Dibenzomethanopentacene-Based Polymers of Intrinsic Microporosity for Use in Gas-Separation Membranes

Dibenzomethanopentacene (DBMP) is shown to be a useful structural component for making Polymers of Intrinsic Microporosity (PIMs) with promise for making efficient membranes for gas separations. DBMP-based monomers for PIMs are readily prepared using a Diels–Alder reaction between 2,3-dimethoxyanthracene and norbornadiene as the key synthetic step. Compared to date for the archetypal PIM-1, the incorporation of DBMP simultaneously enhances both gas permeability and the ideal selectivity for one gas over another. Hence, both ideal and mixed gas permeability data for DBMP-rich co-polymers and an amidoxime modified PIM are close to the current Robeson upper bounds, which define the state-of-the-art for the trade-off between permeability and selectivity, for several important gas pairs. Furthermore, long-term studies (over ≈3 years) reveal that the reduction in gas permeabilities on ageing is less for DBMP-containing PIMs relative to that for other high performing PIMs, which is an attractive property for the fabrication of membranes for efficient gas separations.     

Concentrations of 239,240Pu and 241Am of marine products in coastal waters of Ibaraki

More than 200 samples of marine products have been collected and analyzed for plutonium and almost 100 samples for americium around Hitachi, Tokai and Oarai in the pacific coast of Ibaraki prefecture. The data have shown that the concentration factor (CF) values for plutonium were 330 for bivalve, 770 for abalone (muscle) and 610 for brown algae. For americium, the CF was calculated as 2400 for bivalve, 1000 for abalone (muscle) and 420 for brown algae.     

Determination of fumonisins B1 and B2 in corn and corn flakes by liquid chromatography with immunoaffinity column cleanup: collaborative study.

A liquid chromatographic (LC) method for the determination of fumonisins B1 (FB1) and B2 (FB2) in corn and corn flakes was collaboratively studied by 23 laboratories, which analyzed 5 blind duplicate pairs of each matrix to establish the accuracy, repeatability, and reproducibility characteristics of the method. Fumonisin levels in the corn ranged from <0.05 (blank) to 1.41 microg/g for FB1 and from <0.05 to 0.56 microg/g for FB2, whereas in the corn flakes they ranged from <0.05 to 1.05 microg/g for FB1 and from <0.05 to 0.46 microg/g for FB2. The method involved double extraction with acetonitrile-methanol-water (25 + 25 + 50), cleanup through an immunoaffinity column, and LC determination of the fumonisins after derivatization with o-phthaldialdehyde. Relative standard deviations for the within-laboratory repeatability (RSDr) of the corn analyses ranged from 19 to 24% for FB1 and from 19 to 27% for FB2; for the corn flakes analyses, RSDr ranged from 9 to 21 % for FB1 and from 8 to 22% for FB2. Relative standard deviations for the between-laboratories reproducibility (RSDR) of the corn analyses ranged from 22 to 28% for FB1 and from 22 to 30% for the FB2; for corn flakes analyses, RSDR ranged from 27 to 32% for FB1 and from 26 to 35% for FB2. Mean recoveries of FB1 and FB2 from corn spiked with FB1 at 0.80 microg/g and with FB2 at 0.40 microg/g were 76 and 72%, respectively; for corn flakes spiked at the same levels recoveries were 110 and 97% for FB1 and FB2, respectively. HORRAT ratios for the analyses of corn ranged from 1.44 to 1.53 for FB1 and from 0.96 to 1.48 for FB2, whereas for corn flakes they ranged from 1.60 to 1.82 for FB1 and from 1.39 to 1.68 for FB2.     

Quantitative determination of aflatoxin B1-oxime by column liquid chromatography with ultraviolet detection.

Liquid chromatography was used for the quantification of aflatoxin B1-oxime (AFB1-oxime). The yield of AFB1-oxime in the reaction mixture was 89%, while after purification on silica gel it was 72%. LC analysis of the reaction mixture after silica gel fractionation revealed a retention time of 0.84 min for AFB1-oxime, 8.42 min for AFB1, 1.21 min for unknown 1 and 1.61 min for unknown 2. UV-visible analysis of the reaction mixture after silica gel fractionation showed a lambda(max) of 269 and 361 nm for AFB1-oxime, 263 and 360 nm for AFB1, 273 nm for unknown 1 and 275 nm for unknown 2. Excitation and emission wavelengths were found to be 269 and 368/438 nm for AFB1-oxime, 359/424 nm for AFB1, 270 and 367/450 nm for unknown 1 and 273 and 416/447 nm for unknown 2. The method may find versatile application in monitoring reactions for the preparation of oximes of various analytes for the synthesis of their immunogens.     

