Sample records for solid phase chemical

  1. Sensitive and fast mutation detection by solid phase chemical cleavage

    Hansen, Lise Lotte; Justesen, Just; Kruse, Torben A


    We have developed a solid phase chemical cleavage method (SpCCM) for screening large DNA fragments for mutations. All reactions can be carried out in microtiterwells from the first amplification of the patient (or test) DNA through the search for mutations. The reaction time is significantly...

  2. Ultrarapid mutation detection by multiplex, solid-phase chemical cleavage

    Rowley, G.; Saad, S.; Giannelli, F.; Green, P.M. [Guy`s & St. Thomas`s Hospitals, London (United Kingdom)


    The chemical cleavage of mismatches in heteroduplexes formed by probe and test DNA detects and locates any sequence change in long DNA segments ({approximately}1.8 kb), and its efficiency has been well tested in the analysis of both average (e.g., coagulation factor IX) and large, complex genes (e.g., coagulation factor VIII and dystrophin). In the latter application RT/PCR products allow the examination of all essential sequences of the gene in a minimum number of reactions. We use two specific chemical reactants (hydroxylamine and osmium tetroxide) and piperidine cleavage of the above procedure to develop a very fast mutation screening method. This is based on: (1) 5{prime} or internal fluorescent labeling to allow concurrent screening of three to four DNA fragments and (2) solid-phase chemistry to use a microliter format and reduce the time required for the procedure, from amplification of sequence to gel loading inclusive, to one person-working-day. We test the two variations of the method, one entailing 5{prime} labeling of probe DNA and the other uniform labeling of both probe and target DNA, by detecting 114 known hemophilia B (coagulation factor IX) mutations and by analyzing 129 new patients. Uniform labeling of both probe and target DNA prior to formation of the heteroduplexes leads to almost twofold redundancy in the ability to detect mutations. Alternatively, the latter procedure may offer very efficient though less than 100% screening for sequence changes with only hydroxylamine. The full method with two chemical reactions (hydroxylamine and osmium tetroxide) should allow one person to screen with virtually 100% accuracy more than 300 kb of sequence in three ABI 373 gels in 1 day. 26 refs., 7 figs., 1 tab.

  3. Effect of Microwave Radiation on Enzymatic and Chemical Peptide Bond Synthesis on Solid Phase

    Alessandra Basso


    Full Text Available Peptide bond synthesis was performed on PEGA beads under microwave radiations. Classical chemical coupling as well as thermolysin catalyzed synthesis was studied, and the effect of microwave radiations on reaction kinetics, beads' integrity, and enzyme activity was assessed. Results demonstrate that microwave radiations can be profitably exploited to improve reaction kinetics in solid phase peptide synthesis when both chemical and biocatalytic strategies are used.

  4. The synthesis and chemical durability of Nd-doped single-phase zirconolite solid solutions

    Cai, Xin; Teng, Yuancheng; Wu, Lang; Zhang, Kuibao; Huang, Yi


    Nd-doped single-phase zirconolite solid solutions was synthesized by solid-state reaction and following two steps of acid treatment. The phase composition, microstructure, and chemical durability of the zirconolite solid solutions were investigated. About 15 at% Nd was successfully stabilized into the zirconolite. The element mapping images of Ca, Zr, Nd and Ti show that all the elements are almost distributed homogeneously in the zirconolite waste forms. Product Consistency Test (PCT) was conducted under different pH values (pH = 5, 7 and 9) to evaluate the chemical durability of the Nd-doped zirconolite waste forms. The normalized element release rate of Ca (LRCa) in pH = 5 medium is higher than that of pH = 7 and 9, while the LRNd value remains almost unchanged under different pH values. The LRNd value is as low as 10-5 g m-2 d-1 after 42 days.

  5. Synthesis of silicon carbide nanowires by solid phase source chemical vapor deposition

    NI Jie; LI Zhengcao; ZHANG Zhengjun


    In this paper,we report a simple approach to synthesize silicon carbide(SiC)nanowires by solid phase source chemical vapor deposition(CVD) at relatively low temperatures.3C-SiC nanowires covered by an amorphous shell were obtained on a thin film which was first deposited on silicon substrates,and the nanowires are 20-80 am in diameter and several μm in length,with a growth direction of[200].The growth of the nanowires agrees well on vapor-liquid-solid (VLS)process and the film deposited on the substrates plays an important role in the formation of nanowires.

  6. Solid-phase reduction of Cr2O3 under chemical catalytic conditions

    Simonov, V. K.; Grishin, A. M.


    The kinetics of the solid-phase reduction of Cr2O3 with carbon under chemical catalytic action on the reacting system is studied. A significant intensification of the process in the presence of small amounts of potassium and sodium salts is established. The concepts of the catalyst action mechanism are considered and experimentally substantiated. Manufacture of iron-chromium master alloys with a restricted content of carbon can be organized at low temperatures, and they can be used in steelmaking.

  7. Challenges of infrared reflective spectroscopy of solid-phase explosives and chemicals on surfaces

    Phillips, Mark C.; Suter, Jonathan D.; Bernacki, Bruce E.; Johnson, Timothy J.


    Reliable active and passive hyperspectral imaging and detection of explosives and solid-phase chemical residue on surfaces remains a challenge and an active area of research and development. Both methods rely on reference libraries for material identification, but in many cases the reference spectra do not sufficiently resemble those instrumental signals scattered from real-world objects. We describe a physics-based model using the dispersive complex dielectric constant to explain what is often thought of as anomalous behavior of scattered or non-specular signatures encountered in active and passive sensing of explosives or chemicals on surfaces and show modeling and experimental results for RDX.

  8. The Use of Aryl Hydrazide Linkers for the Solid Phase Synthesis of Chemically Modified Peptides

    Woo, Y; Mitchell, A R; Camarero, J A


    Since Merrifield introduced the concept of solid phase synthesis in 1963 for the rapid preparation of peptides, a large variety of different supports and resin-linkers have been developed that improve the efficiency of peptide assembly and expand the myriad of synthetically feasible peptides. The aryl hydrazide is one of the most useful resin-linkers for the synthesis of chemically modified peptides. This linker is completely stable during Boc- and Fmoc-based solid phase synthesis and yet it can be cleaved under very mild oxidative conditions. The present article reviews the use of this valuable linker for the rapid and efficient synthesis of C-terminal modified peptides, head-to-tail cyclic peptides and lipidated peptides.

  9. Chemical Profile of Sotol Analyzed by Solid Phase Microextraction-Gas Chromatography

    Heliodoro de la Garza


    Full Text Available Problem statement: Sotol is a distilled spirit made from Dasylirion spp., a plant (called sotol that grows in the wilds of Northern Mexico and west Texas and New Mexico. This alcoholic beverage is produced in a similar process to the more common artisanal tequila and mescal. Sotol is also now beginning to achieve international recognition; however there are few commercial examples available, which are elaborated with poor quality and sensorial attributes un-defined. Approach: This is the first study which reported a chemical characterization of the main components of six commercial sotols, establishing the correlations among the samples and determining the similitude levels. Solid Phase Microextraction-Gas Chromatography (SPME-GC was used to analyze the chemical compounds present in the sotols (HaciendaTM, MestenoTM, Coyamito, Los Cuates, un-aged Alacran and rested Alacran. Results: From data obtained of the analysis of main components, a total of 25 chemical compounds were found to be related with six physicochemical characteristics of sotol, explaining 66.1% of the total variance. Rested Alacran and un-aged Alacran sotols were related by the high content of propionic acid, undecanoic acid, acetic acid, buthanol and furfural and by the low contents of phenyl ethanol, decanoic acid and ethyl dodecanoic acid. MestenoTM and Coyamito sotols presented an opposite chemical composition. HaciendaTM sotol contains high concentration of propanol, ethyl acetate, methyl butanol, hexadienal and low levels of ethyl decanoic acid and naftalene, chemical compounds do not found in Los cuates sotol. Conclusion: This study revealed for first time the chemical profile of the sotol demonstrating the necessity to improve the elaboration process of this alcoholic beverage to offer a Mexican product of high quality in the global market.

  10. Altering the interfacial activation mechanism of a lipase by solid-phase selective chemical modification.

    López-Gallego, Fernando; Abian, Olga; Guisán, Jose Manuel


    This study presents a combined protein immobilization, directed mutagenesis, and site-selective chemical modification approach, which was used to create a hyperactivated semisynthetic variant of BTL2. Various alkane chains were tethered at three different positions in order to mimic the lipase interfacial activation exogenously triggered by detergents. Optimum results were obtained when a dodecane chain was introduced at position 320 by solid-phase site-selective chemical modification. The resulting semisynthetic variant showed a 2.5-fold higher activity than the wild-type nonmodified variant in aqueous conditions. Remarkably, this is the maximum hyperactivation ever observed for BTL2 in the presence of detergents such as Triton X-100. We present evidence to suggest that the endogenous dodecane chain hyperactivates the enzyme in a similar fashion as an exogenous detergent molecule. In this way, we also observe a faster irreversible enzyme inhibition and an altered detergent sensitivity profile promoted by the site-selective chemical modification. These findings are also supported by fluorescence studies, which reveal that the structural conformation changes of the semisynthetic variant are different to those of the wild type, an effect that is more pronounced in the presence of detergent. Finally, the optimal immobilized semisynthetic variant was successfully applied to the selective synthesis of oxiran-2-yl butyrate. Significantly, this biocatalyst is 12-fold more efficient than the immobilized wild-type enzyme, producing the S-enantiomer with higher enantiospecificity (ee = 92%).

  11. Understanding the solid phase chemical fractionation of uranium in soil and effect of ageing

    Rout, Sabyasachi, E-mail: [Health Physics Division, Bhabha Atomic Research Centre, Mumbai (India); Kumar, Ajay [Health Physics Division, Bhabha Atomic Research Centre, Mumbai (India); Ravi, P.M.; Tripathi, R.M. [Homi Bhabha National Institute Anushaktinagar, Mumbai (India)


    Highlights: • Apart of U(VI) converted to U(IV) during adsorption to soil. • Ageing leads to rearrangement of chemical fractionation of U in soil. • Organic matter and carbonate minerals responsible for Surface enrichment of U. • There occurs Occlusion of U-Fe-Oxides (Hydroxide) in to silica. - Abstract: The aim of the present work is to understand the solid phase chemical fractionation of Uranium (U) in soil and the mechanism involved. This study integrated batch experiments of U(VI) adsorption to soil, study of U in different soil fractions, ageing impact on fractionation of U and spectroscopic investigation of adsorbed U(VI) using X-ray Photoelectron Spectroscopy (XPS). For the study three soils, pedogenically different (S1: Igneous, S2: Sedimentary and S3: Metamorphic) were amended with U(VI) and chemical fractionation of U was studied by sequential extraction after an interval of one month and 12 months. It was found that there occurs a significant rearrangement of U in different fractions with ageing and no correlation was observed between the U content in different fractions and the adsorbents of respective fractions such as soil organic matter (SOM), Fe/Mn oxides (hydroxides) carbonates, soil cation exchange capacity (CEC). XPS study revealed that surface enrichment of U mainly governed by the carbonate minerals and SOM, whereas bulk concentration was controlled by the oxides (hydroxides) of Si and Al. Occlusion of U-Fe-oxides (hydroxides) on silica was identified as an important mechanism for bulk enrichment (Increase in residual fraction) and depletion of U concentration in reducible fraction.

  12. Layer-by-layer fabrication of chemical-bonded graphene coating for solid-phase microextraction.

    Zhang, Suling; Du, Zhuo; Li, Gongke


    A new fabrication strategy of the graphene-coated solid-phase microextraction (SPME) fiber is developed. Graphite oxide was first used as starting coating material that covalently bonded to the fused-silica substrate using 3-aminopropyltriethoxysilane (APTES) as cross-linking agent and subsequently deoxidized by hydrazine to give the graphene coating in situ. The chemical bonding between graphene and the silica fiber improve its chemical stability, and the obtained fiber was stable enough for more than 150 replicate extraction cycles. The graphene coating was wrinkled and folded, like the morphology of the rough tree bark. Its performance is tested by headspace (HS) SPME of polycyclic aromatic hydrocarbons (PAHs) followed by GC/MS analysis. The results showed that the graphene-coated fiber exhibited higher enrichment factors (EFs) from 2-fold for naphthalene to 17-fold for B(b)FL as compared to the commercial polydimethylsioxane (PDMS) fiber, and the EFs increased with the number of condensed rings of PAHs. The strong adsorption affinity was believed to be mostly due to the dominant role of π-π stacking interaction and hydrophobic effect, according to the results of selectivity study for a variety of organic compounds including PAHs, the aromatic compounds with different substituent groups, and some aliphatic hydrocarbons. For PAHs analysis, the graphene-coated fiber showed good precision (<11%), low detection limits (1.52-2.72 ng/L), and wide linearity (5-500 ng/L) under the optimized conditions. The repeatability of fiber-to-fiber was 4.0-10.8%. The method was applied to simultaneous analysis of eight PAHs with satisfactory recoveries, which were 84-102% for water samples and 72-95% for soil samples, respectively.

  13. Molecular perspectives on solid-state phase transformation and chemical reactivity of drugs: metoclopramide as an example.

    Lin, Shan-Yang


    Here, I provide an overview of the solid-state characteristics, phase transformations and chemical reactions of metoclopramide hydrochloride monohydrate (MCP HCl H2O). Three unique techniques, including thermoanalytical methods, one-step simultaneous differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) microspectroscopy, and hot-stage microscopic (HSM) imaging, have been applied to study the solid-state phase transitions of MCP HCl H2O in continuous dehydration, amorphization and recrystallization processes. I also review the effects of grinding or heating on ion-exchange reactions, milling, compression or colyophilization on Maillard reactions, and γ-ray irradiation or electron beams on radiolysis in the solid state. I also report the exposure of MCP HCl H2O in solution to light, irradiation, oxidants or π-acceptors. This review will serve as a useful keynote for the evolving realm of solid-state chemistry research.

  14. CRYOCHEM, Thermodynamic Model for Cryogenic Chemical Systems: Solid-Vapor and Solid-Liquid-Vapor Phase Equilibria Toward Applications on Titan and Pluto

    Tan, S. P.; Kargel, J. S.; Adidharma, H.; Marion, G. M.


    Until in-situ measurements can be made regularly on extraterrestrial bodies, thermodynamic models are the only tools to investigate the properties and behavior of chemical systems on those bodies. The resulting findings are often critical in describing physicochemical processes in the atmosphere, surface, and subsurface in planetary geochemistry and climate studies. The extremely cold conditions on Triton, Pluto and other Kuiper Belt Objects, and Titan introduce huge non-ideality that prevents conventional models from performing adequately. At such conditions, atmospheres as a whole—not components individually—are subject to phase equilibria with their equilibrium solid phases or liquid phases or both. A molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, the development of which is still in progress, was shown to reproduce the vertical composition profile of Titan's atmospheric methane measured by the Huygens probe (Tan et al., Icarus 2013, 222, 53). Recently, the model was also used to describe Titan's global circulation where the calculated composition of liquid in Ligeia Mare is consistent with the bathymetry and microwave absorption analysis of T91 Cassini fly-by data (Tan et al., 2014, submitted). Its capability to deal with equilibria involving solid phases has also been demonstrated (Tan et al., Fluid Phase Equilib. 2013, 360, 320). With all those previous works done, our attention is now shifting to the lower temperatures in Titan's tropopause and on Pluto's surface, where much technical development remains for CRYOCHEM to assure adequate performance at low temperatures. In these conditions, solid-vapor equilibrium (SVE) is the dominant phase behavior that determines the composition of the atmosphere and the existing ices. Another potential application is for the subsurface phase equilibrium, which also involves liquid, thus three-phase equilibrium: solid-liquid-vapor (SLV). This presentation will discuss the

  15. Mechano-chemical spinodal decomposition: A phenomenological theory of phase transformations in multi-component, crystalline solids

    Rudraraju, Shiva; Garikipati, Krishna


    We present a new phenomenological treatment of phase transformations in multi-component crystalline solids driven by free energy density functions that are non-convex in mechanical and chemical variables. We identify the mechano-chemical spinodal as the region in strain-composition space where the free energy density function is non-convex. Our treatment describes diffusional phase transformations that are accompanied by symmetry breaking structural changes of the crystal unit cell due to mechanical instabilities in the mechano-chemical spinodal. This approach is relevant to phase transformations wherein the structural order parameters can be expressed as linear combinations of strains relative to a high-symmetry reference crystal. Because the local strains in an inhomogeneous, transforming microstructure can be finite, the elasticity problem must account for geometric nonlinearity. Furthermore, for physical consistency and mathematical well-posedness, we regularize the free energy density functions by interf...

  16. Site-Targeted Interfacial Solid-Phase Chemistry: Surface Functionalization of Organic Monolayers via Chemical Transformations Locally Induced at the Boundary between Two Solids.

    Maoz, Rivka; Burshtain, Doron; Cohen, Hagai; Nelson, Peter; Berson, Jonathan; Yoffe, Alexander; Sagiv, Jacob


    Effective control of chemistry at interfaces is of fundamental importance for the advancement of methods of surface functionalization and patterning that are at the basis of many scientific and technological applications. A conceptually new type of interfacial chemical transformations has been discovered, confined to the contact surface between two solid materials, which may be induced by exposure to X-rays, electrons or UV light, or by the application of electrical bias. One of the reacting solids is a removable thin film coating that acts as a reagent/catalyst in the chemical modification of the solid surface on which it is applied. Given the diversity of thin film coatings that may be used as solid reagents/catalysts and the lateral confinement options provided by the use of irradiation masks, conductive AFM probes or stamps, and electron beams in such solid-phase reactions, this approach is suitable for precise targeting of different desired chemical modifications to predefined surface sites spanning the macro- to nanoscale.

  17. EPA Method 525.3 - Determination of Semivolatile Organic Chemicals in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass Spectrometry (GC/MS)

    Method 525.3 is an analytical method that uses solid phase extraction (SPE) and gas chromatography/mass spectrometry (GC/MS) for the identification and quantitation of 125 selected semi-volatile organic chemicals in drinking water.

  18. Unconditionally stable, second-order accurate schemes for solid state phase transformations driven by mechano-chemical spinodal decomposition

    Sagiyama, Koki; Garikipati, Krishna


    We consider solid state phase transformations that are caused by free energy densities with domains of non-convexity in strain-composition space. We refer to the non-convex domains as mechano-chemical spinodals. The non-convexity with respect to composition causes segregation into phases with different crystal structures. If, for one of these crystal structures, the free energy density is also non-convex with respect to strain, there is potential for the corresponding phase to further separate into multiple variants. For mathematical well-posedness the free energy description must be enhanced by interface terms that penalize gradients with respect to strain and composition. A system of PDEs results that couples the classical Cahn-Hilliard equation with those of gradient elasticity. Since the materials systems of interest display finite strains, the appropriate description is Toupin's theory of gradient elasticity at finite strains. The presence of strain and composition gradients in the free energy density le...

  19. The contact angle of wetting of the solid phase of soil before and after chemical modification

    Tyugai Zemfira


    chernozem (9.3 − 17,9 − 29.5º and ferrallitic soils (27.3 − 30.6 − 33,4 and 18.0 − 29.0 − 29.2 º. Relative hydrophobicity of the soil solid phase surface after treatment by Mehra and Jackson (1957 occurs in parallel to the carbon content reduction. Loss of carbon in the samples after the extraction of iron is related to the solubility of the hydrophilic components of humic substances. These results indicate that the main factor, which determines the wettability of soil solid phase, is the organic substance.

  20. Solid-phase synthesis and chemical space analysis of a 190-membered alkaloid/terpenoid-like library.

    Moura-Letts, Gustavo; Diblasi, Christine M; Bauer, Renato A; Tan, Derek S


    Alkaloid and terpenoid natural products display an extensive array of chemical frameworks and biological activities. However such scaffolds remain underrepresented in current screening collections and are, thus, attractive targets for the synthesis of natural product-based libraries that access underexploited regions of chemical space. Recently, we reported a systematic approach to the stereoselective synthesis of multiple alkaloid/terpenoid-like scaffolds using transition metal-mediated cycloaddition and cyclization reactions of enyne and diyne substrates assembled on a tert-butylsulfinamide lynchpin. We report herein the synthesis of a 190-membered library of alkaloid/terpenoid-like molecules using this synthetic approach. Translation to solid-phase synthesis was facilitated by the use of a tert-butyldiarylsilyl (TBDAS) linker that closely mimics the tert-butyldiphenysilyl protecting group used in the original solution-phase route development work. Unexpected differences in stereoselectivity and regioselectivity were observed in some reactions when carried out on solid support. Further, the sulfinamide moiety could be hydrolyzed or oxidized efficiently without compromising the TBDAS linker to provide additional amine and sulfonamide functionalities. Principal component analysis of the structural and physicochemical properties of these molecules confirmed that they access regions of chemical space that overlap with bona fide natural products and are distinct from areas addressed by conventional synthetic drugs and drug-like molecules. The influences of scaffolds and substituents were also evaluated, with both found to have significant impacts on location in chemical space and three-dimensional shape. Broad biological evaluation of this library will provide valuable insights into the abilities of natural product-based libraries to access similarly underexploited regions of biological space.

  1. Confirmatory chemical analyses and solid phase bioassays on sediment from the Columbia River Estuary at Tongue Point, Oregon

    Young, J.S.; Word, J.Q.; Apts, C.W.; Barrows, M.E.; Cullinan, V.I.; Kohn, N.P.


