Adsorption behavior and cross-linking of EHEC and HM-EHEC at hydrophilic and hydrophobic modified surfaces monitored by SPR and QCM-D

The adsorption behavior of ethyl(hydroxyethyl) cellulose EHEC and hydrophobically modified EHEC (HM-EHEC) at hydrophilic and hydrophobic surfaces has been studied using surface plasmon resonance (SPR) and quartz crystal microbalance with dissipation monitoring (QCM-D) methods. The adsorbed amounts measured with the different methods were different due to large amounts of water in the films. The slow adsorption process made it reasonable to assume a continuous polymer reconfiguration process at the surface. This was mostly seen for HM-EHEC at the hydrophobic surface, where a more flexible structure was adopted during the adsorption process. A cross-linking agent was seen to truly interpolymer cross-link EHEC at the hydrophilic surface and HM-EHEC at the hydrophobic surface. For EHEC at a hydrophobic surface and for HM-EHEC at a hydrophilic surface, the polymers adsorbed in an individually phase-separated manner, making an interpolymer cross-linking reaction unsuccessful.     

Individual and simultaneous determination of uric acid and ascorbic acid by flow injection analysis

Flow injection methods for the individual and simultaneous determination of ascorbic acid and uric acid are proposed. A spectrophotometer and a miniamperometric detector are connected in sequence. The calibration graphs for uric acid obtained by measuring its absorbance at 293 nm and its current at +0.6 V are linear up to at least 80 and 70 mug/ml, respectively, with an rsd (n = 10) of 1 % for both methods at mid-range concentrations. The calibration graph for ascorbic acid with amperometric detection is linear up to 80 mg/l. with an rsd (n = 10) of 0.8% at 30 mg/l. The simultaneous determination of uric acid and ascorbic acid is based on measurement of the absorbance of uric acid at 393 nm and amperometric determination of both analytes at +0.6 V. The average relative errors of the analysis of binary mixtures of uric acid and ascorbic acid are 2.2 and 4.2%, respectively.     

Fluid phase equilibria of binary and ternary mixtures of supercritical carbon dioxide with tetradecanoic acid and docosane up to 43 MPa and 393 K: cosolvency effect and miscibility windows

Isothermal pressure (p)-mass fraction (w) phase diagrams were measured for CO₂ + tetradecanoic acid at six temperatures from 328.2 K to 373.2 K and for CO₂ + docosane at four temperatures from 343.2 K to 393.2 K as well as isobaric temperature (T)-mass fraction (w) phase diagrams for both systems at 34.5 MPa. In addition the isothermal and isobaric Gibbs phase prisms at 373.2 K and 34.5 MPa respectively were determined for the ternary system CO₂ + tetradecanoic acid + docosane, and and isobaric miscibility window was found between 333 K and 385 K at 34.5 MPa.     

Surface charge and zeta-potential of metabolically active and dead cyanobacteria

Zeta potential and acid-base titrations of active, inactivated, and dead Planktothrix sp. and Synechococcus sp. cyanobacteria were performed to determine the degree to which cell surface electric potential and proton/hydroxyl adsorption are controlled by metabolism or cell membrane structure. Surface OH(-) excess from potentiometric data, showed differences in surface charge between active and dead cyanobacteria from pH 3 to 10. Average zero salt effect pH (pH(pzse)) of 5.8+/-0.1 and 6.3+/-0.1 were obtained for active Planktothrix sp. and Synechococcus sp., respectively. Similarly for dead cyanobacteria pH(pzse) values of 5.8+/-0.1 and 4.6+/-0.1 were obtained. Zeta potentials of active Planktothrix sp. and Synechococcus sp. were positive at alkaline conditions, with a maximum of +13.7+/-1.5 mV at a pH of 9.0+/-0.1 for both species. This positive potential diminished in the presence of 1 mM HCO(-)(3). The zeta potential of Planktothrix sp. and Synechococcus sp. cells was negative at alkaline pH following their exposure to NaN(3), a metabolic inhibitor. The zeta potential of dead cyanobacteria was negative for Planktothrix sp., from pH 2.5 to 10.5, at -30 to -20 mV. Dead Synechococcus sp. exposed to a pH 2.5 solution recorded negative potentials to a minimum of -30 mV at pH 8, but positive potentials were found at higher pH reaching a maximum of +10 mV at pH 9.1. Zeta potentials for dead, but non-acidified Synechococcus sp. remained negative at -30 mV from an initial pH of 5.6 to 10.5, reflecting differences in cell wall structure between these species. These results indicate that Planktothrix sp. and Synechococcus sp. may metabolically control their surface charge to electrostatically attract bicarbonate anions at alkaline pH, required for photosynthesis.     