A pilot study for the preparation of a new Reference Material based on antarctic krill

The preparation of new Certified Reference Materials (CRMs) of antarctic matrices forms the backbone of an ongoing project in the framework of the Italian National Program for Antarctic Research. The first CRM of this kind (MURST-ISS-A1 Antarctic Marine Sediment) is already available. The second phase focuses on the certification of antarctic krill, a small shrimp extremely abundant in the Southern Ocean. The total mass of krill available for this purpose is approximately 44 kg and results from the combination of three different catches (Ross Sea, Marguerite Bay and Livingston Island, respectively). The quantification of the following elements in the raw mass appears to be affordable by current analytical techniques, values being in the range of (in μg/g) 0.11–0.30 for As, 0.03–0.12 for Cd, 0.06–0.23 for Cr, 6.1–21 for Cu, 5.7–7.6 for Fe, 0.005–0.008 for Hg, 0.7–1.2 for Mn, 0.013– 0.077 for Ni, 0.04–0.57 for Pb and 12–16 for Zn. On the other hand, the average values ascertained in freeze-dried krill are as a rule one order of magnitude higher, i.e., (in μg/g), 3.2 for As, 0.6 for Cd, 1.8 for Cr, 75 for Cu, 61 for Fe, 0.025 for Hg, 4.6 for Mn, 0.7 for Ni, 2.1 for Pb and 81 for Zn. Information on the pretreatment of krill and details on the planned certification campaign are also given. Received: 10 June 1997 / Revised: 24 September 1997 / Accepted: 28 September 1997     

X-ray fluorescence analysis of rare earth elements in rocks using low dilution glass beads.

Major and trace elements (Na, Mg, Al, Si, P, K, Ca, Ti, Mn, Fe, Rb, Sr, Y, Zr, La, Ce, Pr, Nd, Sm, Gd, Dy, Th and U) in igneous rocks were assayed with fused lithium borate glass beads using X-ray fluorescence spectrometry. Low dilution glass beads, which had a 1:1 sample-to-flux ratio, were prepared for determination of rare earth elements. Complete vitrification of 1:1 mixture required heating twice at 1200 degrees C with agitation. Extra pure reagents containing determinants were used for calibrating standards instead of the rock standard. The calibration curves of the 23 elements showed good linearity. Furthermore, the lower limits of detection corresponding to three times the standard deviation for blank measurements were 26 mass ppm for Na2O, 6.7 for MgO, 4.5 for Al2O3, 4.5 for SiO2, 18 for P2O5, 1.1 for K2O, 4.0 for CaO, 3.9 for TiO2, 1.6 for MnO, 0.8 for Fe2O3, 0.5 for Rb, 0.2 for Sr, 0.4 for Y, 0.5 for Zr, 3.3 for La, 6.5 for Ce, 2.7 for Pr, 2.1 for Nd, 1.7 for Sm, 0.7 for Gd, 2.7 for Dy, 0.5 for Th, and 0.6 for U. Using the present method, we determined the contents of these 23 elements in four rhyolitic and granitic rocks from Japan.     

Method validation for determination of 13 elements in honey samples by ICP-MS

A method for simultaneous ICP-MS determination of 13 elements in three types of honey from Poland is described. The method was validated, and the uncertainty budget was set up. The results obtained for the relative expanded uncertainties U _rel (k = 2) were 15.1% for Al, 18.6% for B, 18.8% for Ba, 7.9% for Ca, 24.4% for Cd, 7.24% for Cu, 7.9% for K, 4.8% for Mg, 8.3% for Mn, 12.7% for Na, 14.9% for Ni, 12.5% for Pb and 13.4% for Zn. Traceability of the measurement results was established based on the use of the corn flour CRM INCT-CF-3 and the apple leaves CRM SRM 1515 and by analyzing spiked samples. Recovery rates between 94% (Zn) and 107% (Na) were found. The detection limits of all elements studied showed the suitability of the procedure for routine analyses. Summarizing it can be concluded that the described analytical procedures to measure the mass fractions of 13 elements in honey samples with established traceability and evaluated uncertainty allow to obtain reliable and internationally comparable results.     