    The Department of Economic Development, Ports Division, of the state of Oregon plans to develop a former ship supply and storage site near Tongue Point, Oregon, for commercial shipping. The development would require dredging the adjacent waterway to the Columbia River 40-foot channel to admit commercials vessels. The Portland District of the US Army Corps of Engineers requested the Battelle/Marine Sciences Laboratory (MSL) to conduct confirmatory solid-phase bioassays that would provide technical data for an evaluation of the potential environmental impact of ocean disposal of the dredged material. These confirmatory studies provided chemical and biological information required by ocean dumping regulations to determine suitability of Tongue Point sediments for ocean disposal. Sediment core samples were collected from Cathlamet Bay at Tongue Point in the upper Columbia River estuary. Sediment surface grab samples were collected at reference/control sites offshore from the mouth of the Columbia River (Disposal Site F) and at West Beach, Whidbey Island, Washington. The Tongue Point sediments were mixed into two composited batches. The MSL conducted solid-phase bioassays with these composites and reference sediments on four species of organisms.

  2. Ion suppression in the determination of clenbuterol in urine by solid-phase extraction atmospheric pressure chemical ionisation ion-trap mass spectrometry

    van Hout, M.W.J.; Niederlander, H.A G; de Zeeuw, R.A.; de Jong, G.J.


    Ion suppression effects were observed during the determination of clenbuterol in urine with solid-phase extraction/multiple-stage ion-trap mass spectrometry (SPE/MS3), despite the use of atmospheric pressure chemical ionisation. During SPE, a polymeric stationary phase (polydivinylbenzene) was appli

  3. Iron oxide functionalized graphene nano-composite for dispersive solid phase extraction of chemical warfare agents from aqueous samples.

    Chinthakindi, Sridhar; Purohit, Ajay; Singh, Varoon; Tak, Vijay; Goud, D Raghavender; Dubey, D K; Pardasani, Deepak


    Present study deals with the preparation and evaluation of graphene based magnetic nano-composite for dispersive solid phase extraction of Chemical Weapons Convention (CWC) relevant chemicals from aqueous samples. Nano-composite, Fe3O4@SiO2-G was synthesized by covalently bonding silica coated Fe3O4 onto the graphene sheets. Nerve agents (NA), Sulfur mustard (SM) and their non-toxic environmental markers were the target analytes. Extraction parameters like amount of sorbent, extraction time and desorption conditions were optimized. Dispersion of 20 milligram of sorbent in 200mL of water sample for 20min. followed by methanol/chloroform extraction produced average to good recoveries (27-94%) of targeted analytes. Recoveries of real agents exhibited great dependency upon sample pH and ionic strength. Sarin produced maximum recovery under mild acidic conditions (56% at pH 5) while VX demanded alkaline media (83% at pH 9). Salts presence in the aqueous samples was found to be advantageous, raising the recoveries to as high as 94% for SM. Excellent limits of detection (LOD) for sulphur mustard and VX (0.11ngmL(-1) and 0.19ngmL(-1) respectively) proved the utility of the developed method for the off-site analysis of CWC relevant chemicals.

  4. Solid phase transformations II

    Čermák, J


    This topical volume includes ten invited papers that cover selected areas of the field of solid phase transformations. The first two contributions represent a burgeoning branch; that of the computer simulation of physical phenomena. The following three articles deal with the thermodynamics of phase transformations as a basic theory for describing the phenomenology of phase changes in matter. The next paper describes the interconnections between structural stability and the electronic structure of phases. Two further articles are devoted to displacive transformations; a field where there are ma

  5. Evaluation of alternative environmentally friendly matrix solid phase dispersion solid supports for the simultaneous extraction of 15 pesticides of different chemical classes from drinking water treatment sludge.

    Soares, Karina Lotz; Cerqueira, Maristela Barnes Rodrigues; Caldas, Sergiane Souza; Primel, Ednei Gilberto


    This study describes the development, optimization and validation of a method for the extraction of 15 pesticides of different chemical classes in drinking water treatment sludge (DWTS) by vortex-assisted Matrix Solid Phase Dispersion (MSPD) with determination by gas chromatography coupled to mass spectrometry. It focused on the application of alternative and different solid supports to the extraction step of the MSPD. The main parameters that influenced the extraction were studied in order to obtain better recovery responses. Recoveries ranged from 70 to 120% with RSD below 20% for all analytes. Limits of quantification (LOQ) of the method ranged from 5 to 500 μg kg(-1) whereas the analytical curves showed correlation coefficients above 0.997. The method under investigation used low volume of solvent (5 mL), low sample mass (1.5 g) and low mass of chitin (0.5 g), an environmentally friendly support. It has advantages, such as speed, simplicity and low cost material, over other methods. When the method was applied, 4 out of 15 pesticides were detected in the DWTS samples in concentrations below the LOQ. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Solid-phase microextraction

    Nilsson, Torben

    The objective of this study has been to develop new analytical methods using the rapid, simple and solvent-free extraction technique solid-phase microextraction (SPME) for the quantitative analysis of organic pollutants at trace level in drinking water and environmental samples. The dynamics...

  7. Solid phases of tenoxicam.

    Cantera, Rodrigo G; Leza, María G; Bachiller, Carmen M


    In this report we describe the preparation and characterization of four polymorphic forms of tenoxicam; they are, three 1:1 stoichiometric solvates with acetonitrile, dioxane, and N,N-dimethylformamide, and an amorphous phase obtained by recrystallization in various solvents. Polymorph IV and solvates with dioxane and N,N-dimethylformamide are reported for the first time in this paper. In addition, three solvates were crystallized in acetone, ethyl acetate, and isopropyl alcohol. These solid forms were characterized by X-ray powder diffraction, differential scanning calorimetry, infrared spectroscopy, thermogravimetry, optical microscopy, and elemental analysis. Solid-state properties, intrinsic dissolution rate, and dissolution kinetics from formulated tablets are also provided.

  8. Solid phase transformations

    Čermák, J


    This special-topic book, devoted to ""Solid Phase Transformations"" , covers a broad range of phenomena which are of importance in a number of technological processes. Most commercial alloys undergo thermal treatment after casting, with the aim of imparting desired compositions and/or optimal morphologies to the component phases. In spite of the fact that the topic has lain at the center of physical metallurgy for a long time, there are numerous aspects which are wide open to potential investigative breakthroughs. Materials with new structures also stimulate research in the field, as well as n

  9. Analysis of chemical warfare agents in organic liquid samples with magnetic dispersive solid phase extraction and gas chromatography mass spectrometry for verification of the chemical weapons convention.

    Singh, Varoon; Purohit, Ajay Kumar; Chinthakindi, Sridhar; Goud, Raghavender D; Tak, Vijay; Pardasani, Deepak; Shrivastava, Anchal Roy; Dubey, Devendra Kumar


    A simple, sensitive and low temperature sample preparation method is developed for detection and identification of Chemical Warfare Agents (CWAs) and scheduled esters in organic liquid using magnetic dispersive solid phase extraction (MDSPE) followed by gas chromatography-mass spectrometry analysis. The method utilizes Iron oxide@Poly(methacrylic acid-co-ethylene glycol dimethacrylate) resin (Fe2O3@Poly(MAA-co-EGDMA)) as sorbent. Variants of these sorbents were prepared by precipitation polymerization of methacrylic acid-co-ethylene glycol dimethacrylate (MAA-co-EGDMA) onto Fe2O3 nanoparticles. Fe2O3@poly(MAA-co-EGDMA) with 20% MAA showed highest recovery of analytes. Extractions were performed with magnetic microspheres by MDSPE. Parameters affecting the extraction efficiency were studied and optimized. Under the optimized conditions, method showed linearity in the range of 0.1-3.0μgmL(-1) (r(2)=0.9966-0.9987). The repeatability and reproducibility (relative standard deviations (RSDs) %) were in the range of 4.5-7.6% and 3.4-6.2% respectively for organophosphorous esters in dodecane. Limits of detection (S/N=3/1) and limit of quantification (S/N=10/1) were found to be in the range of 0.05-0.1μgmL(-1) and 0.1-0.12μgmL(-1) respectively in SIM mode for selected analytes. The method was successfully validated and applied to the extraction and identification of targeted analytes from three different organic liquids i.e. n-hexane, dodecane and silicon oil. Recoveries ranged from 58.7 to 97.3% and 53.8 to 95.5% at 3μgmL(-1) and 1μgmL(-1) spiking concentrations. Detection of diethyl methylphosphonate (DEMP) and O-Ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX) in samples provided by the Organization for Prohibition of Chemical Weapons Proficiency Test (OPCW-PT) proved the utility of the developed method for the off-site analysis of CWC relevant chemicals.

  10. Influence of Geometry on a High Surface Area-Solid Phase Microextraction Sampler for Chemical Vapor Collection


    Flow Microfiltration ." Journal of Membrane Science 102(1-3): 31-42. 62 Hook, G. L., C. Jackson Lepage, et al. (2004). "Dynamic solid phase...Xia 2001) In another experiment, 1cm x 1cm and 1cm x 2cm sheets of thin PDMS membrane , with surface areas ~20 and ~40 times greater than a 100 μm...PDMS coated SPME fiber. The membranes were attached to a thin, deactivated stainless steel rod, in a configuration similar to a flag on a flagpole

  11. Selective solid-phase extraction of artificial chemicals from milk samples using multiple-template surface molecularly imprinted polymers.

    Zhang, Jing; Ni, Yan-li; Wang, Ling-ling; Ma, Jin-qin; Zhang, Zhi-qi


    A novel multiple-template surface molecularly imprinted polymer (MTMIP) was synthesized using ofloxacin and 17β-estradiol as templates and modified monodispersed poly(glycidylmethacrylate-co-ethylene dimethacrylate) (PGMA/EDMA ) beads as the support material. Static adsorption, solid-phase extraction and high-performance liquid chromatography were performed to investigate the adsorption properties and selective recognition characteristics of the polymer templates and their structural analogs. The maximum binding capacities of ofloxacin and 17β-estradiol on the MTMIP were 9.0 and 6.6 mg/g, respectively. Compared with the corresponding nonimprinted polymer, the MTMIP exhibited a much higher adsorption performance and selectivity toward three quinolones and three estrogens, which are common drug residues in food. The MTMIP served as a simple and effective pretreatment method and could be successfully applied to the simultaneous analysis of multiple target components in complex samples. Furthermore, the MTMIP may find useful applications as a solid-phase absorbent in the simultaneous determination of trace quinolones and estrogens in milk samples, as the recoveries were in the range 77.6-98.0%.

  12. Chemical modulators of heat shock protein 70 (Hsp70) by sequential, microwave-accelerated reactions on solid phase.

    Wisén, Susanne; Androsavich, John; Evans, Christopher G; Chang, Lyra; Gestwicki, Jason E


    Molecular chaperones, such as Hsp70 and Hsp90, are responsible for a variety of protective, anti-apoptotic functions. While inhibitors of Hsp90, such as geldanamycin and its derivative 17-AAG, are well known and important anti-cancer leads, Hsp70 has received less attention. Interesting lead candidates for Hsp70 share a dihydropyrimidine core; however, the preferred display of pendant functionality is still not clear. Here, we take advantage of the versatility of peptides to explore the requirements for activity. An exploratory compound collection was assembled by performing a Biginelli cyclocondensation at the terminus of a resin-bound beta-peptide. Liberation from solid support yielded peptide-modified dihydropyrimidines and, within this series, we uncovered compounds that alter the ATPase activity of Hsp70 and its bacterial ortholog, DnaK. Moreover, we identified important contributions made by aromatic, hydrophobic groups. These chemical probes could be used to study the roles of this molecular chaperone in disease.

  13. Molecular Modeling of Solid Fluid Phase Behavior

    Peter A. Monson


    This report gives a summary of the achievements under DOE contract No. DOE/ER/14150 during the period September 1, 1990 to December 31, 2007. This project was concerned with the molecular modeling of solid-fluid equilibrium. The focus was on understanding how solid-fluid and solid-solid phase behavior are related to molecular structure, and the research program made a seminal contribution in this area. The project led to 34 journal articles, including a comprehensive review article published in Advances in Chemical Physics. The DOE funding supported the work of 5 Ph.D. students, 2 M.S. students and 5 postdoctoral researchers.

  14. Solid-Phase Random Glycosylation

    Agoston, K.; Kröger, Lars; Dekany, Gyula


    Two different approaches were employed to study solid phase random glycosylations to obtain oligosaccharide libraries. In approach I, Wang resin esters were attached to the acceptors structures. Following their glycosylation and resin cleavage, the peracetylated components of the oligosaccharide ...

  15. Characterizing the scent and chemical composition of Panthera leo marking fluid using solid-phase microextraction and multidimensional gas chromatography-mass spectrometry-olfactometry.

    Soso, Simone B; Koziel, Jacek A


    Lions (Panthera leo) use chemical signaling to indicate health, reproductive status, and territorial ownership. To date, no study has reported on both scent and composition of marking fluid (MF) from P. leo. The objectives of this study were to: 1) develop a novel method for simultaneous chemical and scent identification of lion MF in its totality (urine + MF), 2) identify characteristic odorants responsible for the overall scent of MF as perceived by human panelists, and 3) compare the existing library of known odorous compounds characterized as eliciting behaviors in animals in order to understand potential functionality in lion behavior. Solid-phase microextraction and simultaneous chemical-sensory analyses with multidimensional gas-chromatography-mass spectrometry-olfactometry improved separating, isolating, and identifying mixed (MF, urine) compounds versus solvent-based extraction and chemical analyses. 2,5-Dimethylpyrazine, 4-methylphenol, and 3-methylcyclopentanone were isolated and identified as the compounds responsible for the characteristic odor of lion MF. Twenty-eight volatile organic compounds (VOCs) emitted from MF were identified, adding a new list of compounds previously unidentified in lion urine. New chemicals were identified in nine compound groups: ketones, aldehydes, amines, alcohols, aromatics, sulfur-containing compounds, phenyls, phenols, and volatile fatty acids. Twenty-three VOCs are known semiochemicals that are implicated in attraction, reproduction, and alarm-signaling behaviors in other species.

  16. Solid-phase peptide synthesis

    Jensen, Knud Jørgen


    This chapter provides an introduction to and overview of peptide chemistry with a focus on solid-phase peptide synthesis. The background, the most common reagents, and some mechanisms are presented. This chapter also points to the different chapters and puts them into perspective.......This chapter provides an introduction to and overview of peptide chemistry with a focus on solid-phase peptide synthesis. The background, the most common reagents, and some mechanisms are presented. This chapter also points to the different chapters and puts them into perspective....

  17. Determination of acrylamide in food by solid-phase microextraction coupled to gas chromatography-positive chemical ionization tandem mass spectrometry.

    Lee, Maw-Rong; Chang, Li-Yo; Dou, Jianpeng


    A method has been developed to determine acrylamide in aqueous matrices by using direct immersion solid-phase microextraction (SPME) coupled to gas chromatography-positive chemical ionization tandem mass spectrometry (GC-PCI-MS-MS) in the selected reaction monitoring (SRM) mode. The optimized SPME experimental procedures to extract acrylamide in water solutions were: use of a carbowax/divinylbenzene (CW/DVB)-coated fiber at pH 7, extraction time of 20 min and analyte desorption at 210 degrees C for 3 min. A detection limit of 0.1 microg L(-1) was obtained. The linear range was 1-1000 microg L(-1). The relative standard deviation was 10.64% (n=7). The proposed analytical method was successfully used for the quantification of trace acrylamide in foodstuffs such as French fries (1.2 microg g(-1)) and potato crisps (2.2 microg g(-1)).

  18. Determining octanol-water partition coefficients for extremely hydrophobic chemicals by combining 'slow stirring' and solid phase micro extraction

    Jonker, Michiel T O


    Octanol-water partition coefficients (Kow ) are widely used in fate and effects modelling of chemicals. Still, high quality experimental Kow data are scarce, in particular for very hydrophobic chemicals. This hampers reliable assessments of several fate and effect parameters and the development and

  19. Determination of perfluorinated chemicals in food and drinking water using high-flow solid-phase extraction and ultra-high performance liquid chromatography/tandem mass spectrometry.

    Chang, Ying-Chia; Chen, Wen-Ling; Bai, Fang-Yu; Chen, Pau-Chung; Wang, Gen-Shuh; Chen, Chia-Yang


    For this study, we developed methods of determining ten perfluorinated chemicals in drinking water, milk, fish, beef, and pig liver using high-flow automated solid-phase extraction (SPE) and ultra-high performance liquid chromatography/tandem mass spectrometry. The analytes were separated on a core-shell Kinetex C18 column. The mobile phase was composed of methanol and 10-mM N-methylmorpholine. Milk was digested with 0.5 N potassium hydroxide in Milli-Q water, and was extracted with an Atlantic HLB disk to perform automated SPE at a flow rate ranged from 70 to 86 mL/min. Drinking water was directly extracted by the SPE. Solid food samples were digested in alkaline methanol and their supernatants were diluted and also processed by SPE. The disks were washed with 40% methanol/60% water and then eluted with 0.1% ammonium hydroxide in methanol. Suppression of signal intensity of most analytes by matrixes was lower than 50%; it was generally lower in fish and drinking water but higher in liver. Most quantitative biases and relative standard deviations were lower than 15%. The limits of detection for most analytes were sub-nanograms per liter for drinking water and sub-nanograms per gram for solid food samples. This method greatly shortened the time and labor needed for digestion, SPE, and liquid chromatography. This method has been applied to analyze 14 types of food samples. Perfluorooctanoic acid was found to be the highest among the analytes (median at 3.2-64 ng/g wet weight), followed by perfluorodecanoic acid (0.7-25 ng/g) and perfluorododecanoic acid (0.6-15 ng/g).

  20. SURFACE CHEMKIN-III: A Fortran package for analyzing heterogeneous chemical kinetics at a solid-surface - gas-phase interface

    Coltrin, M.E.; Kee, R.J.; Rupley, F.M.; Meeks, E.


    This document is the user`s manual for the SURFACE CHEMKIN-III package. Together with CHEMKIN-III, this software facilitates the formation, solution, and interpretation of problems involving elementary heterogeneous and gas-phase chemical kinetics in the presence of a solid surface. The package consists of two major software components: an Interpreter and a Surface Subroutine Library. The Interpreter is a program that reads a symbolic description of a user-specified chemical reaction mechanism. One output from the Interpreter is a data file that forms a link to the Surface Subroutine Library, which is a collection of about seventy modular Fortran subroutines that may be called from a user`s application code to return information on chemical production rates and thermodynamic properties. This version of SURFACE CHEMKIN-III includes many modifications to allow treatment of multi-fluid plasma systems, for example modeling the reactions of highly energetic ionic species with a surface. Optional rate expressions allow reaction rates to depend upon ion energy rather than a single thermodynamic temperature. In addition, subroutines treat temperature as an array, allowing an application code to define a different temperature for each species. This version of SURFACE CHEMKIN-III allows use of real (non-integer) stoichiometric coefficients; the reaction order with respect to species concentrations can also be specified independent of the reaction`s stoichiometric coefficients. Several different reaction mechanisms can be specified in the Interpreter input file through the new construct of multiple materials.

  1. Reaction diffusion and solid state chemical kinetics handbook

    Dybkov, V I


    This monograph deals with a physico-chemical approach to the problem of the solid-state growth of chemical compound layers and reaction-diffusion in binary heterogeneous systems formed by two solids; as well as a solid with a liquid or a gas. It is explained why the number of compound layers growing at the interface between the original phases is usually much lower than the number of chemical compounds in the phase diagram of a given binary system. For example, of the eight intermetallic compounds which exist in the aluminium-zirconium binary system, only ZrAl3 was found to grow as a separate

  2. Solid-phase synthesis and chemical space analysis of a 190-membered alkaloid/terpenoid-like library

    Moura-Letts, Gustavo; DiBlasi, Christine M.; Bauer, Renato A.; Tan, Derek S.


    Alkaloid and terpenoid natural products display an extensive array of chemical frameworks and biological activities. However such scaffolds remain underrepresented in current screening collections and are, thus, attractive targets for the synthesis of natural product-based libraries that access underexploited regions of chemical space. Recently, we reported a systematic approach to the stereoselective synthesis of multiple alkaloid/terpenoid-like scaffolds using transition metal-mediated cycl...



    The solid-phase synthesis of isoxazolines on 2-polystyrylsulfonamidoethanol resin isreported. 2-Polystyrylsuifonamidoethanol resin 1 was reacted with acryloyl chloride to afford2-polystyrylsulfonylamidoethyl acrylate resin 2, which was further reacted with brominatedaldoximes by [3+2] cycioaddition to give isoxazoline resin 4. Resin 4 was treated with aqueous 6mol/L HCI solution to obtain isoxazolines in good yield and purity.

  4. Multiple solid-phase microextraction

    Koster, EHM; de Jong, GJ


    Theoretical aspects of multiple solid-phase microextraction are described and the principle is illustrated with the extraction of lidocaine from aqueous solutions. With multiple extraction under non-equilibrium conditions considerably less time is required in order to obtain an extraction yield that

  5. Fractionation, solid-phase immobilization and chemical degradation of long pectin oligogalacturonides. Initial steps towards sequencing of oligosaccharides

    Guillaumie, Fanny; Justesen, Sune Frederik Lamdahl; Mutenda, K.E.


    at 40 or 60 degrees C, and the chemical degradation products released from the support were analyzed by ESIMS. In all cases, the original OGA was degraded into smaller oligomers of various sizes down to the monomer. This work illustrates some of the basic principles underlying a strategy ultimately...

