two‐Step Sequential Catalysis in an Eleven‐Component System

The nanomechanical switch 1 with its three orthogonal binding motifs—the zinc(II) porphyrin, azaterpyridine, and shielded phenanthroline binding station—is quantitatively and reversibly toggled back and forth between four different switching states by means of addition and removal of appropriate metal‐ion inputs. Two of the four switching stages are able to initiate catalytic transformations (ON1, ON2), while the two others shut down any reaction (OFF1, OFF2). Thus, in a cyclic four‐state switching process the sequential transformation A + B + C → AB + C → ABC can be controlled, which proceeds stepwise along the switching states OFF1→ON1 (click reaction: A + B → AB )→OFF2→ON2 (Michael addition: AB + C → ABC )→OFF1. Two consecutive cycles of the sequential catalysis were realized without loss in activity in a reaction system with eleven different components.     

Isomers of uroporphyrin free acids separated by HPLC

A synthetic mixture of uroporphyrin isomers I, II, III and IV as free acids in the synthetic ratio of 1:1:4:2 was resolved by reverse-phase HPLC using a C0:PEL (ODS) 37-50 micron precolumn and a Micro Bondapak C18 analytical column eluted with acetonitrile (4%) in phosphate buffer (pH 6.95). Clinically important I and III isomers of uroporphyrin were readily resolved directly from acidified urine as porphyrin free acids.     

Separation of Twenty Biogenic Amines and Derivatives by a High-performance Liquid Chromatographic Column Switching Technique with On-line Fluorimetric and Electrochemical Detections

Abstract

A new high-performance liquid chromatographic technique including the use of an automated column switching system has been developed for the study of dopamine, norepinephrine, epinephrine and serotonin and their related metabolites in biological samples. Through two runs, it has been possible to separate twenty derivatives and three internal standards which have to be added to samples prior to the extraction procedures. In each case, the column switching system allowed to obtain a clear separation of all the compounds, which will be of importance to avoid any expected interference from other endogenous substances, while decreasing the analysis time. By coupling on-line fluorimetric and electrochemical detections the specificity of the technique was enhanced, since the ratio of the responses of both detectors was an index of the purity of the peaks. In addition, fluorimetric detection was found of value to free the determination of some compunds from the effects of solvent front while electrochemical detection increased the sensitivity. Finally, the column switching system allowed a rapid cleaning of the columns between two analyses. A typical application to a human urine sample was shown.     

High-resolution IR spectroscopy of dimers of HDO with H2O in helium nanodroplets

We report on rotationally resolved IR spectra of dimers of HDO as a deuterium (d) donor with H(2)O, HDO, and D(2)O embedded in superfluid Helium nanodroplets in the 2650-2660 and 2725-2740 cm(-1) regions of the O-D donor stretch and symmetric acceptor stretch vibrations, respectively. By comparing spectra at different levels of deuteration we were able to unambiguously assign the donor stretch signals of H(2)O···DOH, HDO···DOH, and D(2)O···DOH. For H(2)O···DOH, three ΔK(a) = 0 sub-bands were found that were assigned to transitions from the lower and upper acceptor switching states of K(a) = 0 and the lower acceptor switching state of K(a) = 1. In addition, b- and c-type transitions in the acceptor stretch region of HDO···DOH were observed that allowed us to determine the acceptor switching splitting of Δv? = 5.68 cm(-1) in the HDO···DOH vibrational ground state. We suggest that the dominating broadening mechanism is intervibrational relaxation due to coupling of the rovibrational levels of the chromophore via internal droplet excitations.     

Preparative separation of anti‐oxidative constituents from Rubia cordifolia by column‐switching counter‐current chromatography

An effective column‐switching counter‐current chromatography (CCC) protocol combining stepwise elution mode was successfully developed for simultaneous and preparative separation of anti‐oxidative components from ethyl acetate extract of traditional Chinese herbal medicine Rubia cordifolia. The column‐switching CCC system was interfaced by a commercial low‐pressure six‐port switching valve equipped with a sample loop, allowing large volume introduction from the first dimension (1^st‐D) to the second dimension (2^nd‐D). Moreover, to extend the polarity window, three biphasic liquid systems composed of n‐hexane/ethyl acetate/methanol/water (1:2:1:2, 2:3:2:3, 5:6:5:6 v/v) were employed using stepwise elution mode in the 1^st‐D. By valve switching technique the whole interested region of 1^st‐D could be introduced to second dimension for further separation with the solvent system 5:5:4:6 v/v. Using the present column‐switching CCC protocol, 500 mg of crude R. cordifolia extract were separated, producing milligram‐amounts of four anti‐oxidative components over 90% pure. Structures of purified compounds were identified by ¹H and ¹³C NMR.     

Optical switching and alignment of antiferroelectric liquid crystals containing an azo group

The optical properties of two kinds of photochromic antiferroelectric liquid crystal (AFLC) containing an azo group have been examined. Depending on the substituting group at the chiral centre, these AFLCs showed different photoinduced phase transitions by Ar⁺ laser light irradiation. This phase transition has led to a new form of optical switching controlled by a bias voltage. In addition, it was found that these AFLCs caused an azimuthal photoalignment effect regulated by linearly polarized Ar⁺ laser light irradiation. These phenomena were applied to image storage.     

In vitro interaction cocktail assay for nine major cytochrome P450 enzymes with 13 probe reactions and a single LC/MSMS run: analytical validation and testing with monoclonal anti-CYP antibodies

A sensitive and rugged LC/MSMS method was developed for a comprehensive in vitro metabolic interaction screening assay with N-in-1 approach reported earlier. A cocktail consisting of ten cytochrome P450 (CYP)-selective probe substrates with known kinetic, metabolic and interaction properties in vivo was incubated in a pool of human liver microsomes, and metabolites of melatonin (CYP1A2), coumarin (CYP2A6), bupropion (CYP2B6), amodiaquine (CYP2C8) tolbutamide (CYP2C9), omeprazole (CYP2C19 and CYP3A4), dextromethorphan (CYP2D6), chlorzoxazone (CYP2E1), midazolam (CYP3A4) and testosterone (CYP3A4) were simultaneously analysed with a single LC/MSMS run. Altogether, 13 metabolites and internal standard phenacetin were analysed in multiple reaction mode. Polarity switching mode was utilized to acquire negative ion mode electrospray data for hydroxychlorzoxazone and positive ionization data for the rest of the analytes. Fast gradient elution was applied, giving total injection cycle of 8 min. The method was modified for two different LC/MSMS systems, and was validated for linear range, detection limit, accuracy and precision for each metabolite. In addition, cocktail inhibition system was further tested using monoclonal anti-CYP antibodies as inhibitors for each probe reaction.     

Two-dimensional capillary gas chromatography without intermediate trapping. Electron capture detector quantitation of an amino alcohol (KABI 2128) in serum after trifluoroacetylation

A two- dimensional gas chromatograph based on the Deans switching principle is described. The unit comprises two separate ovens, each containing a fused silica capillary column. The columns are joined in a specially designed manifold permitting heart cuts to be performed without significant decrease in efficiency. The switching speed and the retention time stability of the system made it possible to perform heart cuts of only a few seconds' duration. The system has been used under isothermal conditions for the determination of an amino alcohol (KABI 2128) in the low ng/ml range after trifluoroacetylation and with electron capture detection. A much shorter clean-up procedure could be used in combination with the two-dimensional gas chromatograph as compared to a method using a single glass capillary column.