A.C. Voltammetry at large amplitudes: A simplified theoretical approach

A theoretical exposition has been given for the output signal of a.c. voltammetry, that accounts for the presence of six harmonics. It turned out that for fast redox systems and a linear diffusion pattern a simple hyperbolic function could be obtained for the fundamental harmonic valid for high values of the superimposed a.c. voltage. This function can be developed to a series, which resembles for intermediate values of the amplitude the one already given by Smith; for small values of the amplitude the generally accepted expression for a.c. voltammetry is obtained.     

电感耦合等离子体质谱法快速测定苦荞茶中铜、铅、镉、钴、镍

建立了用硝酸-高氯酸消解样品,电感耦合等离子体质谱法(ICP-MS)测定苦荞茶中铜、铅、镉、钴、镍的方法.方法具有灵敏度高、检出限低、精密度好、基体干扰少、准确可靠、快捷、简便的特点.各元素方法检出限(3SD,μg/L)分别为:铜0.009、铅0.023、镉0.015、钴0.022、镍0.035;方法精密度(RSD,n=12)分别为:铜2.5%～3.0%、铅2.1%～2.3%、镉3.0%～3.8%、钴2.5%～2.6%、镍1.5%～1.9%;各元素加标回收率分别为:铜95.0%～105.0%、铅95.0%～105.0%、镉98.0%～105.0%、钴95.0%～105.0%、镍95.0%～105.0%.在线用铑作为内标95.0%～105.0%.方法经国家一级标准物质验证,测定值与标准值吻合.应用于实际样品测定,结果满意.     

Pharmacokinetic applications of capillary electrophoresis

This review briefly discusses the use of capillary electrophoretic (CE) methods for the investigations of different aspects of pharmacokinetics. In most investigations, CE was the method of choice because of its unique features, including high resolving power for chiral or metabolite separation, small sample volume for pediatric pharmacokinetics or for cell-based investigations, in situ microdialysis sampling for rapid eliminations, low UV wavelength detection for nonderivatized analytes, fast and simplified sample processing for existing methods that require tedious sample preparation, or as a second method for verifications. Moreover, instrumental aspects of CE-based assays for pharmacokinetic studies, such as different modes of CE methods for analyzing biological samples, sample stacking for increasing detection sensitivity, and coupling techniques with microdialysis and mass spectrometry, are also discussed in this review. Furthermore, the advantages and limitations of CE methods as well as the future outlook for pharmacokinetic studies are summarized.     

Theoretical analysis of resonant raman scattering: Simulations of lineshapes and excitation profiles

The steady-state response of a three-level system in the presence of a strong laser field is described with the density operator formalism, in order to derive an analytical expression for the intensity of resonance Raman scattering. The Liouville equation for the density operator is written in quantum form for both the molecular system and the radiation field, making use of the dipole and rotating-wave approximations for the matter-radiation interaction, and of the Markov approximation for the molecular decays. The equation is solved exactly for the laser field, and in perturbative way for the generated field. The results account for power broadening of the generated line. Rabi intensity-dip of the generated signal, and for the excitation profiles in the Franck-Condom approximation.     

Optimization of enzymatic biochemical logic for noise reduction and scalability: how many biocomputing gates can be interconnected in a circuit?

We report an experimental evaluation of the "input-output surface" for a biochemical AND gate. The obtained data are modeled within the rate-equation approach, with the aim to map out the gate function and cast it in the language of logic variables appropriate for analysis of Boolean logic for scalability. In order to minimize "analog" noise, we consider a theoretical approach for determining an optimal set for the process parameters to minimize "analog" noise amplification for gate concatenation. We establish that under optimized conditions, presently studied biochemical gates can be concatenated for up to order 10 processing steps. Beyond that, new paradigms for avoiding noise buildup will have to be developed. We offer a general discussion of the ideas and possible future challenges for both experimental and theoretical research for advancing scalable biochemical computing.     