Structure of dihydrochalcones and related derivatives and their scavenging and antioxidant activity against oxygen and nitrogen radical species

Quantum mechanical calculations at B3LYP/6-31G** level of theory were employed to obtain energy (E), ionization potential (IP), bond dissociation enthalpy (O-H BDE) and stabilization energies (DE(iso)) in order to infer the scavenging activity of dihydrochalcones (DHC) and structurally related compounds. Spin density calculations were also performed for the proposed antioxidant activity mechanism of 2,4,6-trihydroxyacetophenone (2,4,6-THA). The unpaired electron formed by the hydrogen abstraction from the phenolic hydroxyl group of 2,4,6-THA is localized on the phenolic oxygen at 2, 6, and 4 positions, the C? and C? carbon atoms at ortho positions, and the C? carbon atom at para position. The lowest phenolic oxygen contribution corresponded to the highest scavenging activity value. It was found that antioxidant activity depends on the presence of a hydroxyl at the C2 and C4 positions and that there is a correlation between IP and O-H BDE and peroxynitrite scavenging activity and lipid peroxidation. These results identified the pharmacophore group for DHC.     

Extraction and spectrophotometric determination of ruthenium and osmium with thiobenzhydrazide

Ruthenium forms a pink complex with thiobenzhydrazide in hot 1.0-4.5M hydrochloric acid medium, which can be extracted with chloroform, and the extract shows maximal absorbance at 520 nm. The chloroform-extractable osmium-thiobenzhydrazide complex formed at pH 2.3-4.8 shows maximal absorption at 385 nm as well as at 480-490 nm. The colour of the extracts of both the complexes is stable for more than 24 hr and can be employed for the spectrophotometry of ruthenium and osmium in the presence of a considerable excess of diverse ions commonly associated with them. Ruthenium and osmium can be quantitatively separated from one another with thiobenzhydrazide.     

Pore accessibility of N2 and Ar in disordered nanoporous solids: theory and experiment

Recently (Nguyen and Bhatia, J. Phys. Chem. C 111:2212–2222, 2007) we have proposed a new algorithm utilising cluster analysis principles to determine pore network accessibility of a disordered material. The algorithm was applied to determine pore accessibility of the reconstructed molecular structure of a saccharose char, obtained in our recent work using hybrid reverse Monte Carlo simulation (Nguyen et al., Mol. Simul. 32:567–577, 2006). The method also identifies kinetically closed pores not accessed by adsorbate molecules at low temperature, when their low kinetic energy cannot overcome the potential barrier at the mouths of pores that can otherwise accommodate them. In the current work, the results are validated by transition state theory calculations for N₂ and Ar adsorption, showing that N₂ can equilibrate in narrow micropores at practical time scales at 300 K, but not at 77 K. Large differences between time scales for micropore entry and exit are predicted at low temperature for N₂, the latter being smaller by over three orders of magnitude. For N₂ at 77 K the time constant for pore entry exceeds 3 hr., while for exit it is 134 days. At 300 K these values are smaller than 1 μs, indicating good accessibility at this temperature. These results are verified by molecular dynamics simulations, which reveal that while N₂ molecules enter and leave all pores frequently at 300 K, entry and exit events for apparently inaccessible pores are absent at 77 K. For Ar at 87 K better accessibility is evident for the saccharose char compared to N₂ at 77 K. This finding is now experimentally shown in this work by comparison of pore size distributions obtained from experimental nitrogen adsorption isotherms of nitrogen and argon at 77 K and 87 K.     