  6. Fractionation, solid-phase immobilization and chemical degradation of long pectin oligogalacturonides. Initial steps towards sequencin of oligosaccharides

    Guillaumie, Fanny; Justesen, Sune F. L.; Mutenda, Kudzai E.


    at 40 or 60 degrees C, and the chemical degradation products released from the support were analyzed by ESIMS. In all cases, the original OGA was degraded into smaller oligomers of various sizes down to the monomer. This work illustrates some of the basic principles underlying a strategy ultimately...

  7. Fractionation, solid-phase immobilization and chemical degradation of long pectin oligogalacturonides. Initial steps towards sequencin of oligosaccharides

    Guillaumie, Fanny; Justesen, Sune F. L.; Mutenda, Kudzai E.


    This work presents the optimized separation of pectin oligomers, their analysis by matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS), their subsequent immobilization to supports, and our initial steps towards solid-support assisted sequencing. The ambient...... pressure strong anion-exchange resin Source 15Q combined with ammonium formate buffer (AF) was used for the separation of unsaturated and saturated pectic oligogalacturonides (OGAs) derived from enzymatic digestion of pectin. Routinely, multi-milligram quantities of defined sizes OGAs with DPs from 5 to 19...

  8. Silica chemically bonded N-propyl kriptofix 21 and 22 with immobilized palladium nanoparticles for solid phase extraction and preconcentration of some metal ions

    Ghaedi, Mehrorang, E-mail: [Chemistry Department, Yasouj University, Yasouj, 75914-353 (Iran, Islamic Republic of); Niknam, Khodabakhsh, E-mail: [Chemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr, 75169 (Iran, Islamic Republic of); Zamani, Saeed; Abasi Larki, Habib [Chemistry Department, Islamic Azad University, Omidiyeh Branch, Omidiyeh (Iran, Islamic Republic of); Roosta, Mostafa [Chemistry Department, Yasouj University, Yasouj, 75914-353 (Iran, Islamic Republic of); Soylak, Mustafa [Chemistry Department, University of Erciyes, 38039 Kayseri (Turkey)


    Silica gel chemically bonded N-propyl kriptofix 21 (SBNPK 21) and N-propyl kriptofix 22 (SBNPK 22) and subsequently immobilized with palladium nanoparticles (PNP-SBNPK 21 and PNP-SBNPK 22) to produce two new complexing lipophilic materials. Then these novel sorbents were applied for the enrichment of some metal ions and their subsequent determination by flame atomic absorption spectroscopy (FAAS). The influences of the variables including pH, amount of solid phase, sample flow rate, eluent conditions and sample volume on the metal ion recoveries were investigated. The detection limit of proposed method was in the interval 2.1–2.3 and 1.7–2.8 ng mL{sup −1} for PNP-SBNPK 21 and PNP-SBNPK 22 respectively, while the preconcentration factor was 80 for two sorbents. The relative standard deviations of recoveries were between 1.23–1.31 and 1.28–1.49 for PNP-SBNPK 21 and PNP-SBNPK 22 respectively. The method has high sorption-preconcentration efficiency even in the presence of various interfering ions. Due to the reasonable selectivity of proposed method, the relative standard deviation of recoveries of all understudied metal ions in some complicated matrices was less than 3.0%. Highlights: • Highly selective sorbents for solid phase extraction were synthesized. • The method has been successfully applied for the determination of trace metals ions. • Excellent properties of the sorbent have been illustrated in detail.


    SUNWeimin; LUOJuntao; 等


    The solid-phase synthesis of isoxazolines on 2-polystyrylsulfonamidoethanol resin is reported.2-Polystyrylsulfonamidoethanol resin 1 was reacted with acryloyl chloride to afford 2-polystyrylsulfonylamidoethyl acrylate resin 2,which was further reacted with brominated aldoximes by [3+2] cycloaddition to give isoxazoline resin 4.Resin 4 was treated with aqueous 6 mol/L HCl solution to obtain isoxazolines in good yield and purity.

  10. Solid phase synthesis of bifunctional antibodies.

    DeSilva, B S; Wilson, G S


    Bifunctional antibodies were prepared using the principle of solid-phase synthesis. The two Fab' fragments were chemically linked together via a bismaleimide crosslinking reagent. The F(ab')2 fragments from intact IgG were prepared using an immobilized pepsin column. Goat, mouse and human antibodies were digested completely within 4 h. The F(ab')2 fragments thus produced did not contain any IgG impurities. The Fab' fragments were produced by reducing the inter-heavy chain disulfide bonds using 2-mercaptoethylamine. The use of the solid-phase reactor in the preparation of the bifunctional antibodies eliminated many of the time-consuming separation steps between the fragmentation and conjugation steps. This procedure facilitates the automation of the bifunctional antibody preparation and the rapid optimization of reaction conditions.

  11. Solid phase syntheses of oligoureas

    Burgess, K.; Linthicum, D.S.; Russell, D.H.; Shin, H.; Shitangkoon, A.; Totani, R.; Zhang, A.J.; Ibarzo, J. [Texas A& M Univ., College Station, TX (United States)


    Isocyanates 7 were formed from monoprotected diamines 3 or 6, which in turn can be easily prepared from commercially available N-BOC- or N-FMOC-protected amino acid derivatives. Isocyanates 7, formed in situ, could be coupled directly to a solid support functionalized with amine groups or to amino acids anchored on resins using CH{sub 2}Cl{sub 2} as solvent and an 11 h coupling time at 25 {degree}C. Such couplings afforded peptidomimetics with an N-phthaloyl group at the N-terminus. The optimal conditions identified for removal of the N-phthaloyl group were to use 60% hydrazine in DMF for 1-3 h. Several sequences of amino acids coupled to ureas (`peptidic ureas`) and of sequential urea units (`oligoureas`) were prepared via solid phase syntheses and isolated by HPLC. Partition coefficients were measured for two of these peptidomimetics, and their water solubilities were found to be similar to the corresponding peptides. A small library of 160 analogues of the YGGFL-amide sequence was prepared via Houghten`s tea bag methodology. This library was tested for binding to the anti-{beta}-endorphin monoclonal antibody. Overall, this paper describes methodology for solid phase syntheses of oligourea derivatives with side chains corresponding to some of the protein amino acids. The chemistry involved is ideal for high-throughput syntheses and screening operations. 51 refs., 3 figs., 2 tabs.

  12. Solid Phase Chemical Synthesis and Structure - Activity Study of Brevinin - 2R and Analogues as Antimicrobial Peptides

    Hashem Yaghoubi


    Full Text Available Background: Brevinin-2R, as 25 amino acids peptide of the skin of Rana ridibunda frog, possesses potent antimicrobial and low hemolytic activity. It has an N-terminal hydrophilic region and a C-terminal loop that is delineated by an intra-disulfide bridge. In our study, Brevinin-2R and its diastereomer as well  as its  cyclic  analogue  were  synthesized  and  characterized  in  order  to investigate its structural features and biological implications.Methods: MIC determination is based on the recommended classical method of national comittee for labratory safety standard (NCLSS and standard by Hancock With some change on cationic peptides. In this study All bacterial strains were obtained from Industrial-Scientific Research center.Results: Both analogues showed lower antimicrobial activities compared to Brevinin-2R. In spite of Brevinin-2R peptide which shows low hemolytic activity, these analogues failed to show any hemolytic activity even at higherconcentrations (up to 400 µ g/ml. Based on proteolytic stability measurements,diastereomer and cyclic analogues displayed 90% and 60% residual antimicrobial activity, respectively, while antimicrobial activity of Brevinin-2R was 20%. The CD analysis revealed that amphipathic α-helical conformation of the synthesized peptides is involved in antimicrobial effects.Conclusion: CD studies and HPLC based measurement of retention time using a reverse phase column indicated that the Brevinin-2R can form an amphipathic loop  resulting  in  an  enhanced  hydrophobicity.  The  hemolytic  activity  ofBrevinin-2R and its analogues appeared to correlate with the retention time aswell as the α-helicity. Accordingly, it seems that the combination of incorporating of D-amino acids into lytic peptides and their cyclization may result in developing new antimicrobial peptides with improved properties for treating infectious diseases.

  13. Determination of atrazine and its major degradation products in soil pore water by solid-phase extraction, chemical derivatization, and gas chromatography/mass spectrometry

    Carter, D.S.


    This report describes a method for the determination of atrazine, desethylatrazine, deisopropylatrazine, didealkylatrazine, and hydroxyatrazine from soil pore waters by use of solid-phase extractionfollowed by chemical derivatization and gas chromatography/mass spectrometry. The analytes are isolated from the pore-water matrix byextraction onto a graphitized carbon-black cartridge. The cartridge is dried under vacuum, and adsorbed analytes are removed by elution with ethyl acetate followed by dichloromethane/methanol (7:3, volume/volume). Water is removed from the ethyl acetate fraction on an anhydrous sodium sulfate column. The combined fractions are solvent exchanged into acetonitrile, evaporated by use of a nitrogen stream, and derivatized by use of N- methyl-N-(tert-butyldimethylsilyl)- trifluoroacetamide. The derivatized extracts are analyzed by capillary-column gaschromatography/electron-impact mass spectrometry in the scan mode. Estimated method detection limits range from 0.03 to 0.07 micrograms per liter. The mean recoveries of all analytes and surrogates determined at 0.74 to 0.82 micrograms per liter in reagent water in soil pore water were 94 percent and 98 percent, respectively. The mean recoveries of all analytes and surrogates determined at 7.4 to 8.2 micrograms per liter in reagent water and in soil pore water were 96 percent and 97 percent,respectively. Recoveries were 90 percent or higher, regardless of analyte concentration or matrix composition, for all compounds excepthydroxyatrazine, whose recoveries were slightly lower (77 percent) at the low concentration.

  14. Magnetic porous carbon derived from Co-doped metal-organic frameworks for the magnetic solid-phase extraction of endocrine disrupting chemicals.

    Hao, Lin; Wei, Jiayi; Zheng, Ruixue; Wang, Chun; Wu, Qiuhua; Wang, Zhi


    Metal-organic frameworks-5 (MOF-5) was explored as a template to prepare porous carbon due to its high surface area, large pore volume, and permanent nanoscale porosity. Magnetic porous carbon, Co@MOF-5-C, was fabricated by the one-step direct carbonization of Co-doped MOF-5. After carbonization, the magnetic cobalt nanoparticles are well dispersed in the porous carbon matrix, and Co@MOF-5-C displays strong magnetism (with the saturation magnetization intensity of 70.17emu/g), high-specific surface area, and large pore volume. To evaluate its extraction performance, the Co@MOF-5-C was applied as an adsorbent for the magnetic solid-phase extraction of endocrine disrupting chemicals, followed by their analysis with high-performance liquid chromatography. The developed method exhibits a good linear response in the range of 0.5-100 ng/mL for pond water and 1.0-100 ng/mL for juice samples. The limits of detection (S/N = 3) for the analytes were in the range of 0.1-0.2 ng/mL. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Development of solid-phase microextraction followed by gas chromatography-mass spectrometry for rapid analysis of volatile organic chemicals in mainstream cigarette smoke.

    Ye, Qing


    In this work, a novel, simple and efficient method based on solid-phase microextraction (SPME) followed by gas chromatography-mass spectrometry (GC-MS) was developed to the analysis of volatile organic chemicals (VOCs) in mainstream cigarette smoke (MCS). Using a simple home-made smoking machine device, extraction and concentration of VOCs in MCS were performed by SPME fiber, and the VOCs adsorbed on fiber were desorbed, and analyzed by GC-MS. The extraction fiber types and the desorption conditions were studied, and the method precision was also investigated. After the investigation, the optimal fiber was divinylbenzene/carboxen/polydemethylsiloxane (DVB/CAR/PDMS), and the optimal desorption condition was 250 degrees C for 3 min. The method precision was from 2% to 11%. Finally, the proposed method was tested by its application of the analysis of VOCs in MCS from 10 brands of cigarettes and one reference cigarette. A total of 70 volatile compounds were identified by the proposed method. The experimental results showed that the proposed method was a simple, rapid, reliable, and solvent-free technique for the determination of VOCs in MCS.

  16. Silica chemically bonded N-propyl kriptofix 21 and 22 with immobilized palladium nanoparticles for solid phase extraction and preconcentration of some metal ions.

    Ghaedi, Mehrorang; Niknam, Khodabakhsh; Zamani, Saeed; Larki, Habib Abasi; Roosta, Mostafa; Soylak, Mustafa


    Silica gel chemically bonded N-propyl kriptofix 21 (SBNPK 21) and N-propyl kriptofix 22 (SBNPK 22) and subsequently immobilized with palladium nanoparticles (PNP-SBNPK 21 and PNP-SBNPK 22) to produce two new complexing lipophilic materials. Then these novel sorbents were applied for the enrichment of some metal ions and their subsequent determination by flame atomic absorption spectroscopy (FAAS). The influences of the variables including pH, amount of solid phase, sample flow rate, eluent conditions and sample volume on the metal ion recoveries were investigated. The detection limit of proposed method was in the interval 2.1-2.3 and 1.7-2.8 ng mL(-1) for PNP-SBNPK 21 and PNP-SBNPK 22 respectively, while the preconcentration factor was 80 for two sorbents. The relative standard deviations of recoveries were between 1.23-1.31 and 1.28-1.49 for PNP-SBNPK 21 and PNP-SBNPK 22 respectively. The method has high sorption-preconcentration efficiency even in the presence of various interfering ions. Due to the reasonable selectivity of proposed method, the relative standard deviation of recoveries of all understudied metal ions in some complicated matrices was less than 3.0%.

  17. Model of phase distribution of hydrophobic organic chemicals in cyclodextrin-water-air-solid sorbent systems as a function of salinity, temperature, and the presence of multiple CDs

    Blanford, W. J.


    Environmental and other applications of cyclodextrins (CD) often require usage of high concentra- tion aqueous solutions of derivatized CDs. In an effort to reduce the costs, these studies also typically use technical grades where the purity of the CD solution and the degree of substitution has not been reported. Further, this grade of CD often included high levels of salt and it is commonly applied in high salinity systems. The mathematical models for water and air partitioning coefficients of hydrophobic organic chemicals (HOC) with CDs that have been used in these studies under-estimate the level of HOC within CDs. This is because those models (1) do not take into account that high concentrations of CDs result in significantly lower levels of water in solution and (2) they do not account for the reduction in HOC aqueous solubility due to the presence of salt. Further, because they have poor knowledge of the CD molar concentration in their solu- tions, it is difficult to draw comparisons between studies. Herein is developed a mathematical model where cyclo- dextrin is treated as a separate phase whose relative volume is calculated from its apparent molar volume in solution and the CD concentration of the solution. The model also accounts for the affects of temperature and the presence of salt in solution through inclusion of modified versions of the Van't Hoff and Setschenow equations. With these capabilities, additional equations have been developed for calculating HOC phase distribution in air-water-CD-solid sorbent systems for a single HOC and between water and CD for a system containing multiple HOCs as well as multiple types of cyclodextrin.

  18. Insights into solid phase characteristics and release of heavy metals and arsenic from industrial sludge via combined chemical, mineralogical, and microanalysis.

    Dung, Tran Thi Thu; Golreihan, Asefeh; Vassilieva, Elvira; Phung, Nguyen Ky; Cappuyns, Valérie; Swennen, Rudy


    This study investigates the solid phase characteristics and release of heavy metals (i.e., Cd, Co, Cu, Cr, Mo, Ni, Pb, and Zn) and arsenic (As) from sludge samples derived from industrial wastewater treatment plants. The emphasis is determining the influence of acidification on element mobilization based on a multidisciplinary approach that combines cascade and pHstat leaching tests with solid phase characterization through X-ray diffraction (XRD), field emission gun electron probe micro analysis (FEG-EPMA), and thermodynamic modeling (Visual MinteQ 3.0). Solid phase characterization and thermodynamic modeling results allow prediction of Ni and Zn leachabilities. FEG-EPMA is useful for direct solid phase characterization because it provides information on additional phases including specific element associations that cannot be detected by XRD analysis. Cascade and pHstat leaching test results indicate that disposal of improperly treated sludges at landfills may lead to extreme environmental risks due to high leachable concentrations of Zn, Ni, Cu, Cr, and Pb. However, high leachabilities under acid conditions of Ni and Zn as observed from pHstat leaching test results may provide a potential opportunity for acid extraction recovery of Ni and Zn from such sludges.

  19. Solid Phase Characterization of Solids Recovered from Failed Sluicer Arm

    Cooke, Gary A. [Hanford Site (HNF), Richland, WA (United States)


    The Enclosure to this memo discusses the solid phase characterization of a solid sample that was retrieved from the single-shell Tank 241-C-111 extended reach sluicer #2. This sluicer, removed from riser #3 on September 25, 2014, was found to have approximately 0.4 gallons of solid tank waste adhering to the nozzle area.

  20. Fabrication of a polymeric ionic liquid-based adsorbent for multiple monolithic fiber solid-phase microextraction of endocrine disrupting chemicals in complicated samples.

    Pei, Miao; Zhang, Zirui; Huang, Xiaojia; Wu, Yuanfei


    A multiple monolithic fiber solid-phase microextraction (MMF-SPME) utilizing polymeric ionic liquid-based adsorbent was prepared. The adsorbent was obtained by in situ copolymerization of an ionic liquid, 1-trimethyl-(4-vinylbenzyl) aminium chloride and dual cross-linkers (divinylbenzene and ethylenedimethacrylate). The effect of preparation conditions including the content of ionic liquid and porogen in the polymerization mixture on extraction performance was studied in detail. Infrared spectroscopy, elemental analysis, scanning electron microscopy and mercury intrusion porosimetry were used to inspect the physicochemical properties of the new adsorbent. The applicability of the new MMF-SPME was demonstrated by the extraction of trace endocrine disrupting chemicals (EDCs). Results indicated that the prepared MMF-SPME could extract EDCs effectively through multi-interactions such as ion-exchange, π-π and hydrophobic interactions. After optimization of extraction parameters, a method of MMF-SPME coupled to high performance liquid chromatography/diode array detection was conducted to detect trace EDCs in complicated samples including environmental water and human urine. The limits of detection (S/N=3) and quantification (S/N=10) for targeted compounds were 0.011-0.065μg/L and 0.036-0.21μg/L, respectively. Satisfactory precision was also achieved by evaluating the repeatability and intermediate precision with relative standard deviations (RSDs) of less than 9% and 10%, respectively. At the same time, the proposed method was successfully applied for the determination of EDCs in water and human urine with spiking recoveries ranged from 70.6% to 119%.

  1. Identification and quantification of seven volatile n-nitrosamines in cosmetics using gas chromatography/chemical ionization-mass spectrometry coupled with head space-solid phase microextraction.

    Choi, Na Rae; Kim, Yong Pyo; Ji, Won Hyun; Hwang, Geum-Sook; Ahn, Yun Gyong


    An analytical method was developed for the identification and quantification of seven volatile n-nitrosamines (n-nitrosodimethylamine [NDMA], n-nitrosoethylmethylamine [NMEA], n-nitrosodiethylamine [NDEA], n-nitrosodipropylamine [NDPA], n-nitrosodibutylamine [NDBA], n-nitrosopiperidine [NPIP], and n-nitrosopyrrolidine [NPYR]) in water insoluble cream type cosmetics. It was found that the head space-solid phase microextraction (HS-SPME) was suitable for extraction, clean up, and pre-concentration of n-nitrosamines in the cream type samples so its optimal conditions were investigated. Identification and quantification of n-nitrosamines using single quadrupole gas chromatography/mass spectrometry (GC/MS) in chemical ionization (CI) mode were carried out with accurate mass measurements. Their accurate masses of protonated molecular ions were obtained within 10 mDa of the theoretical masses when sufficiently high signal was acquired from the unique calibration method using mass and isotope accuracy. For the method validation of quantification, spiking experiments were carried out to determine the linearity, recovery, and method detection limit (MDL) using three deuterated internal standards. The average recovery was 79% within 20% relative standard deviation (RSD) at the concentration of 50 ng/g. MDLs ranged from 0.46 ng/g to 36.54 ng/g, which was satisfactory for the directive limit of 50 ng/g proposed by the European Commission (EC). As a result, it was concluded that the method could be provided for the accurate mass screening, confirmation, and quantification of n-nitrosamines when applied to cosmetic inspection.

  2. Facile synthesis of PbSe hollow nanostructure assemblies via a solid/liquid-phase chemical route and their electrogenerated chemiluminescence properties.