Post-column oxidative derivatization for the liquid chromatographic determination of phenothiazines

A first post-column chemical derivatization method for the liquid chromatographic determination of phenothiazines is presented. Peroxyacetic acid is introduced as a derivatizing agent for phenothiazines, yielding the colored radical cations or fluorescent sulfoxides, depending on reaction conditions. Both reaction products were successfully employed for the detection of the phenothiazines after their liquid chromatographic separation. The fluorescence spectroscopic detection of the sulfoxides proved to be the more robust and sensitive method. Limits of detection ranged from 4 nM for triflupromazine and trimeprazine to 300 nM for phenothiazine for the fluorescence spectroscopic detection of the sulfoxide and from 0.3 μM for phenothiazine and triflupromazine to 2 μM for trifluperazine for the UV–Vis spectroscopic detection of the radical cation. The calibration functions for the fluorimetric sulfoxide determination ranged from two to more than three decades, starting at the limit of quantification.     

Probing the electronic structure and property of neutral and charged arsenic clusters (As(n)(+1,0,-1), n≤8) using Gaussian-3 theory

The structures and energies of As(n) (n = 2-8) neutrals, anions, and cations have been systematically investigated by means of the G3 schemes. The electron affinities, ionization potentials, binding energies, and several dissociation energies have been calculated and compared with limited experimental values. The results revealed that the potential surfaces of neutral As(n) clusters are very shallow, and two types of structural patterns compete with each other for the ground-state structure of As(n) with n ≥ 6. One type is derived from the benzvalene form of As(6), and another is derived from the trigonal prism of As(6). The previous photoelectron spectrum (taken from J. Chem. Phys. 1998 , 109 , 10727 ) for As(3) has been reassigned in light of the G3 results. The experimental electron affinities of As(3) were measured to be 1.81 eV, not 1.45 eV. We inferred from the conclusion of G3 and density functional theory that the experimental electron affinities of 1.7 and 3.51 eV for As(5) are unreliable. The reliable electron affinities were predicted to be 0.83 eV for As(2), 1.80 eV for As(3), 0.54 eV for As(4), 3.01 eV for As(5), 2.08 eV for As(6), 2.93 eV for As(7), and 2.02 eV for As(8). The G3 ionization potentials were calculated to be 9.87 eV for As(2), 7.33 eV for As(3), 8.65 eV for As(4), 6.68 eV for As(5), 7.97 eV for As(6), 6.58 eV for As(7), and 7.65 eV for As(8). The binding energies per atom were evaluated to be 1.99 eV for As(2), 2.01 eV for As(3), 2.61 eV for As(4), 2.39 eV for As(5), 2.51 eV for As(6), 2.55 eV for As(7), and 2.67 eV for As(8). These theoretical values of As(2), As(3), and As(4) are in excellent agreement with those of experimental results. Several dissociation energies were carried out to examine relative stabilities. This characterized the even-numbered clusters as more stable than the odd-numbered species.     

Electrokinetic phenomena at grafted polyelectrolyte layers

During the last decades the electrokinetic theory of Smoluchowski (Z. Phys. Chem. 92 (1918) 129) was extended to be applicable for soft surfaces (grafted polyelectrolyte layers (PL), biological and artificial membranes, etc.) by either using the Debye approximation or numerical solutions. In the theory of Ohshima (Colloids Surf. A 103 (1995) 249) the nonlinearized Poisson-Boltzmann (PB) equation for thick and uniform PL is solved analytically and a general hydrodynamic equation is derived in an integral form. These advantages in the theory of Ohshima provided a base for the further development of a generalized electrokinetic theory for soft surfaces. In his theory the final equation for the electroosmotic (electrophoretic) velocity is specified for the case of the complete dissociation of ionic sites within PL. Accordingly, the equation may be used only if the difference between pK and pH is very large. However, it turned out that an analytical solution of the nonlinearized PB equation for thick PL is possible for any degree of dissociation. This was achieved using the approximation of excluded coions if the absolute value of the reduced Donnan potential is larger than 2 and due to the simplification in the case of weak dissociation, when the absolute value of the reduced Donnan potential is less than 2. Combining this generalized double layer (DL) theory for PL and the theory of Ohshima enables to obtain an analytical equation for electroosmosis for the general case of any degree of dissociation. This equation creates for the first time a theoretical base for the interpretation of electrokinetic fingerprinting (EF) for the characterization of soft surfaces.     