Extraction and flame spectrophotometric determination of palladium and rhodium

Solvent extraction methods involving toluene, chloroform, 4-methyl-2-pentanone and pentyl acetate were studied for palladium and rhodium chelates. The palladiurn-salicylaldoxime chelate was extracted quantitatively into 4-methyl-2-pentanone at pH 3. The rhodium-diethyldithiocarbamate chelate was completely extracted into 4-methyl-2-pentanone at pH 8. The optimum combustion conditions for each of the organic extracts were then studied. The position of maximum emission intensity in the flame mantle was determined for each chelate and solvent system ; readings were taken at 363.5 mμ for palladium, and 369.2 mμ for rhodium. For palla-dium, when 4-methyl-2-pentanone was used instead of water as solvent, the emission intensity increased 21-fold. For rhodium, this kctone increased the sensitivity 27 times compared with water. A method is suggested for the separation and determination of palladium and rhodium in the same sample.     

Vinyl-Divinyl Copolymerization: Copolymerization and Network Formation from Styrene and p- and m-Divinylbenzene

The composition of copolymers of p- and m-divinylbenzene with styrene was determined by infrared spectrometry during copolymerization and compared with values calculated on the assumption that the polymerizing system is homogeneous, and the reactivities both of the vinyl groups in the monomers and of the pendant vinyl groups are independent of the extent of copolymerization. At lower conversions the content of all divinylbenzene units, and especially that of the pendant vinyl groups in the copolymer, is lower than calculated, whereas at higher conversions a fraction of pendant vinyl groups does not react. The conversions at the gel point do not depend on the concentration of divinylbenzene; at higher percentages of the divinyl monomer or dilution of the system they are higher for p- than for m-divinylbenzene, although p-divinylbenzene copolymers contain more divinylbenzene units at the same conversion. The deviations are explained by inhomogeneous copolymerization caused by locally different concentration of the vinyl     

Temperature-dependent transitions between normal and inverse equilibrium isotope effects for coordination and oxidative addition of C-H and H-H bonds to a transition metal center

The temperature dependence of the equilibrium isotope effects (EIEs) for coordination and oxidative addition of C-H and H-H bonds to the tungstenocene species {[H2Si(C5H4)2]W} has been determined with the aid of DFT (B3LYP) calculations. The EIE for coordination of CH4 and CD4 does not exhibit typical van't Hoff type behavior in which there is a monotonic variation of EIE with temperature; rather, the temperature dependence of the EIE exhibits a maximum, with inverse values (<1) at low temperature and normal values (>1) at high temperatures. The temperature dependence of the EIE for oxidative addition of CH4 and CD4 differs significantly from that for coordination, with the EIE being normal at all temperatures and approaching infinity at 0 K. In contrast to oxidative addition of methane which is normal at all temperatures, the EIE for oxidative addition of H2 and D2 exhibits a transition from inverse to normal upon raising the temperature. The existence of inverse EIEs in these systems at low temperatures is a result of the zero point energy changes for the products upon isotopic substitution being greater than those for the reactants (H2 or CH4).     

Determination of chlorprothixene and amitryptyline hydrochlorides by UV-derivative spectrophotometry and UV-solid-phase spectrophotometry

Two methods for spectrophotometric determination of chlorprothixene and amitryptyline hydrochlorides were proposed. One of them is based on spectral analysis of their derivative spectra. The measurement of the value at 316.0 nm of first derivative was used for construction of calibration graph for chlorprothixene. The Beer law was obeyed in the concentration range 0.5-50.0 microg ml(-1). The amplitude of the second derivative at 261.4 nm was used for determination of amitryptyline in the range 0.5-75.0 microg ml(-1). The second proposed method is utilized the use of solid sorbent for simultaneous preconcentration and assay of studied compounds. For this purpose the filtration gel Sephadex G100 was applied. The elaborated solid-phase spectrophotometric method was used for determination of chlorprothixene at 268.0 nm in the range 2.5-75.0 microg ml(-1) and amitryptyline at 238.0 nm in the concentration range 10.0-75.0 microg ml(-1).     