    Han, Min; Li, Yanrong; Niu, Hongyan; Liu, Lili; Chen, Kunji; Bao, Jianchun; Dai, Zhihui; Zhu, Jianming


    Spherical PbSe hollow nanostructure assemblies (HNSAs) were synthesized by a simple one-pot solid/liquid-phase reaction in which solid KPbI(3)⋅2 H(2)O and SeO(2) are heated in oleic acid/dodecylamine/1-octadecene at 250 °C for 30 min. XRD analysis shows that the obtained product is cubic-phase PbSe and well crystallized. FESEM and TEM images reveal that the obtained spherical PbSe assemblies are made up of small, irregular, and fused hollow nanostructure building blocks. On the basis of temperature- and time-dependent investigations as well as control experiments, molten-salt corrosion of solid PbSe nanocrystal aggregates formed in situ during the high-temperature ripening stage is suggested to explain the formation of such novel assemblies. Moreover, when the reaction temperature is further increased to 280 or 320 °C with other conditions unchanged, cubic and orthorhombic mixed-phase PbSe HNSAs is generated. The obtained PbSe HNSAs exhibit excellent electrogenerated chemiluminescence (ECL) performance. Two strong and stable emission peaks at about -1.4 and +1.5 V (vs. Ag/AgCl) are observed. In particular, the ECL intensity is influenced by the crystal phase of PbSe. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. A comparison of observables for solid-solid phase transitions

    Smilowitz, Laura B [Los Alamos National Laboratory; Henson, Bryan F [Los Alamos National Laboratory; Romero, Jerry J [Los Alamos National Laboratory


    The study of solid-solid phase transformations is hindered by the difficulty of finding a volumetric probe to use as a progress variable. Solids are typically optically opaque and heterogeneous. Over the past several years, second harmonic generation (SHG) has been used as a kinetic probe for a solid-solid phase transition in which the initial and final phases have different symmetries. Bulk generation of SHG is allowed by symmetry only in noncentrosymmetric crystallographic space groups. For the organic energetic nitramine octahydro-1,3 ,5,7 -tetranitro-1,3 ,5,7 -tatrazocine (HMX), the beta phase is centro symmetric (space group P2{sub 1}/c) and the delta phase iS noncentrosymmetric (space group P6{sub 1}22) making SHG an extremely sensitive, essentially zero background probe of the phase change progress. We have used SHG as a tool to follow the progress of the transformation from beta to delta phase during the solid-solid transformation. However, kinetic models of the transformation derived using different observables from several other groups have differed, showing later onset for the phase change and faster progression to completion. In this work, we have intercompared several techniques to understand these differences. The three techniques discussed are second harmonic generation, Raman spectroscopy, and differential scanning calorimetry (DSC). The progress of the beta to delta phase transition in HMX observed with each of these different probes will be discussed and advantages and disadvantages of each technique described. This paper compares several different observables for use in measuring the kinetics of solid-solid phase transitions. Relative advantages and disadvantages for each technique are described and a direct comparison of results is made for the beta to delta polymorphic phase transition of the energetic nitramine, octahydro-1,3,5,7-tetranitro-1,3,5,7-tatrazocine.

  4. Development of a dynamic headspace solid-phase microextraction procedure coupled to GC–qMSD for evaluation the chemical profile in alcoholic beverages

    Rodrigues, F.; Caldeira, M; Câmara, José de Sousa


    In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC–qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as th...

  5. Full automation of solid-phase microextraction/on-fiber derivatization for simultaneous determination of endocrine-disrupting chemicals and steroid hormones by gas chromatography-mass spectrometry.

    Yang, Lihua; Lan, Chongyu; Liu, Hongtao; Dong, Jun; Luan, Tiangang


    A fully automated method using direct immersion solid-phase microextraction (DI-SPME) and headspace on-fiber silylation for simultaneous determinations of exogenous endocrine-disrupting chemicals (EDCs) and endogenous steroid hormones in environmental aqueous and biological samples by gas chromatography-mass spectrometry (GC-MS) was developed and compared to a previously reported manual method. Three EDCs and five endocrine steroid hormones were selected to evaluate this method. The extraction and derivatization time, ion strength, pH, incubation temperature, sample volume, and extraction solvent were optimized. Satisfactory results in pure water were obtained in terms of linearity of calibration curve (R2=0.9932-1.0000), dynamic range (3 orders of magnitude), precision (4-9% RSD), as well as LOD (0.001-0.124 microg L(-1)) and LOQ (0.004-0.413 microg L(-1)), respectively. These results were similar to those obtained using a manual method, and moreover, the precision was improved. This new automated method has been applied to the determinations of target compounds in real samples used in our previous study on a manual SPME method. Exogenous octylphenol (OP), technical grade nonylphenol (t-NP), and diethylstilbestrol (DES) were at 0.13, 5.03, and 0.02 microg L(-1) in river water and 3.76, 13.25, and 0.10 microg L(-1) in fish serum, respectively. Natural steroid hormones estrone (E1), 17beta-estradiol (E2), and testosterone (T) were at 0.19, 0.11, and 6.22 microg L(-1) in river water; and in female fish serum E1, E2, and pregnenolone (PREG) were at 1.37, 1.95, and 6.25 microg L(-1), respectively. These results were confirmed by the manual method. The developed fully automated SPME and on-fiber silylation procedures showed satisfactory applications in environmental analysis and the performances show improved precision and a reduced analysis time compared to the manual method.

  6. Development of a dynamic headspace solid-phase microextraction procedure coupled to GC-qMSD for evaluation the chemical profile in alcoholic beverages

    Rodrigues, F.; Caldeira, M. [Centro de Quimica da Madeira, Departamento de Quimica, Universidade da Madeira, Campus Universitario da Penteada, 9000-390 Funchal (Portugal); Camara, J.S. [Centro de Quimica da Madeira, Departamento de Quimica, Universidade da Madeira, Campus Universitario da Penteada, 9000-390 Funchal (Portugal)], E-mail:


    In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC-qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as the type of fibre coating, extraction time and temperature, sample stirring and ionic strength, were optimized. The performance of five commercially available SPME fibres was evaluated and compared, namely polydimethylsiloxane (PDMS, 100 {mu}m); polyacrylate (PA, 85 {mu}m); polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 {mu}m); carboxen{sup TM}/polydimethylsiloxane (CAR/PDMS, 75 {mu}m) and the divinylbenzene/carboxen on polydimethylsiloxane (DVB/CAR/PDMS, 50/30 {mu}m) (StableFlex). An objective comparison among different alcoholic beverages has been established in terms of qualitative and semi-quantitative differences on volatile and semi-volatile compounds. These compounds belong to several chemical families, including higher alcohols, ethyl esters, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, furanic compounds, terpenoids, C13-norisoprenoids and volatile phenols. The optimized extraction conditions and GC-qMSD, lead to the successful identification of 44 compounds in white wines, 64 in beers and 104 in whiskys. Some of these compounds were found in all of the examined beverage samples. The main components of the HS-SPME found in white wines were ethyl octanoate (46.9%), ethyl decanoate (30.3%), ethyl 9-decenoate (10.7%), ethyl hexanoate (3.1%), and isoamyl octanoate (2.7%). As for beers, the major compounds were isoamyl alcohol (11.5%), ethyl octanoate (9.1%), isoamyl acetate (8.2%), 2-ethyl-1-hexanol (5.9%), and octanoic acid (5.5%). Ethyl

  7. Development of a dynamic headspace solid-phase microextraction procedure coupled to GC-qMSD for evaluation the chemical profile in alcoholic beverages.

    Rodrigues, F; Caldeira, M; Câmara, J S


    In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC-qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as the type of fibre coating, extraction time and temperature, sample stirring and ionic strength, were optimized. The performance of five commercially available SPME fibres was evaluated and compared, namely polydimethylsiloxane (PDMS, 100 microm); polyacrylate (PA, 85 microm); polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 microm); carboxentrade mark/polydimethylsiloxane (CAR/PDMS, 75 microm) and the divinylbenzene/carboxen on polydimethylsiloxane (DVB/CAR/PDMS, 50/30 microm) (StableFlex). An objective comparison among different alcoholic beverages has been established in terms of qualitative and semi-quantitative differences on volatile and semi-volatile compounds. These compounds belong to several chemical families, including higher alcohols, ethyl esters, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, furanic compounds, terpenoids, C13-norisoprenoids and volatile phenols. The optimized extraction conditions and GC-qMSD, lead to the successful identification of 44 compounds in white wines, 64 in beers and 104 in whiskys. Some of these compounds were found in all of the examined beverage samples. The main components of the HS-SPME found in white wines were ethyl octanoate (46.9%), ethyl decanoate (30.3%), ethyl 9-decenoate (10.7%), ethyl hexanoate (3.1%), and isoamyl octanoate (2.7%). As for beers, the major compounds were isoamyl alcohol (11.5%), ethyl octanoate (9.1%), isoamyl acetate (8.2%), 2-ethyl-1-hexanol (5.9%), and octanoic acid (5

  8. Chemical and morphological characteristics of solid metal-bearing phases deposited in snow and stream sediment as indicators of their origin.

    Miler, Miloš; Gosar, Mateja


    Detailed scanning electron microscopy/energy dispersive spectroscopy of metal-bearing particles in snow deposits and stream sediment from a steelworks area was performed. Identified metal-bearing phases were apportioned according to their chemical and morphological characteristics to anthropogenic phases and secondary weathering products. Anthropogenic metal-bearing phases are the most abundant in both media and are represented by various irregular ferrous oxides, ferrous alloys, spherical ferrous oxides, and ferrous silicates with variable contents of Cr, Mn, Ni, V, W, and Mo. Secondary weathering products are Al silicates, Fe oxy-hydroxides, and Fe oxy-hydroxy sulfates with minor contents of transition metals, resulting from weathering of anthropogenic phases and Pb-Zn ore minerals from a closed Pb-Zn mine located upstream from the study area. Comparison of anthropogenic metal-bearing phases in both media showed agreement in their compositions and morphologies and indicated their sources are high-temperature processes in steel production. It also showed that spherical metal-bearing phases were transported by the same transport medium, which is the atmosphere, while other phases were transported into stream sediment mostly by other pathways, such as precipitation runoff over contaminated surfaces.

  9. Solid phase microextraction device using aerogel

    Miller, Fred S.; Andresen, Brian D.


    A sample collection substrate of aerogel and/or xerogel materials bound to a support structure is used as a solid phase microextraction (SPME) device. The xerogels and aerogels may be organic or inorganic and doped with metals or other compounds to target specific chemical analytes. The support structure is typically formed of a glass fiber or a metal wire (stainless steel or kovar). The devices are made by applying gel solution to the support structures and drying the solution to form aerogel or xerogel. Aerogel particles may be attached to the wet layer before drying to increase sample collection surface area. These devices are robust, stable in fields of high radiation, and highly effective at collecting gas and liquid samples while maintaining superior mechanical and thermal stability during routine use. Aerogel SPME devices are advantageous for use in GC/MS analyses due to their lack of interfering background and tolerance of GC thermal cycling.

  10. Solid-solid phase transitions via melting in metals

    Pogatscher, S.; Leutenegger, D.; Schawe, J. E. K.; Uggowitzer, P. J.; Löffler, J. F.


    Observing solid-solid phase transitions in-situ with sufficient temporal and spatial resolution is a great challenge, and is often only possible via computer simulations or in model systems. Recently, a study of polymeric colloidal particles, where the particles mimic atoms, revealed an intermediate liquid state in the transition from one solid to another. While not yet observed there, this finding suggests that such phenomena may also occur in metals and alloys. Here we present experimental evidence for a solid-solid transition via the formation of a metastable liquid in a `real' atomic system. We observe this transition in a bulk glass-forming metallic system in-situ using fast differential scanning calorimetry. We investigate the corresponding transformation kinetics and discuss the underlying thermodynamics. The mechanism is likely to be a feature of many metallic glasses and metals in general, and may provide further insight into phase transition theory.

  11. Application of solid-phase microextraction and gas chromatography-mass spectrometry for measuring chemicals in saliva of synthetic leather workers.

    Wang, Ven-Shing; Lu, Ming-Yen


    Saliva is of interest as a diagnostic aid for oral and systemic diseases, to monitor therapeutic drugs, and detect illicit drug abuse. It is also attractive for biological monitoring of exposure to hazardous solvents. The major advantage of this indicator over other biological monitoring targets is that the saliva is noninvasive and less confidential in comparison with blood and urine. Salivary analysis is generally acceptable by study subjects and can be applied to investigation of a wide variety of compounds. However, very few studies have been conducted on the saliva matrix to monitor exposure to hazardous solvents. The aim of this study is to establish an analytical method, headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS), by which the saliva matrix can be monitored for multiple compounds with various polarities, such as methyl ethyl ketone (MEK), isopropyl alcohol (IPA), and N,N-dimethyl formamide (DMF) (common solvents used in synthetic leather manufacture), as well as acetone (ACE) and N-methyl formamide (NMF) (metabolites of IPA and DMF, respectively). We studied this technique as an alternative biological monitoring method for investigating exposure to hazardous solvents. A Carboxen/Polydimethylsiloxane (CAR/PDMS 75 microm) fiber coating was employed for this study, and various extraction and desorption parameters were evaluated. The extraction efficiency and reproducibility of analyses was improved by pre-incubation. The limits of detection were 0.004, 0.003, 0.006, 0.05, and 0.10 microg/mL for ACE, MEK, IPA, DMF, and NMF, respectively. Method validation was performed on standards spiked in blank saliva, and a correlation was made between HS-SPME and traditional solvent pretreatment methods. It was found that correlation coefficients (r) were greater than 0.996 for each analyte, with no significant differences (p>0.05) between two methods. However, the SPME method achieved lower limits of detection

  12. Solid-phase oligosaccharide and glycopeptide synthesis using glycosynthases

    Tolborg, Jakob Fjord; Petersen, Lars; Jensen, Knud Jørgen;


    Enzymatic approaches for the preparation of oligosaccharides are interesting alternatives to traditional chemical synthesis, the main advantage being the regio- and stereoselectivity offered without the need for protecting groups. The use of solid-phase techniques offers easy workup procedures an...


    Ning Yang; Wei Wang; Wei Ge; Jinghai Li


    @@ Introduction Gas-solid two-phase flow is often encountered in chemical reactors for the process industry. For industrial users, design, scale-up, control and optimization for these reactors require a good understanding of the hydrodynamics of gas-solid two-phase flow. For researchers, exploration and prediction of the complex phenomena call for a good comprehension of the heterogeneous structure and of the dominant mechanisms of gas-solid and solid-solid interactions.

  14. Binary Solid-Liquid Phase Equilibria

    Ellison, Herbert R.


    Indicates some of the information that may be obtained from a binary solid-liquid phase equilibria experiment and a method to write a computer program that will plot an ideal phase diagram to which the experimental results may be compared. (Author/CP)

  15. Development and characterization of a nanodendritic silver-based solid-phase extraction sorbent for selective enrichment of endocrine-disrupting chemicals in water and milk samples.

    Gao, Yuanji; Xia, Bing; Liu, Jie; Ji, Baocheng; Ma, Fengwei; Ding, Lisheng; Li, Bangjing; Zhou, Yan


    In this study, 4-[4-phenylazo-phenoxy] butyl-1-thiol (AzSH) functionalized nanodendritic silver (AzS@AgNDs) materials were prepared as a solid-phase extraction (SPE) sorbent for the selective extraction of estrogens. AzS@AgNDs possess an extremely large surface-to-volume ratio and a small average particle size. The performance of the material was evaluated by selective enrichment of hexestrol, diethylstilbestrol, dienestrol and bisphenol A in water and milk samples followed by rapid ultra-performance liquid chromatography-electrospray ionization mass spectrometry (UPLC-ESI-MS) analyses. The results exhibited that AzS@AgNDs had excellent adsorption capability for the targeted estrogens. The limits of detection of the four estrogens ranged from 0.1 to 5.0 pg/mL. The recoveries of the estrogens spiked into tap water were over the range of 83.6-105.3% with relative standard deviations of 2.8-6.0%. The results indicated the capability of this method for the rapid determination of estrogens in milk and other environmental water samples. In addition, this method would be useful for the determination of human exposure and health risk assessments trace level of endocrine-disrupting compounds (EDCs) in drinking water.

  16. Molecularly imprinted layer-coated silica nanoparticles for selective solid-phase extraction of bisphenol A from chemical cleansing and cosmetics samples

    Zhu Rong; Zhao Wenhui; Zhai Meijuan; Wei Fangdi; Cai Zheng; Sheng Na [School of Pharmacy, Nanjing Medical University, Hanzhong Road 140, Nanjing, Jiangsu 210029 (China); Hu Qin, E-mail: [School of Pharmacy, Nanjing Medical University, Hanzhong Road 140, Nanjing, Jiangsu 210029 (China)


    Highly selective molecularly imprinted layer-coated silica nanoparticles for bisphenol A (BPA) were synthesized by molecular imprinting technique with a sol-gel process on the supporter of silica nanoparticles. The BPA-imprinted silica nanoparticles were characterized by fourier transform infrared spectrometer, transmission electron microscope, dynamic adsorption and static adsorption tests. The equilibrium association constant, K{sub a}, and the apparent maximum number of binding sites, Q{sub max}, were estimated to be 1.25 x 10{sup 5} mL {mu}mol{sup -1} and 16.4 {mu}mol g{sup -1}, respectively. The BPA-imprinted silica nanoparticles solid-phase extraction (SPE) column had higher selectivity for BPA than the commercial C18-SPE column. The results of the study indicated that the prepared BPA-imprinted silica nanoparticles exhibited high adsorption capacity and selectivity, and offered a fast kinetics for the rebinding of BPA. The BPA-imprinted silica nanoparticles were successfully used in SPE to selectively enrich and determine BPA from shampoo, bath lotion and cosmetic cream samples.

  17. Molecularly imprinted layer-coated silica nanoparticles for selective solid-phase extraction of bisphenol A from chemical cleansing and cosmetics samples.

    Zhu, Rong; Zhao, Wenhui; Zhai, Meijuan; Wei, Fangdi; Cai, Zheng; Sheng, Na; Hu, Qin


    Highly selective molecularly imprinted layer-coated silica nanoparticles for bisphenol A (BPA) were synthesized by molecular imprinting technique with a sol-gel process on the supporter of silica nanoparticles. The BPA-imprinted silica nanoparticles were characterized by fourier transform infrared spectrometer, transmission electron microscope, dynamic adsorption and static adsorption tests. The equilibrium association constant, K(a), and the apparent maximum number of binding sites, Q(max), were estimated to be 1.25 x 10(5) mL micromol(-1) and 16.4 micromol g(-1), respectively. The BPA-imprinted silica nanoparticles solid-phase extraction (SPE) column had higher selectivity for BPA than the commercial C18-SPE column. The results of the study indicated that the prepared BPA-imprinted silica nanoparticles exhibited high adsorption capacity and selectivity, and offered a fast kinetics for the rebinding of BPA. The BPA-imprinted silica nanoparticles were successfully used in SPE to selectively enrich and determine BPA from shampoo, bath lotion and cosmetic cream samples.

  18. Solid phase sequencing of biopolymers

    Cantor, Charles R.; Hubert, Koster


    This invention relates to methods for detecting and sequencing target nucleic acid sequences, to mass modified nucleic acid probes and arrays of probes useful in these methods, and to kits and systems which contain these probes. Useful methods involve hybridizing the nucleic acids or nucleic acids which represent complementary or homologous sequences of the target to an array of nucleic acid probes. These probes comprise a single-stranded portion, an optional double-stranded portion and a variable sequence within the single-stranded portion. The molecular weights of the hybridized nucleic acids of the set can be determined by mass spectroscopy, and the sequence of the target determined from the molecular weights of the fragments. Probes may be affixed to a solid support such as a hybridization chip to facilitate automated molecular weight analysis and identification of the target sequence.

  19. Solid phase sequencing of biopolymers

    Cantor, Charles (Del Mar, CA); Koster, Hubert (La Jolla, CA)


    This invention relates to methods for detecting and sequencing target nucleic acid sequences, to mass modified nucleic acid probes and arrays of probes useful in these methods, and to kits and systems which contain these probes. Useful methods involve hybridizing the nucleic acids or nucleic acids which represent complementary or homologous sequences of the target to an array of nucleic acid probes. These probes comprise a single-stranded portion, an optional double-stranded portion and a variable sequence within the single-stranded portion. The molecular weights of the hybridized nucleic acids of the set can be determined by mass spectroscopy, and the sequence of the target determined from the molecular weights of the fragments. Nucleic acids whose sequences can be determined include DNA or RNA in biological samples such as patient biopsies and environmental samples. Probes may be fixed to a solid support such as a hybridization chip to facilitate automated molecular weight analysis and identification of the target sequence.

  20. Measurements of solids concentration and axial solids velocity in gas-solid two-phase flows.

    Nieuwland, J.J.; Meijer, R.; Kuipers, J.A.M.; Swaaij, van W.P.M.


    Several techniques reported in the literature for measuring solids concentration and solids velocity in (dense) gas-solid two-phase flow have been briefly reviewed. An optical measuring system, based on detection of light reflected by the suspended particles, has been developed to measure local soli

  1. Development of a solid-phase microextraction fiber by chemical binding of polymeric ionic liquid on a silica coated stainless steel wire.

    Pang, Long; Liu, Jing-Fu


    A novel approach was developed for the fabrication of solid-phase microextraction (SPME) fiber by coating stainless steel fiber with a polymeric ionic liquid (PIL) through covalent bond. The stainless steel fiber was sequentially coated with a gold film by replacement reaction between Fe and Au when immerged in chloroauric acid, assembled with a monolayer of 3-(mercaptopropyl) triethoxysilane on the gold layer through the Au-S bond, and coated with a silica layer by the hydrolysis and polycondensation reaction of the surface-bonded siloxane moieties and the active silicate solution. Then, 1-vinyl-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazolium chloride ionic liquid was anchored on the silica layer by covalent bond, and the PIL film was further formed by free radical copolymerization between 1-vinyl-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazdium and vinyl-substituted imidazolium with azobisisobutyronitrile (AIBN) as initiator. Parameters influencing the preparation of PIL fiber were optimized, and the developed SPME fiber has a coating thickness of ~20 μm with good thermal stability and long lifetime. The performance of the PIL fiber was evaluated by analysis of polycyclic aromatic hydrocarbons (PAHs) in water samples. The developed PIL fiber showed good linearity between 0.5 and 20 μg l(-1) with regression coefficient in the range of 0.963-0.999, detection limit ranging from 0.05 to 0.25 μg l(-1), and relative standard deviation of 9.2-29% (n=7). This developed PIL fiber exhibited comparable analytical performance to commercial 7 μm thickness PDMS fiber in the extraction of PAHs. The spiked recoveries for three real water samples at 0.5-5 μg l(-1) levels were 49.6-111% for the PIL fiber and 40.8-103% for the commercial PDMS fiber.