Michaelis-Menten speeds up tau-leaping under a wide range of conditions

This paper examines the benefits of Michaelis-Menten model reduction techniques in stochastic tau-leaping simulations. Results show that although the conditions for the validity of the reductions for tau-leaping remain the same as those for the stochastic simulation algorithm (SSA), the reductions result in a substantial speed-up for tau-leaping under a different range of conditions than they do for SSA. The reason of this discrepancy is that the time steps for SSA and for tau-leaping are determined by different properties of system dynamics.     

On-chip screening method for cell migration genes based on a transfection microarray

Cell migration plays a major role in a variety of biological processes and a detailed understanding of associated mechanisms should lead to advances in the medical sciences, for example, in drug discovery for cancer therapy. However, the traditional methods used for analysis of cell migration cannot easily be scaled up for high-throughput screening. In this study, we have attempted to develop a novel simple method for high-throughput phenotypic screening for the identification of genes that are required for cell migration. As the appropriate cell line for the method, we found NBT-L2b cells that would be suitable for screening of migration-related genes in our method without influence by other cellular processes. Moreover, the idea for printing both the labeled fibronectin, for identification of the starting region of a cell, and the green fluorescent protein (GFP) expression vector, for identification of cells that had been transfected with siRNA and of the end point of migration, brings a rapid and efficient high-throughput screening procedure. Our new method will lead to an enhanced understanding of cell migration.     

Basic calculations about the limit of detection and its optimal determination

The limit of detection (LOD) is based strictly on an accepted probability for a false positive decision (type 1 error). For the needed standard deviation of the blank, a basic value for the calculation, three experimental different methods are described, which should be applicable in every case. Table values for simple but exact calculation, not only for single, but also for mean values, and with probabilities for the type 1 error of 1% and 5% are presented. Demands for an acceptable uncertainty of the LOD and for the validation of the result are specified.     

Traditional medicine in Syria: folk medicine in Aleppo governorate

The use of Traditional Arabic Medicine (TAM) for various diseases has been popular but scarcely studied in Syria. In the present study, we carried out ethnobotanical and ethnopharmacological research on the plants traditionally used to cure various diseases in northern Syria. The information was collected from the city and villages of the Aleppo governorate "Mohaafazah" in the north of Syria, collecting data directly on the basis of a detailed survey of inhabitants and herbalists. In this survey, we found that hundreds of plant species are still in use in TAM for the treatment of various diseases. We selected the most common 100 species, used in the treatment of more than 25 diseases. Among these plants, 53 are used for treating gastrointestinal disorders, 38 for respiratory system diseases, including asthma, bronchitis and cough, 34 for skin diseases, 21 for diabetes, 17 for kidney and urinary disorders, 16 for cardiac disorders, 14 for infertility and sexual impotency, 13 for treating liver diseases, 13 for several types of cancer, 9 for enhancing breast milk excretion, 8 for weight loss, 5 for reducing cholesterol, and three for weight gain. Plants were collected and identified: scientific Latin names, local names, the used parts of the plant, the herbal preparations and the local medical uses are described. Scientific literature concerning the activity of the investigated species is also reported and discussed according to their traditional uses.     

顶空固相微萃取-气相色谱-质谱联用分析纺织品中挥发性有机物

建立了顶空固相微萃取（HSSPME）-气相色谱（GC）-质谱（MS）联用测定纺织品中甲苯、4-乙烯基环己烯、苯乙烯、萘和1-苯基环己烯5种挥发性有机物（VOCs）的分析方法。选择聚二甲基硅氧烷（PDMS）作为萃取涂层,优化了SPME的萃取条件,包括平衡时间、萃取时间、萃取温度、顶空体积、离子强度、搅拌速度、解吸温度和时间以及GC—MS仪器条件。对于甲苯、4-乙烯基环己烯、苯乙烯、萘和1-苯基环己烯方法线性范围分别为0．087～870、3．32～3320、2．28～2280、0．015～150和0．050～50．0ng／g;检出限分别为0．005、0．042、0．670、0．008和0．011ng／g。实际样品加标回收率在80．1％～122％之间,RSD在0．8％～8．6％之间。方法符合纺织品中痕量VOCs的快速分析要求。