Dielectric relaxation of acetonitrile and propionitrile in benzene and carbon tetrachloride solutions

Dielectric permittivities and losses have been measured at wavelengths of 3 × 10⁴, 10.0, 3.23, 1.95, 1.25, and 0.40 cm at three temperatures 24, 40, and 60°C for benzene and carbon tetrachloride solutions of acetonitrile and propionitrile at a fixed concentration of 25 mole per cent. The far-infrared spectra in the range 10–150 cm⁻¹ of dilute solutions of both the nitriles have been investigated. A single relaxation time has been obtained for acetonitrile at each temperature whereas the dielectric data of propionitrile indicate the presence of multiple dispersion regions at microwave frequencies.     

The nuclear education and staffing challenge: Rebuilding critical skills in nuclear science and technology

Summary The U.S. Department of Energy supports 24 fellowships for students to attend six-week programs at either San Jose State University in California, or Brookhaven National Laboratory (BNL) in New York. The American Chemical Society through the Division of Nuclear Science and Technology operates both schools. The twelve students at the BNL program are enrolled in the State University of New York at Stony Brook (SUNYSB) and receive 3 college credits for the lecture course (CHE-361) and 3 additional credits for the laboratory course (CHE-362). In addition to lectures and laboratories, students tour various nuclear facilities offsite, at BNL, and at SUNYSB. Opportunities are given the students to interact with faculty and scientists within the profession through the Guest Lecture Program. Further details are discussed along with results of student surveys for the years 1999 through 2002.     

舰艇用LZN-2型高性能阻尼材料释放物定性定量分析与评价

舰艇舱室多为密闭环境,舱室内使用的非金属材料释放物是舱室污染的主要来源,因此对所选用的非金属材料必须进行常温释放物的定性定量分析。由于舰艇的特殊性,不仅要求非金属材料在常温条件下释放物的浓度符合舰艇舱室容许浓度,还要求材料在高温条件(火灾或爆炸)下不产生高毒性的物质。本文根据有关军用标准和规程对舰船用LZN-2型高性能阻尼材料常温释放物和高温热解物进行定性、定量分析,从而对其使用的安全性进行评估。     

BCN化合物的合成与表征

以石墨和六方氮化硼(h-BN)粉为原料,利用高能机械球磨和高温高压技术对BCN化合物的形成、结构及相变进行了研究.经120h球磨制备出BCN非晶体.在1400cm^-1附近,BCN非晶有一宽化的强红外吸收峰,在740和1630cm^-1附近观察到弱的红外吸收峰;在1330cm^-1附近观察到一宽化的Raman散射峰.BCN非晶中B_1s的结合能为191.9eV,C_1s的结合能为284.9和286.8eV,N_1s的结合能为398.3和400.5eV.将BCN非晶在4GPa和1473K下退火45min后转化为六方结构的BCN晶体,其晶格常数为a=0.2505nm,c=0.6664nm.其红外光谱特征吸收峰分别出现在1398,1103,1024,925和802cm^-1.Raman散射峰分别出现在1328,1358,1582和1614cm^-1.并对非晶BCN的形成和相转变机制进行了研究.     

Thermal Conductivity of Aqueous KI and KBr Solutions at High Temperatures and High Pressures

Experimental measurements are reported for the thermal conductivity of H₂O + KI and H₂O + KBr solutions using a parallel-plate apparatus. The measurements cover the temperature range from 293 to 473 K at pressures to 100 MPa for salt concentrations between 2.5 and 25 wt.%. The accuracy of the measurements was estimated to be ±1.6%. The data are compared with the experimental and correlation results of other investigators. For a given concentration, the thermal conductivity was found to vary linearly with pressure. The thermal conductivity at low concentrations below 25 wt.% shows a linear dependence on concentration for all isotherms. Each isobar at a given concentration shows a thermal conductivity maximum at temperatures between 405 and 417 K. The apparent molar thermal conductivity values at 293 K for aqueous KI and KBr are calculated from derived experimental data.     