  2. Multiplexed Colorimetric Solid-Phase Extraction

    Gazda, Daniel B.; Fritz, James S.; Porter, Marc D.


    Multiplexed colorimetric solid-phase extraction (MC-SPE) is an extension of colorimetric solid-phase extraction (C-SPE) an analytical platform that combines colorimetric reagents, solid phase extraction, and diffuse reflectance spectroscopy to quantify trace analytes in water. In CSPE, analytes are extracted and complexed on the surface of an extraction membrane impregnated with a colorimetric reagent. The analytes are then quantified directly on the membrane surface using a handheld diffuse reflectance spectrophotometer. Importantly, the use of solid-phase extraction membranes as the matrix for impregnation of the colorimetric reagents creates a concentration factor that enables the detection of low concentrations of analytes in small sample volumes. In extending C-SPE to a multiplexed format, a filter holder that incorporates discrete analysis channels and a jig that facilitates the concurrent operation of multiple sample syringes have been designed, enabling the simultaneous determination of multiple analytes. Separate, single analyte membranes, placed in a readout cartridge create unique, analyte-specific addresses at the exit of each channel. Following sample exposure, the diffuse reflectance spectrum of each address is collected serially and the Kubelka-Munk function is used to quantify each water quality parameter via calibration curves. In a demonstration, MC-SPE was used to measure the pH of a sample and quantitate Ag(I) and Ni(II).

  3. Phase 2, Solid waste retrieval strategy

    Johnson, D.M.


    Solid TRU retrieval, Phase 1 is scheduled to commence operation in 1998 at 218W-4C-T01 and complete recovery of the waste containers in 2001. Phase 2 Retrieval will recover the remaining buried TRU waste to be retrieved and provide the preliminary characterization by non-destructive means to allow interim storage until processing for disposal. This document reports on researching the characterization documents to determine the types of wastes to be retrieved and where located, waste configurations, conditions, and required methods for retrieval. Also included are discussions of wastes encompassed by Phase 2 for which there are valid reasons to not retrieve.

  4. Distribution of Pb and its chemical fractions in liquid and solid phases of digested pig and dairy slurries%猪、奶牛粪厌氧发酵中Pb的形态转化及其分布特征

    靳红梅; 付广青; 常志州; 叶小梅


    Anaerobic digestion treatment effectively degrades the organic matter and causes obvious variations in physical and chemical properties of digested slurries, such as water content, pH, oxidation reduction potential and microbial activities. These changes may influence the chemical fraction of Pb, which is a critical factor in predicting its toxicity, environmental mobility, bioavailability and optimum removal methods. The speciation and phytotoxic effects of lead from sewage sludge and composted manure have been widely studied. There has been no study about the transfer and distribution of Pb during anaerobic digestion of manure slurries. The aim of the present work was to analyze the distribution of Pb in both liquid and solid phase after anaerobic digestion of pig slurries and dairy slurries, and their chemical speciation in solid fraction of digested residuals. The continuous stirred tank reactor (CSTR) at condition of medium temperature [(37 ± 2)℃] was operated for 130 d. Lead in liquid and solid phases of raw materials and digested slurries was analyzed by first passing through a 0.45 µm filter paper. The chemical fractions in digested slurry solids were extracted by BCR method. Results showed that total amount of Pb was decreased 70% and 19% in digested pig slurries (DPS) and dairy slurries (DDS), respectively, , compared with raw slurries. The percentages of Pb in liquid fractions of DPS and DDS were 29%and 17%, which decreased by 17%and 58%. The decrease of Pb in DDS was significantly lower than that in DPS. One reason is that 90%of solids in DDS were discharged during the anaerobic digestion. Another reason is that Pb in digested slurries mainly exists as the solid form. Thus the amount of Pb left in the reactor for dairy manure digestion was significantly lower than that for pig manure digest. Due to the high removal efficiency, easy operation and low treatment cost of heavy metals in solid phase, transformation of liquid phase of heavy metals to the

  5. Megabar pressure phases of solid hydrogen

    Chen, Nancy Hueling

    The behavior of solid Hsb2, Dsb2, and HD at low temperatures high pressures was investigated. The experimental data were obtained by combining high pressure diamond anvil cell apparatus with cryogenic and spectroscopic techniques. Megabar pressures (1 bar = 10sp5 Pa) and liquid helium temperatures were accessible. The observed phases and phase lines are discussed with respect to orientational order, crystal structure, and electronic properties. The orientational order-disorder phase transition in HD was studied by Raman spectroscopy. Due to the distinguishability of the nuclei in an HD molecule, the observed phase line exhibits surprising behavior relative to that expected for the homonuclear molecules Hsb2 and Dsb2. The megabar pressure phase diagram of solid Dsb2 was investigated by infrared and Raman spectroscopy. The broken symmetry phase (BSP) transition line and the D-A phase line were observed to meet at a triple point. The relative arrangement of phase lines in P-T space, combined with group theoretical analysis of observed infrared and Raman spectra within the phases, sets symmetry restrictions on the allowed crystal structures. The electronic properties of the high pressure H-A and D-A phases were examined, since these recently discovered phases were suspected of being metallic. Acquired broadband infrared absorption spectra extending to 10 mum were analyzed in terms of the Drude model for metals. No evidence indicating metallic behavior was found. Refinements in high pressure techniques were explored, in order to increase the maximum pressures attainable. A method of extending ruby fluorescence pressure measurements to multimegabar pressures was developed, which involved excitation of ruby fluorescence with red, rather than blue or green laser light.

  6. QCD Phase Diagram with Imaginary Chemical Potential

    Nakamura Atsushi


    Full Text Available We report our recent results on the QCD phase diagram obtained from the lattice QCD simulation. The location of the phase boundary between hadronic and QGP phases in the two-flavor QCD phase diagram is investigated. The imaginary chemical potential approach is employed, which is based on Monte Carlo simulations of the QCD with imaginary chemical potential and analytic continuation to the real chemical potential region.

  7. Analysis of Odorants in Marking Fluid of Siberian Tiger (Panthera tigris altaica Using Simultaneous Sensory and Chemical Analysis with Headspace Solid-Phase Microextraction and Multidimensional Gas Chromatography-Mass Spectrometry-Olfactometry

    Simone B. Soso


    Full Text Available Scent-marking is the most effective method of communication in the presence or absence of a signaler. These complex mixtures result in a multifaceted interaction triggered by the sense of smell. The objective was to identify volatile organic compound (VOC composition and odors emitted by total marking fluid (MF associated with Siberian tigers (Panthera tigris altaica. Siberian tiger, an endangered species, was chosen because its MF had never been analyzed. Solid phase microextraction (SPME for headspace volatile collection combined with multidimensional gas chromatography-mass spectrometry-olfactometry for simultaneous chemical and sensory analyses were used. Thirty-two VOCs emitted from MF were identified. 2-acetyl-1-pyrroline, the sole previously identified compound responsible for the “characteristic” odor of P. tigris MF, was identified along with two additional compounds confirmed with standards (urea, furfural and four tentatively identified compounds (3-methylbutanamine, (R-3-methylcyclopentanone, propanedioic acid, and 3-hydroxybutanal as being responsible for the characteristic aroma of Siberian tiger MF. Simultaneous chemical and sensory analyses improved characterization of scent-markings and identified compounds not previously reported in MF of other tiger species. This research will assist animal ecologists, behaviorists, and zookeepers in understanding how scents from specific MF compounds impact tiger and wildlife communication and improve management practices related to animal behavior. Simultaneous chemical and sensory analyses is applicable to unlocking scent-marking information for other species.

  8. [Solid phase techniques in blood group serology].

    Uthemann, H; Sturmfels, L; Lenhard, V


    As alternatives to hemagglutination, solid-phase red blood cell adherence assays are of increasing importance. The adaptation of the new techniques to microplates offers several advantages over hemagglutination. Using microplates the assays may be processed semiautomatically, and the results can be read spectrophotometrically and interpreted by a personal computer. In this paper, different red blood cell adherence assays for AB0 grouping, Rh typing, Rh phenotyping, antibody screening and identification, as well as crossmatching will be described.

  9. Recent advances in solid phase peptide synthesis

    White, P.D.


    Since its introduction by Merrifield half a century ago, solid phase peptide synthesis has evolved to become the enabling technology for the development of peptide therapeutics. Using modern methods, 100 - 1000s of peptides can be routinely synthesised in parallel for screening as leads for drug development and peptide APIs are produced in ton scale. In this talk I consider the state of art and report on recent advances to overcome remaining issues such as aspartimide formation, racemisation ...

  10. Change of physical and chemical properties of the solid phase during biomass pyrolysis; Aenderung der physikalisch-chemischen Eigenschaften des Feststoffs waehrend der Biomassepyrolyse

    Klose, Wolfgang [Kassel Univ. (Germany). Inst. fuer Thermische Energietechnik; Rincon, Sonia; Gomez, Alexander [Universidad Nacional de Colombia, Bogota (Colombia). Dept. de Ingenieria Mecanica y Mecatronica


    The effects of the final pyrolysis temperature on the development of the chemical composition and on the porosity of biomass undergoing pyrolysis are investigated through experiments in a thermobalance at laboratory scale of grams. Changes in the grain size of individual particles of biomass during pyrolysis are also investigated as a function of temperature in a microscope equipped with heating and camera. Oil palm shells are selected as raw materials due to their availability as biomass residue and their physical and chemical characteristics. These experiments are important for reactor design purposes in the field of thermochemical conversion, offering important information for the mathematical modelling of the processes. (orig.)

  11. Zirconia-based solid state chemical gas sensors

    Zhuiykov, S


    This paper presents an overview of chemical gas sensors, based on solid state technology, that are sensitive to environmental gases, such as O sub 2 , SO sub x , NO sub x , CO sub 2 and hydrocarbons. The paper is focussed on performance of electrochemical gas sensors that are based on zirconia as a solid electrolyte. The paper considers sensor structures and selection of electrode materials. Impact of interfaces on sensor performance is discussed. This paper also provides a brief overview of electrochemical properties of zirconia and their effect on sensor performance. Impact of auxiliary materials on sensors performance characteristics, such as sensitivity, selectivity, response time and recovery time, is also discussed. Dual gas sensors that can be applied for simultaneous monitoring of the concentration of both oxygen and other gas phase components, are briefly considered


    We evaluated a method for delivering ferrous iron into the subsurface to enhance chemical reduction of Cr(VI) in a chromite ore processing solid waste (COPSW). The COPSW is characterized by high pH (8.5 -11.5), high Cr(VI) concentrations in the solid phase (up to 550 mg kg-1) and...

  13. Indigenous microbial capability in solid manure residues to start-up solid-phase anaerobic digesters.

    Yap, S D; Astals, S; Jensen, P D; Batstone, D J; Tait, S


    Batch solid-phase anaerobic digestion is a technology for sustainable on-farm treatment of solid residues, but is an emerging technology that is yet to be optimised with respect to start-up and inoculation. In the present study, spent bedding from two piggeries (site A and B) were batch digested at total solids (TS) concentration of 5, 10 and 20% at mesophilic (37°C) and thermophilic (55°C) temperatures, without adding an external inoculum. The results showed that the indigenous microbial community present in spent bedding was able to recover the full methane potential of the bedding (140±5 and 227±6L CH4 kgVSfed(-1) for site A and B, respectively), but longer treatment times were required than for digestion with an added external inoculum. Nonetheless, at high solid loadings (i.e. TS level>10%), the digestion performance was affected by chemical inhibition due to ammonia and/or humic acid. Thermophilic temperatures did not influence digestion performance but did increase start-up failure risk. Further, inoculation of residues from the batch digestion to subsequent batch enhanced start-up and achieved full methane potential recovery of the bedding. Inoculation with liquid residue (leachate) was preferred over a solid residue, to preserve treatment capacity for fresh substrate. Overall, the study highlighted that indigenous microbial community in the solid manure residue was capable of recovering full methane potential and that solid-phase digestion was ultimately limited by chemical inhibition rather than lack of suitable microbial community. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Development of headspace solid-phase microextraction method for ...

    ... solid-phase microextraction method for the analysis of pesticide residues in fruit and ... Journal of Applied Sciences and Environmental Management ... interface temperature) and solid phase microextraction parameters (fiber coating type, ...

  15. Oscillatory burning of solid propellants including gas phase time lag.

    T'Ien, J. S.


    An analysis has been performed for oscillatory burning of solid propellants including gas phase time lag. The gaseous flame is assumed to be premixed and laminar with a one-step overall chemical reaction. The propellant is assumed to decompose according to the Arrenhius Law, with no condensed phase reaction. With this model, strong gas phase resonance has been found in certain cases at the characteristic gas-phase frequencies, but the peaking of the acoustic admittance is in the direction favoring the damping of pressure waves. At still higher frequencies, moderate wave-amplifying ability was found. The limit of low frequency response obtained previously by Denison and Baum was recovered, and the limitations of the quasi-steady theory were investigated.

  16. Oscillatory burning of solid propellants including gas phase time lag.

    T'Ien, J. S.


    An analysis has been performed for oscillatory burning of solid propellants including gas phase time lag. The gaseous flame is assumed to be premixed and laminar with a one-step overall chemical reaction. The propellant is assumed to decompose according to the Arrenhius Law, with no condensed phase reaction. With this model, strong gas phase resonance has been found in certain cases at the characteristic gas-phase frequencies, but the peaking of the acoustic admittance is in the direction favoring the damping of pressure waves. At still higher frequencies, moderate wave-amplifying ability was found. The limit of low frequency response obtained previously by Denison and Baum was recovered, and the limitations of the quasi-steady theory were investigated.

  17. Wax Precipitation Modeled with Many Mixed Solid Phases

    Heidemann, Robert A.; Madsen, Jesper; Stenby, Erling Halfdan


    The behavior of the Coutinho UNIQUAC model for solid wax phases has been examined. The model can produce as many mixed solid phases as the number of waxy components. In binary mixtures, the solid rich in the lighter component contains little of the heavier component but the second phase shows sub...

  18. Solid-phase extraction-gas chromatography and solid-phase extraction-gas chromatography-mass spectrometry determination of corrosion inhibiting long-chain primary alkyl amines in chemical treatment of boiler water in water-steam systems of power plants.

    Kusch, Peter; Knupp, Gerd; Hergarten, Marcus; Kozupa, Marian; Majchrzak, Maria


    Gas chromatography with simultaneous flame-ionization detection (FID) and a nitrogen-phosphorus detection (NPD) as well as gas chromatography-mass spectrometry (GC/MS) has been used to characterize long-chain primary alkyl amines after derivatization with trifluoroacetic anhydride (TFAA). Electron impact ionization- (EI) and negative chemical ionization (NCI) mass spectra of trifluoroacetylated derivatives of the identified tert-octadecylamines are presented for the first time. The corrosion inhibiting alkyl amines were applied in a water-steam circuit of energy systems in the power industry. Solid-phase extraction (SPE) with octadecyl bonded silica (C18) sorbents followed by gas chromatography were used for quantification of the investigated tert-octadecylamines in boiler water, superheated steam and condensate samples from the power plant. The estimated values were: 89 microg l(-1)(n = 5, RSD = 7.8%), 45 microg l(-1) (n = 5, RSD = 5.4%) and 37 microg l(-1)(n = 5, RSD = 2.3%), respectively.

  19. Parallel solid-phase synthesis of diaryltriazoles

    Matthias Wrobel


    Full Text Available A series of substituted diaryltriazoles was prepared by a solid-phase-synthesis protocol using a modified Wang resin. The copper(I- or ruthenium(II-catalyzed 1,3-cycloaddition on the polymer bead allowed a rapid synthesis of the target compounds in a parallel fashion with in many cases good to excellent yields. Substituted diaryltriazoles resemble a molecular structure similar to established terphenyl-alpha-helix peptide mimics and have therefore the potential to act as selective inhibitors for protein–protein interactions.

  20. Chemical thermodynamics and the phase rule

    Franzen, H.F.; Myers, C.E.


    An attempt is made to show that the Gibbs Phase Rule can, in a sense, be obtained without using chemical thermodynamics per se but by using an assumption which is implicit in applications of thermodynamics. This development will be followed by some comments on some important thermodynamic relationships with particular emphasis on the distinction between chemical components and chemical species.

  1. The role of chemical interactions in ion-solid processes

    Dodson, B.W.


    Computer simulation of low-energy ion-solid processes has greatly broadened in scope in recent years. In particular, realistic descriptions of the ion-solid and solid-solid interactions can now be utilized. The molecular dynamics technique, in which the equations of motion of the interacting atoms are numerically integrated, can now be used to characterize ion-solid interactions in a range of model material systems. Despite practical limitations of this procedure, a number of substantial results have appeared. The available results are examined to investigate the qualitative influence that chemical interactions have on low-energy ion-solid processes. 26 refs., 4 figs.

  2. Density-functional theory for fluid-solid and solid-solid phase transitions

    Bharadwaj, Atul S.; Singh, Yashwant


    We develop a theory to describe solid-solid phase transitions. The density functional formalism of classical statistical mechanics is used to find an exact expression for the difference in the grand thermodynamic potentials of the two coexisting phases. The expression involves both the symmetry conserving and the symmetry broken parts of the direct pair correlation function. The theory is used to calculate phase diagram of systems of soft spheres interacting via inverse power potentials u (r ) =ɛ "close="1 /n )">σ /r n , where parameter n measures softness of the potential. We find that for 1 /n ≥0.154 the body-centred-cubic (bcc) structure is preferred. The bcc structure transforms into the fcc structure upon increasing the density. The calculated phase diagram is in good agreement with the one found from molecular simulations.

  3. Determination of 2-, 3-, 4-methylpentanoic and cyclohexanecarboxylic acids in wine: development of a selective method based on solid phase extraction and gas chromatography-negative chemical ionization mass spectrometry and its application to different wines and alcoholic beverages.

    Gracia-Moreno, Elisa; Lopez, Ricardo; Ferreira, Vicente


    A method to analyse 2-methylpentanoic, 3-methylpentanoic and 4-methylpentanoic acids as well as cyclohexanecarboxylic acid has been developed and applied to wine and other alcoholic beverages. Selective isolation with solid phase extraction, derivatization with 2,3,4,5,6-pentafluorobenzyl bromide at room temperature for 30 minutes, and further analysis by gas chromatography-mass spectrometry in negative chemical ionization mode provides detection limits between 0.4 and 2.4 ng/L. Good linearity up to 3.6 μg/L, satisfactory reproducibility (RSD<10%) and signal recovery of around 100% represent a robust method of analysis. Concentration data of these analytes in wine and other alcoholic beverages are reported for the first time. The levels found ranged from the method detection limits to 2630 ng/L, 2040 ng/L and 3810 ng/L for 2-, 3- and 4-methylpentanoic acids, respectively, and to 1780 ng/L for cyclohexanecarboxylic acid. There are significant differences depending on the type of wine or beverage. Distilled beverages, beer and aged wines have higher contents in methylpentanoic and cyclohexanecarboxylic acids.

  4. Gas-phase chemical dynamics

    Weston, R.E. Jr.; Sears, T.J.; Preses, J.M. [Brookhaven National Laboratory, Upton, NY (United States)


    Research in this program is directed towards the spectroscopy of small free radicals and reactive molecules and the state-to-state dynamics of gas phase collision, energy transfer, and photodissociation phenomena. Work on several systems is summarized here.

  5. Gas phase chemical detection with an integrated chemical analysis system



    Microfabrication technology has been applied to the development of a miniature, multi-channel gas phase chemical laboratory that provides fast response, small size, and enhanced versatility and chemical discrimination. Each analysis channel includes a sample preconcentrator followed by a gas chromatographic separator and a chemically selective surface acoustic wave detector array to achieve high sensitivity and selectivity. The performance of the components, individually and collectively, is described.

  6. Critical Regimes of Two-Phase Flows with a Polydisperse Solid Phase

    Barsky, Eugene


    This book brings to light peculiarities of the formation of critical regimes of two-phase flows with a polydisperse solid phase. A definition of entropy is formulated on the basis of statistical analysis of these peculiarities. The physical meaning of entropy and its correlation with other parameters determining two-phase flows are clearly defined. The interrelations and main differences between this entropy and the thermodynamic one are revealed. The main regularities of two-phase flows both in critical and in other regimes are established using the notion of entropy. This parameter serves as a basis for a deeper insight into the physics of the process and for the development of exhaustive techniques of mass exchange estimation in such flows. The book is intended for graduate and postgraduate students of engineering studying two-phase flows, and to scientists and engineers engaged in specific problems of such fields as chemical technology, mineral dressing, modern ceramics, microelectronics, pharmacology, po...

  7. Solid Phase Characterization of Tank 241-C-108 Residual Waste Solids Samples

    Cooke, Gary A.; Pestovich, John A.; Huber, Heinz J.


    This report presents the results for solid phase characterization (SPC) of solid samples removed from tank 241-C-108 (C-108) on August 12-13,2012, using the off-riser sampler. Samples were received at the 222-S Laboratory on August 13 and were described and photographed. The SPC analyses that were performed include scanning electron microscopy (SEM) using the ASPEX(R)l scanning electron microscope, X-ray diffraction (XRD) using the Rigaku(R) 2 MiniFlex X-ray diffractometer, and polarized light microscopy (PLM) using the Nikon(R) 3 Eclipse Pol optical microscope. The SEM is equipped with an energy dispersive X-ray spectrometer (EDS) to provide chemical information. Gary A. Cooke conducted the SEM analysis, John A. Pestovich performed the XRD analysis, and Dr. Heinz J. Huber performed the PLM examination. The results of these analyses are presented here.