Enantioselective Total Synthesis of Pseudopteroxazole and Ileabethoxazole

Enantioselective total syntheses of pseudopteroxazole ( 1 ) and ileabethoxazole ( 2 ) are presented. The two original stereocenters were constructed in excellent enantioselectivity and good diastereoselectivity through Carreira's asymmetric dual catalytic allylation, which shows potential for accessing diastereoisomers at C2 and C3 of 1 and 2 . Cationic cyclizations of 13 and 24 demonstrated an effective pathway for the construction of the opposite configurations at C1 in 1 and 2 . Additionally, an approach for the introduction of methyl at C4 is a feasible solution for structural modifications at C4 in 1 and 2 .     

Determination of iron and nickel in water and brine by solvent extraction and atomic absorption spectroscopy

A rapid, reliable and sensitive atomic absorption method for the determination of traces of iron and nickel in concentrated brine and in water has been developed. A simple, single extraction procedure is effective for iron in water at concentrations of 0.4–200 p.p.b. and in 25% (w/w) sodium chloride solutions at concentrations between 0.8 p.p.b. and 200 p.p.b. A similar procedure has been developed for nickel concentrations in the range 2–200 p.p.b. in water and 4–200 p.p.b. in brine. Extraction for 15 min with MIBK from a system buffered at pH 7 yields optimum results. The complexing agents are 0.2% solutions of 8-hydroxyquinoline and dimethylglyoxime for iron and nickel, respectively.     

Spatial distribution of the temperature and the number densities of electrons and atomic and ionic species in an inductively coupled RF argon plasma

A survey of the literature shows that the values found for the excitation parameters (temperature and electron number density) in an inductively coupled radio-frequency argon plasma at atmospheric pressure (ICP) depend on the plasma configuration and the measuring procedure. The present study proposes a novel method for measuring excitation temperatures that does not require a knowledge of transition probabilities. The experimental work concerns measurements of the spatial distributions of the temperature, the number densities of the electrons and various atomic and ionic species in a low-power (～0.5 kW) ICP for analytical purposes operated at either of two extreme carrier gas flow rates. Observations were made at three different heights above the induction coil. At high flow rate (～51/min) the familiar hollow configuration of the plasma is demonstrated by off-axis maxima for the temperature and the number densities of electrons and atomic species at all observation heights. At low flow rate (～1 l./min), the radial atom number density distributions are parabolically shaped and constricted to a smaller channel at all observation heights. The authors conclude from the results that both the plasma configurations are not in a state of complete local thermal equilibrium at observation heights used for analytical work (i.e., above the coil).     

Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes

Single-crystalline and uniform nanopolyhedra, nanorods, and nanocubes of cubic CeO2 were selectively prepared by a hydrothermal method at temperatures in the range of 100-180 degrees C under different NaOH concentrations, using Ce(NO3)3 as the cerium source. According to high-resolution transmission electron microscopy, they have different exposed crystal planes: {111} and {100} for polyhedra, {110} and {100} for rods, and {100} for cubes. During the synthesis, the formation of hexagonal Ce(OH)3 intermediate species and their transformation into CeO2 at elevated temperature, together with the base concentration, have been demonstrated as the key factors responsible for the shape evolution. Oxygen storage capacity (OSC) measurements at 400 degrees C revealed that the oxygen storage takes place both at the surface and in the bulk for the as-obtained CeO2 nanorods and nanocubes, but is restricted at the surface for the nanopolyhedra just like the bulk one, because the {100}/{110}-dominated surface structures are more reactive for CO oxidation than the {111}-dominated one. This result suggests that high OSC materials might be designed and obtained by shape-selective synthetic strategy.