  8. Automated mini-column solid-phase extraction cleanup for high-throughput analysis of chemical contaminants in foods by low-pressure gas chromatography – tandem mass spectrometry

    This study demonstrated the application of an automated high-throughput mini-cartridge solid-phase extraction (mini-SPE) cleanup for the rapid low-pressure gas chromatography – tandem mass spectrometry (LPGC-MS/MS) analysis of pesticides and environmental contaminants in QuEChERS extracts of foods. ...

  9. Solid Phase Synthesis of Polymacromer and Copolymacromer Brushes


    REPORT Solid Phase Synthesis of Polymacromer and Copolymacromer Brushes 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: We report a novel solid phase...form poly-macromer brushes wherein macromonomers are linked via triazole groups. After each addition step, the terminal alkyne group can be deprotected...Research Triangle Park, NC 27709-2211 15. SUBJECT TERMS Solid Phase Synthesis , polymers and copolymers Hernán R. Rengifo, Cristian Grigoras, Benjamin I

  10. Use of geotextile tubes with chemical amendments to dewater dairy lagoon solids.

    Worley, J W; Bass, T M; Vendrell, P F


    Three geo-textile filtration tubes were used to dewater lagoon solids from a first stage dairy lagoon using chemical amendments (aluminum sulfate and a polymer) to enhance the separation process. This experiment had previously been done without chemical amendment. The chemical amendments speeded the dewatering process so that filling could be accomplished sooner, and also increased the removal rate of nutrients, especially phosphorus into the solid phase. Chemically amended slurry was pumped from the lagoon into the tube with the filtered liquid seeping from the tube and returning to the lagoon. Each tube was filled five to six times at 2-5-day intervals, and then allowed to dewater for 2 weeks before sampling the solid fraction in the tube. Separation efficiency improved from 79% to 99% for phosphorous and from 92% to 100% for organic nitrogen with chemical amendment. Time required for dewatering was significantly reduced by chemical amendment. Cost for the tube was approximately $10/m(3) of recovered solids with no chemical amendment and cost including the chemicals was approximately $14/m(3) of recovered solids.

  11. The growth and tensile deformation behavior of the silver solid solution phase with zinc

    Wu, Jiaqi, E-mail: [Department of Electrical Engineering and Computer Science, University of California, Irvine, CA 92697-2660 (United States); Materials and Manufacturing Technology, University of California, Irvine, CA 92697-2660 (United States); Lee, Chin C. [Department of Electrical Engineering and Computer Science, University of California, Irvine, CA 92697-2660 (United States); Materials and Manufacturing Technology, University of California, Irvine, CA 92697-2660 (United States)


    The growth of homogeneous silver solid solution phase with zinc are conducted at two different compositions. X-ray diffraction (XRD) and Scanning electron microscope/Energy dispersive X-ray spectroscopy (SEM/EDX) are carried out for phase identification and chemical composition verification. The mechanical properties of silver solid solution phase with zinc are evaluated by tensile test. The engineering and true stress vs. strain curves are presented and analyzed, with those of pure silver in comparison. According to the experimental results, silver solid solution phase with zinc at both compositions show tempered yield strength, high tensile strength and large uniform strain compared to those of pure silver. Fractography further confirmed the superior ductility of silver solid solution phase with zinc at both compositions. Our preliminary but encouraging results may pave the way for the silver based alloys to be applied in industries such as electronic packaging and structure engineering.

  12. Stable solid-phase Rh antigen.

    Yared, M A; Moise, K J; Rodkey, L S


    Numerous investigators have attempted to isolate the Rh antigens in a stable, immunologically reactive form since the discovery of the Rh system over 56 years ago. We report here a successful and reproducible approach to solubilizing and adsorbing the human Rh antigen(s) to a solid-phase matrix in an antigenically active form. Similar results were obtained with rabbit A/D/F red blood cell antigens. The antigen preparation was made by dissolution of the red blood cell membrane lipid followed by fragmentation of the residual cytoskeleton in an EDTA solution at low ionic strength. The antigenic activity of the soluble preparations was labile in standard buffers but was stable in zwitterionic buffers for extended periods of time. Further studies showed that the antigenic activity of these preparations was enhanced, as was their affinity for plastic surfaces, in the presence of acidic zwitterionic buffers. Adherence to plastic surfaces at low pH maintained antigenic reactivity and specificity for antibody was retained. The data show that this approach yields a stable form of antigenically active human Rh D antigen that could be used in a red blood cell-free assay for quantitative analysis of Rh D antibody and for Rh D antibody immunoadsorption and purification.

  13. QCD phase diagram with isospin chemical potential

    Brandt, Bastian B


    In this contribution we investigate the phase diagram of QCD in the presence of an isospin chemical potential. To alleviate the infrared problems of the theory associated with pion condensation, we introduce the pionic source as an infrared regulator. We discuss various methods to extrapolate the results to vanishing pionic source, including a novel method based on the singular value spectrum of the massive Dirac operator, a leading-order reweighting and a spline Monte-Carlo fit. Our main results concern the phase transition boundary between the normal and the pion condensation phases and the chiral/deconfinement transition temperature as a function of the chemical potential. In addition, we perform a quantitative comparison between our direct results and a Taylor-expansion obtained at zero chemical potential to assess the applicability range of the latter.

  14. Preparation of Ion Exchange Films for Solid-Phase Spectrophotometry and Solid-Phase Fluorometry

    Hill, Carol M.; Street, Kenneth W.; Tanner, Stephen P.; Philipp, Warren H.


    Atomic spectroscopy has dominated the field of trace inorganic analysis because of its high sensitivity and selectivity. The advantages gained by the atomic spectroscopies come with the disadvantage of expensive and often complicated instrumentation. Solid-phase spectroscopy, in which the analyte is preconcentrated on a solid medium followed by conventional spectrophotometry or fluorometry, requires less expensive instrumentation and has considerable sensitivity and selectivity. The sensitivity gains come from preconcentration and the use of chromophore (or fluorophore) developers and the selectivity is achieved by use of ion exchange conditions that favor the analyte in combination with speciative chromophores. Little work has been done to optimize the ion exchange medium (IEM) associated with these techniques. In this report we present a method for making ion exchange polymer films, which considerably simplify the solid-phase spectroscopic techniques. The polymer consists of formaldehyde-crosslinked polyvinyl alcohol with polyacrylic acid entrapped therein. The films are a carboxylate weak cation exchanger in the calcium form. They are mechanically sturdy and optically transparent in the ultraviolet and visible portion of the spectrum, which makes them suitable for spectrophotometry and fluorometry.

  15. Investigation of binary solid phases by calorimetry and kinetic modelling

    Matovic, M.


    The traditional methods for the determination of liquid-solid phase diagrams are based on the assumption that the overall equilibrium is established between the phases. However, the result of the crystallization of a liquid mixture will typically be a non-equilibrium or metastable state of the solid

  16. Solid-phase microextraction for bioconcentration studies according to OECD TG 305

    Duering, Rolf-Alexander; Boehm, Leonard [Land Use and Nutrition (IFZ) Justus Liebig University Giessen, Institute of Soil Science and Soil Conservation, Research Centre for BioSystems, Giessen (Germany); Schlechtriem, Christian [Fraunhofer Institute for Molecular Biology and Applied Ecology (IME), Schmallenberg (Germany)


    An important aim of the European Community Regulation on chemicals and their safe use is the identification of (very) persistent, (very) bioaccumulative, and toxic substances. In other regulatory chemical safety assessments (pharmaceuticals, biocides, pesticides), the identification of such (very) persistent, (very) bioaccumulative, and toxic substances is of increasing importance. Solid-phase microextraction is especially capable of extracting total water concentrations as well as the freely dissolved fraction of analytes in the water phase, which is available for bioconcentration in fish. However, although already well established in environmental analyses to determine and quantify analytes mainly in aqueous matrices, solid-phase microextraction is still a rather unusual method in regulatory ecotoxicological research. Here, the potential benefits and drawbacks of solid-phase microextraction are discussed as an analytical routine approach for aquatic bioconcentration studies according to OECD TG 305, with a special focus on the testing of hydrophobic organic compounds characterized by log K{sub OW}> 5. (orig.)

  17. Solid-solid phase transitions determined by differential scanning calorimetry.

    Murrill, E.; Whitehead, M. E.; Breed, L.


    Data are presented to show that tris(hydroxymethyl)acetic acid, monochloropentaerythritol, monofluoropentaerythritol, difluoropentaerythritol, monoaminopentaerythritol, and diaminopentaerythritol exhibit solid-state transitions to a plastic crystalline state. Transitional enthalpies in many of these substances are lower than might be expected by analogy with related structures, suggesting that some configurational contributions to their entropy increments have been inhibited.

  18. Solid-solid phase transitions determined by differential scanning calorimetry.

    Murrill, E.; Whitehead, M. E.; Breed, L.


    Data are presented to show that tris(hydroxymethyl)acetic acid, monochloropentaerythritol, monofluoropentaerythritol, difluoropentaerythritol, monoaminopentaerythritol, and diaminopentaerythritol exhibit solid-state transitions to a plastic crystalline state. Transitional enthalpies in many of these substances are lower than might be expected by analogy with related structures, suggesting that some configurational contributions to their entropy increments have been inhibited.

  19. Computational thermal, chemical, fluid, and solid mechanics for geosystems management.

    Davison, Scott; Alger, Nicholas; Turner, Daniel Zack; Subia, Samuel Ramirez; Carnes, Brian; Martinez, Mario J.; Notz, Patrick K.; Klise, Katherine A.; Stone, Charles Michael; Field, Richard V., Jr.; Newell, Pania; Jove-Colon, Carlos F.; Red-Horse, John Robert; Bishop, Joseph E.; Dewers, Thomas A.; Hopkins, Polly L.; Mesh, Mikhail; Bean, James E.; Moffat, Harry K.; Yoon, Hongkyu


    This document summarizes research performed under the SNL LDRD entitled - Computational Mechanics for Geosystems Management to Support the Energy and Natural Resources Mission. The main accomplishment was development of a foundational SNL capability for computational thermal, chemical, fluid, and solid mechanics analysis of geosystems. The code was developed within the SNL Sierra software system. This report summarizes the capabilities of the simulation code and the supporting research and development conducted under this LDRD. The main goal of this project was the development of a foundational capability for coupled thermal, hydrological, mechanical, chemical (THMC) simulation of heterogeneous geosystems utilizing massively parallel processing. To solve these complex issues, this project integrated research in numerical mathematics and algorithms for chemically reactive multiphase systems with computer science research in adaptive coupled solution control and framework architecture. This report summarizes and demonstrates the capabilities that were developed together with the supporting research underlying the models. Key accomplishments are: (1) General capability for modeling nonisothermal, multiphase, multicomponent flow in heterogeneous porous geologic materials; (2) General capability to model multiphase reactive transport of species in heterogeneous porous media; (3) Constitutive models for describing real, general geomaterials under multiphase conditions utilizing laboratory data; (4) General capability to couple nonisothermal reactive flow with geomechanics (THMC); (5) Phase behavior thermodynamics for the CO2-H2O-NaCl system. General implementation enables modeling of other fluid mixtures. Adaptive look-up tables enable thermodynamic capability to other simulators; (6) Capability for statistical modeling of heterogeneity in geologic materials; and (7) Simulator utilizes unstructured grids on parallel processing computers.

  20. Chemical pathways and kinetic rates of the N(4S) + N2 → N3 solid phase reaction: could the N3 radical be a temperature sensor of nitrogen ices in dense molecular clouds?

    Mencos, Alejandro; Nourry, Sendres; Krim, Lahouari


    Even though the N3 radical has not yet been detected in the interstellar medium, its formation still remains a challenge. For a long time, bombardments of N2 ices by energetic particles were the only way to from the azide radical as it was thought that ultraviolet (UV) photons were not strong enough to fragment the molecular nitrogen into N atoms. Consequently, it had been suggested that N3 could be used as discriminator between ice radiolysis and ice photolysis until a very recent study that has shown that photodecomposition of molecular nitrogen by UV photons might also be a source of the azide radical. In contrast to all these nitrogen ice bombarding experiments, only two laboratory studies have investigated the N3 formation where the reactants N and N2 mixed in the gas phase were co-condensed at 12 K, and this raised a new question concerning whether N + N2 → N3 took place in the solid phase or in the gas phase. The experimental results of these two studies are contradictory and the problem of the characterization of N3 formation by co-condensing atomic N and molecular N2 has persisted to the present day. In this paper, we give a clear answer to this question, by investigating the kinetic rates of the N(4S) + N2 → N3 reaction in the solid phase in the temperature range of 3-35 K. We find a rate constant of 7.7 × 10-23 s-1 molecule-1 cm3 for the azide radical formation in the solid phase and we provide new information on the N3 infrared signature, which could be used to characterize the temperature and the structure of nitrogen ices.

  1. Solid-phase synthesis of siRNA oligonucleotides.

    Beaucage, Serge L


    Since the discovery of RNA interference (RNAi) as a means to silence the expression of specific genes, small interfering RNA (siRNA) oligonucleotides have been recognized as powerful tools for targeting therapeutically important mRNAs and eliciting their destruction. This discovery has created a high demand for synthetic oligoribonucleotides as potential therapeutics and has spurred a renaissance in the development of rapid, efficient methods for solid-phase RNA synthesis. The design and implementation of 2'-hydroxyl protecting groups that provide ribonucleoside phosphoramidites with coupling kinetics and coupling efficiencies comparable to those of deoxyribonucleoside phosphoramidites are key to the production of RNA oligonucleotides in sufficient quantity and purity for pharmaceutical applications. In this context, various siRNAs were chemically modified to identify the biophysical and biochemical parameters necessary for effective and stable RNAi-mediated gene-silencing activities.



    Velocities of solid phase and liquid phase in debris flow are one key problem to research on impact and abrasion mechanism of banks and control structures under action of debris flow. Debris flow was simplified as two-phase liquid composed of solid phase with the same diameter particles and liquid phase with the same mechanical features. Assume debris flow was one-dimension two-phase liquid moving to one direction,then general equations of velocities of solid phase and liquid phase were founded in twophase theory. Methods to calculate average pressures, volume forces and surface forces of debris flow control volume were established. Specially, surface forces were ascertained using Bingham's rheology equation of liquid phase and Bagnold's testing results about interaction between particles of solid phase. Proportional coefficient of velocities between liquid phase and solid phase was put forward, meanwhile, divergent coefficient between theoretical velocity and real velocity of solid phase was provided too. To state succinctly before, method to calculate velocities of solid phase and liquid phase was obtained through solution to general equations. The method is suitable for both viscous debris flow and thin debris flow. Additionally, velocities every phase can be identified through analyzing deposits in-situ after occurring of debris flow. It is obvious from engineering case the result in the method is consistent to that in real-time field observation.

  3. The role of solid-solid phase transitions in mantle convection

    Faccenda, Manuele; Dal Zilio, Luca


    With changing pressure and temperature conditions, downwelling and upwelling crustal and mantle rocks experience several solid-solid phase transitions that affect the mineral physical properties owing to structural changes in the crystal lattice and to the absorption or release of latent heat. Variations in density, together with phase boundary deflections related to the non-null reaction slope, generate important buoyancy forces that add to those induced by thermal perturbations. These buoyancy forces are proportional to the density contrast between reactant and product phases, their volume fraction, the slope and the sharpness of the reaction, and affect the style of mantle convection depending on the system composition. In a homogeneous pyrolitic mantle there is little tendency for layered convection, with slabs that may stagnate in the transition zone because of the positive buoyancy caused by post-spinel and post-ilmenite reactions, and hot plumes that are accelerated by phase transformations in the 600-800 km depth range. By adding chemical and mineralogical heterogeneities as on Earth, phase transitions introduce bulk rock and volatiles filtering effects that generate a compositional gradient throughout the entire mantle, with levels that are enriched or depleted in one or more of these components. Phase transitions often lead to mechanical softening or hardening that can be related to a different intrinsic mechanical behaviour and volatile solubility of the product phases, the heating or cooling associated with latent heat, and the transient grain size reduction in downwelling cold material. Strong variations in viscosity would enhance layered mantle convection, causing slab stagnation and plume ponding. At low temperatures and relatively dry conditions, reactions are delayed due to the sluggish kinetics, so that non-equilibrium phase aggregates can persist metastably beyond the equilibrium phase boundary. Survival of low-density metastable olivine

  4. Determination of Human-Health Pharmaceuticals in Filtered Water by Chemically Modified Styrene-Divinylbenzene Resin-Based Solid-Phase Extraction and High-Performance Liquid Chromatography/Mass Spectrometry

    Furlong, Edward T.; Werner, Stephen L.; Anderson, Bruce D.; Cahill, Jeffery D.


    In 1999, the Methods Research and Development Program of the U.S. Geological Survey National Water Quality Laboratory began the process of developing a method designed to identify and quantify human-health pharmaceuticals in four filtered water-sample types: reagent water, ground water, surface water minimally affected by human contributions, and surface water that contains a substantial fraction of treated wastewater. Compounds derived from human pharmaceutical and personal-care product use, which enter the environment through wastewater discharge, are a newly emerging area of concern; this method was intended to fulfill the need for a highly sensitive and highly selective means to identify and quantify 14 commonly used human pharmaceuticals in filtered-water samples. The concentrations of 12 pharmaceuticals are reported without qualification; the concentrations of two pharmaceuticals are reported as estimates because long-term reagent-spike sample recoveries fall below acceptance criteria for reporting concentrations without qualification. The method uses a chemically modified styrene-divinylbenzene resin-based solid-phase extraction (SPE) cartridge for analyte isolation and concentration. For analyte detection and quantitation, an instrumental method was developed that used a high-performance liquid chromatography/mass spectrometry (HPLC/MS) system to separate the pharmaceuticals of interest from each other and coextracted material. Immediately following separation, the pharmaceuticals are ionized by electrospray ionization operated in the positive mode, and the positive ions produced are detected, identified, and quantified using a quadrupole mass spectrometer. In this method, 1-liter water samples are first filtered, either in the field or in the laboratory, using a 0.7-micrometer (um) nominal pore size glass-fiber filter to remove suspended solids. The filtered samples then are passed through cleaned and conditioned SPE cartridges at a rate of about 15

  5. Analysis of solid-liquid phase change heat transfer enhancement

    张寅平; 王馨


    Solid-liquid phase change processes have two important features: the process is an approximately isothermal process and the heat of fusion of phase change material tends to be much greater than its specific heat. Therefore, if any phase change material adjacent to a hot or cold surface undergoes phase change, the heat transfer rate on the surface will be noticeably enhanced. This paper presents a novel insight into the mechanisms of heat transfer enhancement induced by solid-liquid phase change based on the analogy analysis for heat conduction with an internal heat source and solid-liquid phase change heat transfer. Three degrees of surface heat transfer enhancement for different conditions are explored, and corresponding formulae are written to describe them. The factors influencing the degrees of heat transfer enhancement are clarified and their effects quantitatively analyzed. Both the novel insight and the analysis contribute to effective application of phase change heat transfer enhancement technique.

  6. Studies on solid phase synthesis,characterization and fluorescent property of the new rare earth complexes

    Shi, Jianwei; Xiaoxu TENG; Wang, Linling; Long, Rong


    Rare earth-β-diketone ligand complex luminescent material has stable chemical properties and excellent luminous property. Using europium oxide and (γ-NTA) as raw materials, novel rare earth-β-dione complexes are synthesized by solid state coordination chemistry. The synthesis temperature and milling time are discussed for optimization. Experimental results show that the suitable reaction situation is at 50 ℃ and 20 h for solid-phase synthesis. The compositions and structures of the complexes...

  7. Chemical Identification at the Solid-Liquid Interface.

    Söngen, Hagen; Marutschke, Christoph; Spijker, Peter; Holmgren, Eric; Hermes, Ilka; Bechstein, Ralf; Klassen, Stefanie; Tracey, John; Foster, Adam S; Kühnle, Angelika


    Solid-liquid interfaces are decisive for a wide range of natural and technological processes, including fields as diverse as geochemistry and environmental science as well as catalysis and corrosion protection. Dynamic atomic force microscopy nowadays provides unparalleled structural insights into solid-liquid interfaces, including the solvation structure above the surface. In contrast, chemical identification of individual interfacial atoms still remains a considerable challenge. So far, an identification of chemically alike atoms in a surface alloy has only been demonstrated under well-controlled ultrahigh vacuum conditions. In liquids, the recent advent of three-dimensional force mapping has opened the potential to discriminate between anionic and cationic surface species. However, a full chemical identification will also include the far more challenging situation of alike interfacial atoms (i.e., with the same net charge). Here we demonstrate the chemical identification capabilities of dynamic atomic force microscopy at solid-liquid interfaces by identifying Ca and Mg cations at the dolomite-water interface. Analyzing site-specific vertical positions of hydration layers and comparing them with molecular dynamics simulations unambiguously unravels the minute but decisive difference in ion hydration and provides a clear means for telling calcium and magnesium ions apart. Our work, thus, demonstrates the chemical identification capabilities of dynamic AFM at the solid-liquid interface.

  8. In situ transmission electron microscopy of solid-liquid phase transition of silica encapsulated bismuth nanoparticles

    Hu, Jianjun; Hong, Yan; Muratore, Chris; Su, Ming; Voevodin, Andrey A.


    The solid-liquid phase transition of silica encapsulated bismuth nanoparticles was studied by in situ transmission electron microscopy (TEM). The nanoparticles were prepared by a two-step chemical synthesis process involving thermal decomposition of organometallic precursors for nucleating bismuth and a sol-gel process for growing silica. The microstructural and chemical analyses of the nanoparticles were performed using high-resolution TEM, Z-contrast imaging, focused ion beam milling, and X-ray energy dispersive spectroscopy. Solid-liquid-solid phase transitions of the nanoparticles were directly recorded by electron diffractions and TEM images. The silica encapsulation of the nanoparticles prevented agglomeration and allowed particles to preserve their original volume upon melting, which is desirable for applications of phase change nanoparticles with consistently repeatable thermal properties.

  9. Inhibition of a solid phase reaction among excipients that accelerates drug release from a solid dispersion with aging.

    Mizuno, Masayasu; Hirakura, Yutaka; Yamane, Ikuro; Miyanishi, Hideo; Yokota, Shoji; Hattori, Munetaka; Kajiyama, Atsushi


    Hydrophobic drug substances can be formulated as a solid dispersion or solution using macromolecular matrices with high glass transition temperatures to attain satisfactory dissolution. However, very few marketed products have previously relied on solid dispersion technology due to physical and chemical instability problems, and processing difficulties. In the present study, a modified release product of a therapeutic drug for hypertension, Barnidipine hydrochloride, was developed. The drug product consisted of solid dispersion based on a matrix of carboxymethylethylcellulose (CMEC), which was produced using the spray-coating method. An enteric coat layer was sprayed on the surface of the solid dispersion to control drug release. Interestingly, the release rate accelerated as the drug product aged, while there were no indications of deceleration of the release rate which was due to crystallization of the drug substance. To prevent changes in the dissolution kinetics during storage periods, a variety of processing conditions were tried. It was found that not only use of non-aqueous solvents but also a reduction in coating temperatures consistently resulted in stable solid dispersions. The molecular bases of dissolution of the drug substance from those matrices were investigated. The molecular weight of CMEC was found to be a dominant factor that determined dissolution kinetics, which followed zero-order release, suggesting an involvement of an osmotic pumping mechanism. While dissolution was faster using a higher molecular weight CMEC, the molecular weight of CMEC in the drug product slowly increased with aging (solid phase reaction) depending on the processing conditions, causing the time-induced elevation of dissolution. While no crystalline components were found in the solid dispersion, the amorphous structure maintained a degree of non-equilibrium by nature. Plasticization by water in the coating solution relaxed the amorphous system and facilitated phase

  10. Impact of Using a High Surface Area Solid Phase Micro Extraction Device and Fast Gas Chromatography Heating Rates in the Sampling and Analysis of Trace Level Chemical Warfare Agents and CWA-Like Compounds


    rest of the inner diameter of the column is filled with inert carrier gas (the mobile phase), often helium or hydrogen . Chemical compounds are...Sample of Liquid CWA-Degradation Product The VX degradation compound, 2-(diisopropylaminoethyl)ethyl sulfide (2-DES) was diluted in methylene chloride...demonstrated separation of CWA mixture components ranging in molecular weight from m/z 140 (sarin) to 466 (T2 toxin ) with a field-portable GC/MS system

  11. Automated solid-phase synthesis of oligosaccharides containing sialic acids

    Chian-Hui Lai


    Full Text Available A sialic acid glycosyl phosphate building block was designed and synthesized. This building block was used to prepare α-sialylated oligosaccharides by automated solid-phase synthesis selectively.


    B. S. Chandravanshi

    cation exchange-solid phase extraction (SCX-SPE) was investigated as an .... Stock solutions, with a concentration of 1.00 mg/mL were prepared ... Johannesburg, South Africa) connected to a vacuum pump (Vacuubrand, GMBH, Germany).

  13. Combinatorial Solid-Phase Synthesis of Balanol Analogues

    Nielsen, John; Lyngsø, Lars Ole


    The natural product balanol has served as a template for the design and synthesis of a combinatorial library using solid-phase chemistry. Using a retrosynthetic analysis, the structural analogues have been assembled from three relatively accessible building blocks. The solid-phase chemistry inclu...... including MSNT-mediated esterification of both support-bound alcohols and carboxylic acids has been implemented successfully. Copyright (C) 1996 Elsevier Science Ltd....

  14. Combinatorial Solid-Phase Synthesis of Balanol Analogues

    Nielsen, John; Lyngsø, Lars Ole


    The natural product balanol has served as a template for the design and synthesis of a combinatorial library using solid-phase chemistry. Using a retrosynthetic analysis, the structural analogues have been assembled from three relatively accessible building blocks. The solid-phase chemistry inclu...... including MSNT-mediated esterification of both support-bound alcohols and carboxylic acids has been implemented successfully. Copyright (C) 1996 Elsevier Science Ltd....

  15. Automated solid-phase peptide synthesis to obtain therapeutic peptides

    Veronika Mäde


    Full Text Available The great versatility and the inherent high affinities of peptides for their respective targets have led to tremendous progress for therapeutic applications in the last years. In order to increase the drugability of these frequently unstable and rapidly cleared molecules, chemical modifications are of great interest. Automated solid-phase peptide synthesis (SPPS offers a suitable technology to produce chemically engineered peptides. This review concentrates on the application of SPPS by Fmoc/t-Bu protecting-group strategy, which is most commonly used. Critical issues and suggestions for the synthesis are covered. The development of automated methods from conventional to essentially improved microwave-assisted instruments is discussed. In order to improve pharmacokinetic properties of peptides, lipidation and PEGylation are described as covalent conjugation methods, which can be applied by a combination of automated and manual synthesis approaches. The synthesis and application of SPPS is described for neuropeptide Y receptor analogs as an example for bioactive hormones. The applied strategies represent innovative and potent methods for the development of novel peptide drug candidates that can be manufactured with optimized automated synthesis technologies.

  16. Fabrication of polyaniline-coated halloysite nanotubes by in situ chemical polymerization as a solid-phase microextraction coating for the analysis of volatile organic compounds in aqueous solutions.

    Abolghasemi, Mir Mahdi; Arsalani, Naser; Yousefi, Vahid; Arsalani, Mahmood; Piryaei, Marzieh


    We have synthesized an organic-inorganic polyaniline-halloysite nanotube composite by an in situ polymerization method. This nanocomposite is immobilized on a stainless-steel wire and can be used as a fiber coating for solid-phase microextraction. It was found that our new solid-phase microextraction fiber is an excellent adsorbent for the extraction of some volatile organic compounds in aqueous samples in combination with gas chromatography and mass spectrometry. The coating can be prepared easily, is mechanically stable, and exhibits relatively high thermal stability. It is capable of extracting phenolic compounds from water samples. Following thermal desorption, the phenols were quantified by gas chromatography with mass spectrometry. The effects of extraction temperature, extraction time, sample ionic strength, stirring rate, pH, desorption temperature and desorption time were studied. Under optimal conditions, the repeatability for one fiber (n = 5), expressed as the relative standard deviation, is between 6.2 and 9.1%. The detection limits range from 0.005 to 4 ng/mL. The method offers the advantage of being simple to use, with a shorter analysis time, lower cost of equipment and higher thermal stability of the fiber in comparison to conventional methods of analysis.

  17. Nanoscale chemical analysis and imaging of solid oxide cells

    Hauch, Anne; Bowen, Jacob R.; Kuhn, Luise Theil;


    The performance of solid oxide cells (SOCs) is highly dependent on triple phase boundaries (TPBs). Therefore, detailed TPB characterization is crucial for their further development. We demonstrate that it is possible to prepare a similar to 50 nm thick transmission electron microscopy (TEM) lamel...... of nanoscale impurity phases at the TPBs has been obtained with a few nanometers lateral resolution. (c) 2008 The Electrochemical Society....

  18. The Structural Phase Transition in Solid DCN

    Dietrich, O. W.; Mackenzie, Gordon A.; Pawley, G. S.


    Neutron scattering measurements on deuterated hydrogen cyanide have shown that the structural phase change from a tetragonal to an orthorhombic form at 160K is a first-order transition. A transverse acoustic phonon mode, which has the symmetry of the phase change, was observed at very low energies...... and showed 'softening' as the transition temperature was approached from above....

  19. Magnetic Solid Phase Extraction Applied to Food Analysis

    Israel S. Ibarra


    Full Text Available Magnetic solid phase extraction has been used as pretreatment technique for the analysis of several compounds because of its advantages when it is compared with classic methods. This methodology is based on the use of magnetic solids as adsorbents for preconcentration of different analytes from complex matrices. Magnetic solid phase extraction minimizes the use of additional steps such as precipitation, centrifugation, and filtration which decreases the manipulation of the sample. In this review, we describe the main procedures used for synthesis, characterization, and application of this pretreatment technique which were applied in food analysis.

  20. Fuel spill identification using solid-phase extraction and solid-phase microextraction. 1. Aviation turbine fuels.

    Lavine, B K; Brzozowski, D M; Ritter, J; Moores, A J; Mayfield, H T


    The water-soluble fraction of aviation jet fuels is examined using solid-phase extraction and solid-phase microextraction. Gas chromatographic profiles of solid-phase extracts and solid-phase microextracts of the water-soluble fraction of kerosene- and nonkerosene-based jet fuels reveal that each jet fuel possesses a unique profile. Pattern recognition analysis reveals fingerprint patterns within the data characteristic of fuel type. By using a novel genetic algorithm (GA) that emulates human pattern recognition through machine learning, it is possible to identify features characteristic of the chromatographic profile of each fuel class. The pattern recognition GA identifies a set of features that optimize the separation of the fuel classes in a plot of the two largest principal components of the data. Because principal components maximize variance, the bulk of the information encoded by the selected features is primarily about the differences between the fuel classes.

  1. N-Acyliminium Intermediates in Solid-Phase Synthesis

    Quement, Sebastian Thordal le; Petersen, Rico; Meldal, M.


    N-Acyliminium ions are powerful intermediates in synthetic organic chemistry. Examples of their use are numerous in solution-phase synthesis, but there are unmerited few reports on these highly reactive electrophiles in solid-phase synthesis. The present review covers the literature to date and i...

  2. Solid phase extraction method for determination of mitragynine in ...

    mitragynine in urine and its application to mitragynine excretion ... Purpose: To develop a solid phase extraction (SPE) method that utilizes reverse-phase high performance .... solution of MG (1 mg/mL) which was further ... Facility, Prince of Songkla University and carried ..... d), which permit unrestricted use, distribution,.

  3. Heterogeneous Ferroelectric Solid Solutions Phases and Domain States

    Topolov, Vitaly


    The book deals with perovskite-type ferroelectric solid solutions for modern materials science and applications, solving problems of complicated heterophase/domain structures near the morphotropic phase boundary and applications to various systems with morphotropic phases. In this book domain state–interface diagrams are presented for the interpretation of heterophase states in perovskite-type ferroelectric solid solutions. It allows to describe the stress relief in the presence of polydomain phases, the behavior of unit-cell parameters of coexisting phases and the effect of external electric fields. The novelty of the book consists in (i) the first systematization of data about heterophase states and their evolution in ferroelectric solid solutions (ii) the general interpretation of heterophase and domain structures at changing temperature, composition or electric field (iii) the complete analysis of interconnection domain structures, unit-cell parameters changes, heterophase structures and stress relief.

  4. Anisotropic kinetics of solid phase transition from first principles: alpha-omega phase transformation of Zr.

    Guan, Shu-Hui; Liu, Zhi-Pan


    Structural inhomogeneity is ubiquitous in solid crystals and plays critical roles in phase nucleation and propagation. Here, we develop a heterogeneous solid-solid phase transition theory for predicting the prevailing heterophase junctions, the metastable states governing microstructure evolution in solids. Using this theory and first-principles pathway sampling simulation, we determine two types of heterophase junctions pertaining to metal α-ω phase transition at different pressures and predict the reversibility of transformation only at low pressures, i.e. below 7 GPa. The low-pressure transformation is dominated by displacive Martensitic mechanism, while the high-pressure one is controlled by the reconstructive mechanism. The mechanism of α-ω phase transition is thus highly pressure-sensitive, for which the traditional homogeneous model fails to explain the experimental observations. The results provide the first atomic-level evidence on the coexistence of two different solid phase transition mechanisms in one system.

  5. The Structural Phase Transition in Solid DCN

    Dietrich, O. W.; Mackenzie, Gordon A.; Pawley, G. S.


    Neutron scattering measurements on deuterated hydrogen cyanide have shown that the structural phase transition from a tetragonal to an orthorhombic form at 160 K is a first order transition. A transverse acoustic phonon mode, which has the symmetry of the transition was observed at very low energ...... energies and showed “softening” as the transition was approached from above.......Neutron scattering measurements on deuterated hydrogen cyanide have shown that the structural phase transition from a tetragonal to an orthorhombic form at 160 K is a first order transition. A transverse acoustic phonon mode, which has the symmetry of the transition was observed at very low...

  6. Chemical forms of solid fission products in the irradiated uranium—plutonium mixed nitride fuel

    Arai, Yasuo; Maeda, Atsushi; Shiozawa, Ken-ichi; Ohmichi, Toshihiko


    Chemical forms of solid fission products in the irradiated (U, Pu)N fuel were estimated by both thermodynamic equilibrium calculation and electron microprobe analysis on burnup simulated samples prepared by carbothermic reduction. Besides the MX type matrix phase dissolving zirconium, niobium, yttrium and rare earth elements, the existence of two kinds of inclusion was recognized. One is URu 3 type intermetallic compound constituted by uranium and platinum group elements. The other is an alloy containing molybdenum as a principal constituent. Furthermore, the swelling rate due to solid fission products precipitation was evaluated to be about 0.5% per %FIMA.

  7. Holographic phase transitions at finite chemical potential

    Mateos, David; Matsuura, Shunji; Myers, Robert C.; Thomson, Rowan M.


    Recently, holographic techniques have been used to study the thermal properties of Script N = 2 super-Yang-Mills theory, with gauge group SU(Nc) and coupled to Nf coupling. Here we consider the phase diagram as a function of temperature and baryon chemical potential μb. For fixed μb transitions separating a region with vanishing baryon density and one with nonzero density. For fixed μb>Nc Mq there is no phase transition as a function of the temperature and the baryon density is always nonzero. We also compare the present results for the grand canonical ensemble with those for canonical ensemble in which the baryon density is held fixed [1].

  8. Phase coexistence in ferroelectric solid solutions: Formation of monoclinic phase with enhanced piezoelectricity

    Xiaoyan Lu


    Full Text Available Phase morphology and corresponding piezoelectricity in ferroelectric solid solutions were studied by using a phenomenological theory with the consideration of phase coexistence. Results have shown that phases with similar energy potentials can coexist, thus induce interfacial stresses which lead to the formation of adaptive monoclinic phases. A new tetragonal-like monoclinic to rhombohedral-like monoclinic phase transition was predicted in a shear stress state. Enhanced piezoelectricity can be achieved by manipulating the stress state close to a critical stress field. Phase coexistence is universal in ferroelectric solid solutions and may provide a way to optimize ultra-fine structures and proper stress states to achieve ultrahigh piezoelectricity.

  9. A review on solid phase extraction of actinides and lanthanides with amide based extractants.

    Ansari, Seraj A; Mohapatra, Prasanta K


    Solid phase extraction is gaining attention from separation scientists due to its high chromatographic utility. Though both grafted and impregnated forms of solid phase extraction resins are popular, the later is easy to make by impregnating a given organic extractant on to an inert solid support. Solid phase extraction on an impregnated support, also known as extraction chromatography, combines the advantages of liquid-liquid extraction and the ion exchange chromatography methods. On the flip side, the impregnated extraction chromatographic resins are less stable against leaching out of the organic extractant from the pores of the support material. Grafted resins, on the other hand, have a higher stability, which allows their prolong use. The goal of this article is a brief literature review on reported actinide and lanthanide separation methods based on solid phase extractants of both the types, i.e., (i) ligand impregnation on the solid support or (ii) ligand functionalized polymers (chemically bonded resins). Though the literature survey reveals an enormous volume of studies on the extraction chromatographic separation of actinides and lanthanides using several extractants, the focus of the present article is limited to the work carried out with amide based ligands, viz. monoamides, diamides and diglycolamides. The emphasis will be on reported applied experimental results rather than on data pertaining fundamental metal complexation. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Structural control of Fe-based alloys through diffusional solid/solid phase transformations in a high magnetic field.

    Ohtsuka, Hideyuki


    A magnetic field has a remarkable influence on solid/solid phase transformations and it can be used to control the structure and function of materials during phase transformations. The effects of magnetic fields on diffusional solid/solid phase transformations, mainly from austenite to ferrite, in Fe-based alloys are reviewed. The effects of magnetic fields on the transformation temperature and phase diagram are explained thermodynamically, and the transformation behavior and transformed structures in magnetic fields are discussed.

  11. Development of novel solid-phase protein formulations

    Montalvo Ortiz, Brenda Liz

    Proteins are the next-generation drugs for the treatment of several diseases. However, the number of protein drugs is still limited due to the physical or chemical instability of proteins during processing, formulation, storage, and delivery. The formulation of proteins at the solid state has advantages over liquid state, such as improved stability during long-term storage and delivery and decreases transportation costs. In this dissertation, we developed new solid-phase protein formulations in which the integrity of the protein was not compromised. The long term goal of this research was to use these protein formulations to improve protein stability in drug delivery devices, such as poly(lactic-co-glycolic) acid (PLGA). The first solid-phase protein formulation developed in this investigation was named "glassification". We proposed glassification as an alternative protein dehydration technique to the common used one, lyophilization, because this last method involves a series of steps which are detrimental to protein structure and stability. The glassification method consisted on protein dehydration by the use of organic solvents. As a result of the glassification process a small (micrometer size range) protein solid bead was obtained. The proteins used to study the glassification process were lysozyme (LYS), alpha-chymotrypsin (CHYMO) and horseradish peroxidase (HRP). These studies revealed that the glassification process itself did not alter protein structure and the activity was preserved. Ethyl acetate was the most effective organic solvent for protein glassification because it led to the highest protein residual activity, no insoluble aggregate formation and is a relatively non-toxic solvent, which allow the incorporation of these protein microparticles in PLGA microspheres. The incorporation of spherical HRP microparticles into PLGA microspheres resulted in superior properties when compared with encapsulated lyophilized HRP powder, such as improved release

  12. Vacuum-assisted headspace solid phase microextraction of polycyclic aromatic hydrocarbons in solid samples.

    Yiantzi, Evangelia; Kalogerakis, Nicolas; Psillakis, Elefteria


    For the first time, Vacuum Assisted Headspace Solid Phase Microextraction (Vac-HSSPME) is used for the recovery of polycyclic aromatic hydrocarbons (PAHs) from solid matrices. The procedure was investigated both theoretically and experimentally. According to the theory, reducing the total pressure increases the vapor flux of chemicals at the soil surface, and hence improves HSSPME extraction kinetics. Vac-HSSPME sampling could be further enhanced by adding water as a modifier and creating a slurry mixture. For these soil-water mixtures, reduced pressure conditions may increase the volatilization rates of compounds with a low K(H) present in the aqueous phase of the slurry mixture and result in a faster HSSPME extraction process. Nevertheless, analyte desorption from soil to water may become a rate-limiting step when significant depletion of the aqueous analyte concentration takes place during Vac-HSSPME. Sand samples spiked with PAHs were used as simple solid matrices and the effect of different experimental parameters was investigated (extraction temperature, modifiers and extraction time). Vac-HSSPME sampling of dry spiked sand samples provided the first experimental evidence of the positive combined effect of reduced pressure and temperature on HSSPME. Although adding 2 mL of water as a modifier improved Vac-HSSPME, humidity decreased the amount of naphthalene extracted at equilibrium as well as impaired extraction of all analytes at elevated sampling temperatures. Within short HSSPME sampling times and under mild sampling temperatures, Vac-HSSPME yielded linear calibration curves in the range of 1-400 ng g(-1) and, with the exception of fluorene, regression coefficients were found higher than 0.99. The limits of detection for spiked sand samples ranged from 0.003 to 0.233 ng g(-1) and repeatability from 4.3 to 10 %. Finally, the amount of PAHs extracted from spiked soil samples was smaller compared to spiked sand samples, confirming that soil could bind target

  13. Ionic liquids in solid-phase microextraction: a review.

    Ho, Tien D; Canestraro, Anthony J; Anderson, Jared L


    Solid-phase microextraction (SPME) has undergone a surge in popularity within the field of analytical chemistry in the past two decades since its introduction. Owing to its nature of extraction, SPME has become widely known as a quick and cost-effective sample preparation technique. Although SPME has demonstrated extraordinary versatility in sampling capabilities, the technique continues to experience a tremendous growth in innovation. Presently, increasing efforts have been directed towards the engineering of novel sorbent material in order to expand the applicability of SPME for a wider range of analytes and matrices. This review highlights the application of ionic liquids (ILs) and polymeric ionic liquids (PILs) as innovative sorbent materials for SPME. Characterized by their unique physico-chemical properties, these compounds can be structurally-designed to selectively extract target analytes based on unique molecular interactions. To examine the advantages of IL and PIL-based sorbent coatings in SPME, the field is reviewed by gathering available experimental data and exploring the sensitivity, linear calibration range, as well as detection limits for a variety of target analytes in the methods that have been developed.

  14. Solid-phase techniques in blood transfusion serology.

    Beck, M L; Plapp, F V; Sinor, L T; Rachel, J M


    For nearly a century, erythrocyte agglutination has persisted as the most widely used method for the demonstration of antigen-antibody reaction in immunohematology. So far, no other system has been developed which can match its simplicity, versatility, and general reliability. The major disadvantage of agglutination reactions is the lack of an objective endpoint, which has severely hindered attempts to automate routine pretransfusion tests. To overcome this problem, we have designed a series of solid-phase assays for ABO and Rh grouping, antibody screening, compatibility, and hepatitis tests. Each of these solid-phase assays shares a common endpoint of red cell adherence, which is easily interpreted visually or spectrophotometrically. Computer interface permits the automatic interpretation and recording of results. We believe this solid-phase system should finally bring the blood bank laboratory into the age of automation.

  15. Comparison of solid-phase and eluate assays to gauge the ecotoxicological risk of organic wastes on soil organisms.

    Domene, Xavier; Alcañiz, Josep M; Andrés, Pilar


    Development of methodologies to assess the safety of reusing polluted organic wastes in soil is a priority in Europe. In this study, and coupled with chemical analysis, seven organic wastes were subjected to different aquatic and soil bioassays. Tests were carried out with solid-phase waste and three different waste eluates (water, methanol, and dichloromethane). Solid-phase assays were indicated as the most suitable for waste testing not only in terms of relevance for real situations, but also because toxicity in eluates was generally not representative of the chronic effects in solid-phase. No general correlations were found between toxicity and waste pollutant burden, neither in solid-phase nor in eluate assays, showing the inability of chemical methods to predict the ecotoxicological risks of wastes. On the contrary, several physicochemical parameters reflecting the degree of low organic matter stability in wastes were the main contributors to the acute toxicity seen in collembolans and daphnids.


    Yu-ying Li; Jia-song He


    Solid phase transition of the a form crystals to the β form crystals in syndiotactic polystyrene (sPS) samples has occurred in supercritical CO2. This transformation is different from those detected under other conditions. The effects of some factors (e.g. time, temperature, and pressure) on the solid phase transformation of sPS in supercritical CO2 were analyzed in detail. Experimental results show that longer time, higher temperature or higher pressure favors the transformation of the α form crystals to the β form crystals.

  17. Chemical thermodynamics of the Hg1212 phase

    Tsuchiya, Tetsuo; Fueki, Kazuo


    The single phase of Hg1212 was synthesized by the simple oxide method using starting materials containing HgO 16% in excess. Stability regions of Hg1212 and pure HgO were determined by measuring the decomposition temperature as a function of oxygen partial pressure, and thermodynamic diagrams showing the stability domains of HgO and Hg1212 were constructed. The thermodynamical condition of formation of Hg1212 was discussed using the diagrams. It was found by chemical analysis that the valence of Hg is always 2 + and the valence of Ce changes with the oxygen content. TC (zero) changed from 122 to 118 K when the oxygen content was increased from 6.10 to 6.22.

  18. Laser-induced solid-solid phase transition in As under pressure: a theoretical prediction

    Zijlstra, Eeuwe S; Huntemann, Nils; Garcia, Martin E [Theoretische Physik, Universitaet Kassel, Heinrich-Plett-Strasse 40, 34132 Kassel (Germany)], E-mail:


    In arsenic, a pressure-induced solid-solid phase transition from the A7 into the simple cubic structure has been experimentally demonstrated (Beister et al 1990 Phys. Rev. B 41 5535). In this paper, we present calculations, which predict that this phase transition can also be induced by an ultrashort laser pulse in As under pressure. In addition, calculations for the pressure-induced phase transition are presented. Using density functional theory in the generalized gradient approximation, we found that the pressure-induced phase transition takes place at 26.3 GPa and is accompanied by a volume change {delta}V=0.5 a{sub 0}{sup 3} atom{sup -1}. The laser-induced phase transition is predicted for an applied pressure of 23.8 GPa and an absorbed laser energy of 2.8 mRy atom{sup -1}.

  19. All solid-state SBS phase conjugate mirror

    Dane, C.B.; Hackel, L.A.


    A stimulated Brillouin scattering (SBS) phase conjugate laser mirror uses a solid-state nonlinear gain medium instead of the conventional liquid or high pressure gas medium. The concept has been effectively demonstrated using common optical-grade fused silica. An energy threshold of 2.5 mJ and a slope efficiency of over 90% were achieved, resulting in an overall energy reflectivity of >80% for 15 ns, 1 um laser pulses. The use of solid-state materials is enabled by a multi-pass resonant architecture which suppresses transient fluctuations that would otherwise result in damage to the SBS medium. This all solid state phase conjugator is safer, more reliable, and more easily manufactured than prior art designs. It allows nonlinear wavefront correction to be implemented in industrial and defense laser systems whose operating environments would preclude the introduction of potentially hazardous liquids or high pressure gases. 8 figs.

  20. The Effects of Solid Phase Additives on Sintering Properties of Alumina Bioceramic

    WANG Xin-yu; LI Shi-pu; HE Jian-hua; JIANG Xin; LI Jian-hua


    In order to reduce the sintering temperature and improve the preparing conditions of alumina bioceramics,the Mg-Zr-Y composite solid phase additives were added into high purity Al2O3 micro-powder by chemical coprecipitation method.The powder was shaped under 200MPa cold isostatic pressure,and then the biscuits were sintered at 1600℃ under normal pressure.The sintered alumina materials were tested and the sintering mechanism was discussed.The results show that physical properties of the material were improved comparatively.The Mg-Zr-Y composite solid additives could promote the sintering of alumina bioceramics and the mechanism is solid phase sintering.

  1. Solid and solution phase combinatorial synthesis of ureas

    Nieuwenhuijzen, JW; Conti, PGM; Ottenheijm, HCJ; Linders, JTM


    An efficient parallel synthesis of ureas based on amino acids is described, both in solution and on solid phase. 1,1'-Carbonylbisbenzotriazole 2 is used as the coupling reagent. The ureas 5 and 10 were obtained in high yield (80-100%) and purity (71-97%). (C) 1998 Elsevier Science Ltd. All rights re

  2. Solid Phase Synthesis of Ethyl β-Substituted Indolepropionates

    刘占祥; 阮秀秀; 黄宪


    A facile solid phase synthesis of ethyl β-substituted indolepropionates is reported. Condensation between indole, polymer-supported cyclic malonic acid ester and aldehyde yielded the trimolecular adducts, which was cleaved by pyridine/EtOH to release the final products in good yield with high purity.

  3. Recent Approaches Toward Solid Phase Synthesis of β-Lactams

    Mandal, Bablee; Ghosh, Pranab; Basu, Basudeb

    Since the discovery of penicillin in 1929, β-lactam antibiotics have been recognized as potentially chemotherapeutic drugs of incomparable effectiveness, conjugating a broad spectrum of activity with very low toxicity. The primary motif azetidin-2-one ring (β-lactam) has been considered as specific pharmacophores and scaffolds. With the advent of combinatorial chemistry and automated parallel synthesis coupled with ample interests from the pharmaceutical industries, recent trends have been driven mostly by adopting solid phase techniques and polymer-supported synthesis of β-lactams. The present survey will present an overview of the developments on the polymer-supported and solid phase techniques for the preparation of β-lactam ring or β-lactam containing antibiotics published over the last decade. Both unsubstituted and substitutions with different functional groups at various positions of β-lactams have been synthesized using solid phase technology. However, Wang resin and application of Staudinger [2+2] cycloaddition reaction have remained hitherto the major choice. It may be expected that other solid phase approaches involving different resins would be developed in the coming years.

  4. Solid-phase synthesis of 3-amino-2-pyrazolines

    Lyngsø, Lars O.; Nielsen, John


    The development of a solid-phase synthesis of 3-amino-2-pyrazolines is described. Conjugate addition of hydrazines to α,β-unsaturated nitriles followed by cyclization yields 3-amino-2-pyrazolines. Acylation or sulfonation of the free amino-group yields a 24 member library of 3-amino-2- pyrazolines....

  5. Solid-phase synthesis of 3-amino-2-pyrazolines

    Nielsen, John


    The development of a solid-phase synthesis of 3-amino-2-pyrazolines is described. Conjugate addition of hydrazines to alpha,beta-unsaturated nitriles followed by cyclization yields 3-amino-2-pyrazolines. Acylation or sulfonation of the free amino-group yields a 24 member library of 3-amino-2...

  6. Solid-phase synthesis of complex and pharmacologically interesting heterocycles

    Nielsen, Thomas Eiland


    Efficient routes for the creation of heterocycles continue to be one of the primary goals for solid-phase synthesis. Recent advances in this field rely most notably on transition-metal-catalysis and N-acyliminium chemistry to mediate a range of cyclization processes for the generation of compounds...

  7. Solid-phase synthesis of 3-amino-2-pyrazolines

    Lyngsø, Lars O.; Nielsen, John


    The development of a solid-phase synthesis of 3-amino-2-pyrazolines is described. Conjugate addition of hydrazines to α,β-unsaturated nitriles followed by cyclization yields 3-amino-2-pyrazolines. Acylation or sulfonation of the free amino-group yields a 24 member library of 3-amino-2- pyrazolines....

  8. Solid-phase synthesis of complex and pharmacologically interesting heterocycles

    Nielsen, Thomas Eiland


    Efficient routes for the creation of heterocycles continue to be one of the primary goals for solid-phase synthesis. Recent advances in this field rely most notably on transition-metal-catalysis and N-acyliminium chemistry to mediate a range of cyclization processes for the generation of compounds...

  9. Solid-phase microextraction for the analysis of biological samples

    Theodoridis, G; Koster, EHM; de Jong, GJ


    Solid-phase microextraction (SPME) has been introduced for the extraction of organic compounds from environmental samples. This relatively new extraction technique has now also gained a lot of interest in a broad field of analysis including food, biological and pharmaceutical samples. SPME has a num

  10. Solid Phase Characterization of Tank 241-C-105 Grab Samples

    Ely, T. M. [Washington River Protection Solutions LLC, Richland, WA (United States); LaMothe, M. E. [Washington River Protection Solutions LLC, Richland, WA (United States); Lachut, J. S. [Washington River Protection Solutions LLC, Richland, WA (United States)


    The solid phase characterization (SPC) of three grab samples from single-shell Tank 241-C-105 (C-105) that were received at the laboratory the week of October 26, 2015, has been completed. The three samples were received and broken down in the 11A hot cells.

  11. Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys.

    Zhang, Yanwen; Stocks, G Malcolm; Jin, Ke; Lu, Chenyang; Bei, Hongbin; Sales, Brian C; Wang, Lumin; Béland, Laurent K; Stoller, Roger E; Samolyuk, German D; Caro, Magdalena; Caro, Alfredo; Weber, William J


    A grand challenge in materials research is to understand complex electronic correlation and non-equilibrium atomic interactions, and how such intrinsic properties and dynamic processes affect energy transfer and defect evolution in irradiated materials. Here we report that chemical disorder, with an increasing number of principal elements and/or altered concentrations of specific elements, in single-phase concentrated solid solution alloys can lead to substantial reduction in electron mean free path and orders of magnitude decrease in electrical and thermal conductivity. The subsequently slow energy dissipation affects defect dynamics at the early stages, and consequentially may result in less deleterious defects. Suppressed damage accumulation with increasing chemical disorder from pure nickel to binary and to more complex quaternary solid solutions is observed. Understanding and controlling energy dissipation and defect dynamics by altering alloy complexity may pave the way for new design principles of radiation-tolerant structural alloys for energy applications.

  12. Solid-State NMR Studies of Chemically Lithiated CFx

    Leifer, N. D.; Johnson, V. S.; Ben-Ari, R.; Gan, H.; Lehnes, J. M.; Guo, R.; Lu, W.; Muffoletto, B. C.; Reddy, T.; Stallworth, P. E.; Greenbaum, S. G.


    Three types of fluorinated carbon, all in their original form and upon sequential chemical lithiations via n-butyllithium, were investigated by 13C and 19F solid-state NMR methods. The three starting CFx materials [where x = 1 (nominally)] were fiber based, graphite based, and petroleum coke based. The aim of the current study was to identify, at the atomic/molecular structural level, factors that might account for differences in electrochemical performance among the different kinds of CFx. Differences were noted in the covalent F character among the starting compounds and in the details of LiF production among the lithiated samples. PMID:20676233

  13. Determining the solid phases hosting arsenic in Mekong Delta sediments

    Wucher, M.; Stuckey, J. W.; McCurdy, S.; Fendorf, S.


    The major river systems originating from the Himalaya deposit arsenic bearing sediment into the deltas of South and Southeast Asia. High rates of sediment and organic carbon deposition combined with frequent flooding leads to anaerobic processes that release arsenic into the pore-water. Arsenic concentrations in the groundwater of these sedimentary basins are often above the World Health Organization drinking water standard of 10 μg As L-1. As a result, 150 million people are at risk of chronic arsenic poisoning through water and rice consumption. The composition of the iron bearing phases hosting the arsenic in these deltaic sediments is poorly understood. Here we implemented a suite of selective chemical extractions to help constrain the types of arsenic bearing solid phases, which were complimented with synchrotron-based X-ray absorption spectroscopy and X-ray diffraction analyses to define the arsenic and iron mineralogy of the system. Sediment cores were collected in triplicate from a seasonally-inundated wetland in Cambodia at depths of 10, 50, 100, and 150 centimeters. We hypothesize that (i) arsenic will be predominantly associated with iron oxides, and (ii) the ratio of crystalline to amorphous iron oxides will increase with sediment depth (and age). We performed four selective extractions in parallel to quantify the various pools of arsenic. First, 1 M MgCl2 was used to extract electrostatically-bound arsenic (labile forms) from the sediment. Second, 1 M NaH2PO4 targeted strongly adsorbed arsenic. Third, 1 M HCl was used to liberated arsenic coprecipitated with amorphous Fe/Mn oxides, carbonates, and acid-volatile sulfides. Finally, a dithionite extraction was used to account for arsenic associated with reducible Fe/Mn oxides. Through this work, we identified the composition of the phases hosting arsenic at various depths through the soil profile, improving our understanding of how arsenic persists in the aquifer. In addition, defining the arsenic and

  14. R. Bruce Merrifield and Solid-Phase Peptide Synthesis: A Historical Assessment

    Mitchell, A R


    Bruce Merrifield, trained as a biochemist, had to address three major challenges related to the development and acceptance of solid-phase peptide synthesis (SPPS). The challenges were (1) to reduce the concept of peptide synthesis on a insoluble support to practice, (2) overcome the resistance of synthetic chemists to this novel approach, and (3) establish that a biochemist had the scientific credentials to effect the proposed revolutionary change in chemical synthesis. How these challenges were met is discussed in this article.

  15. Fmoc solid-phase synthesis of peptide thioesters by masking as trithioortho esters

    Brask, Jesper; Albericio, F.; Jensen, Knud Jørgen


    Total chemical synthesis of proteins by chemoselective ligation relies on C-terminal peptide thioesters as building blocks. Their preparation by standard Fmoc solid-phase peptide synthesis is made difficult by the lability of thioesters to aminolysis by the secondary amines used for removal of th...... of the Fmoc group. Here we present a novel backbone amide linker (BAL) strategy for their synthesis in which the thioester functionality is masked as a trithioortho ester throughout the synthesis....

  16. Phase field modeling of flexoelectricity in solid dielectrics

    Chen, H. T.; Zhang, S. D.; Soh, A. K.; Yin, W. Y.


    A phase field model is developed to study the flexoelectricity in nanoscale solid dielectrics, which exhibit both structural and elastic inhomogeneity. The model is established for an elastic homogeneous system by taking into consideration all the important non-local interactions, such as electrostatic, elastic, polarization gradient, as well as flexoelectric terms. The model is then extended to simulate a two-phase system with strong elastic inhomogeneity. Both the microscopic domain structures and the macroscopic effective piezoelectricity are thoroughly studied using the proposed model. The results obtained show that the largest flexoelectric induced polarization exists at the interface between the matrix and the inclusion. The effective piezoelectricity is greatly influenced by the inclusion size, volume fraction, elastic stiffness, and the applied stress. The established model in the present study can provide a fundamental framework for computational study of flexoelectricity in nanoscale solid dielectrics, since various boundary conditions can be easily incorporated into the phase field model.

  17. Distribution of Dechlorinating Bacteria between the Aqueous and Solid Phases

    Cápiro, N. L.; Hatt, J. K.; Wang, Y.; Loeffler, F. E.; Pennell, K. D.


    Microbial monitoring of aquifers relies on nucleic acid biomarker analysis, which is typically performed with biomass recovered from groundwater samples; however, it is unclear what fraction of the target population(s) is associated with groundwater (i.e., planktonic cells) or is attached to solid phases (i.e., biofilms). Understanding how the titer of target organism(s) in groundwater correlates with the true cell titers of the target organism in the aquifer (i.e., planktonic plus attached cells) is critical for a meaningful interpretation of the data, the prediction of bioremediation performance, and the implementation of site management strategies. To evaluate the distribution of active cells between resident solid phase and the aqueous phase, one-dimensional columns were packed under water-saturated conditions with Bio-Dechlor INOCULUM, a PCE-to ethene-dechlorinating bacterial consortium containing both multiple Dehalococcoides (Dhc) strains and Geobacter lovleyi strain SZ (GeoSZ). The columns were packed with two distinct solid matrices: a low organic content sandy Federal Fine Ottawa soil or Appling soil with higher organic matter content. Influent reduced mineral salts medium supplied at a groundwater pore-water velocity of 0.3 m/day contained both 10 mM lactate as electron donor and 0.33 mM PCE as electron acceptor. Routine collection of biomass from column side ports and effluent samples measured the titers of target cells in the aqueous phase and determined when steady state conditions had been reached. A second set of column experiments evaluated delivery and filtration effects by the solid matrix (i.e., Federal Fine Ottawa sand versus Appling soil) under the same conditions except that electron donor or acceptor were omitted (no growth conditions). Quantitative real-time PCR (qPCR) analysis using Dhc and GeoSZ 16S rRNA gene-targeted primer and probe sets determined the planktonic cell counts, and destructive sampling of the columns allowed measurement

  18. Solid-phase synthesis of molecularly imprinted nanoparticles.

    Canfarotta, Francesco; Poma, Alessandro; Guerreiro, Antonio; Piletsky, Sergey


    Molecularly imprinted polymers (MIPs) are synthetic materials, generally based on acrylic or methacrylic monomers, that are polymerized in the presence of a specific target molecule called the 'template' and capable of rebinding selectively to this target molecule. They have the potential to be low-cost and robust alternatives to biomolecules such as antibodies and receptors. When prepared by traditional synthetic methods (i.e., with free template in solution), their usefulness has been limited by high binding site heterogeneity, the presence of residual template and the fact that the production methods are complex and difficult to standardize. To overcome some of these limitations, we developed a method for the synthesis of MIP nanoparticles (nanoMIPs) using an innovative solid-phase approach, which relies on the covalent immobilization of the template molecules onto the surface of a solid support (glass beads). The obtained nanoMIPs are virtually free of template and demonstrate high affinity for the target molecule (e.g., melamine and trypsin in our published work). Because of an affinity separation step performed on the solid phase after polymerization, poor binders and unproductive polymer are removed, so the final product has more uniform binding characteristics. The overall protocol, starting from the immobilization of the template onto the solid phase and including the purification and characterization of the nanoparticles, takes up to 1 week.

  19. Direct molecular dynamics simulation of liquid-solid phase equilibria for a three-component plasma.

    Hughto, J; Horowitz, C J; Schneider, A S; Medin, Zach; Cumming, Andrew; Berry, D K


    The neutron-rich isotope ²²Ne may be a significant impurity in carbon and oxygen white dwarfs and could impact how the stars freeze. We perform molecular dynamics simulations to determine the influence of ²²Ne in carbon-oxygen-neon systems on liquid-solid phase equilibria. Both liquid and solid phases are present simultaneously in our simulation volumes. We identify liquid, solid, and interface regions in our simulations using a bond angle metric. In general we find good agreement for the composition of liquid and solid phases between our MD simulations and the semianalytic model of Medin and Cumming. The trace presence of a third component, neon, does not appear to strongly impact the chemical separation found previously for two-component carbon and oxygen systems. This suggests that small amounts of ²²Ne may not qualitatively change how the material in white dwarf stars freezes. However, we do find systematically lower melting temperatures (higher Γ) in our MD simulations compared to the semianalytic model. This difference seems to grow with impurity parameter Q_{imp} and suggests a problem with simple corrections to the linear mixing rule for the free energy of multicomponent solid mixtures that is used in the semianalytic model.

  20. Multicomponent chemical imaging of pharmaceutical solid dosage forms with broadband CARS microscopy.

    Hartshorn, Christopher M; Lee, Young Jong; Camp, Charles H; Liu, Zhen; Heddleston, John; Canfield, Nicole; Rhodes, Timothy A; Hight Walker, Angela R; Marsac, Patrick J; Cicerone, Marcus T


    We compare a coherent Raman imaging modality, broadband coherent anti-Stokes Raman scattering (BCARS) microscopy, with spontaneous Raman microscopy for quantitative and qualitative assessment of multicomponent pharmaceuticals. Indomethacin was used as a model active pharmaceutical ingredient (API) and was analyzed in a tabulated solid dosage form, embedded within commonly used excipients. In comparison with wide-field spontaneous Raman chemical imaging, BCARS acquired images 10× faster, at higher spatiochemical resolution and with spectra of much higher SNR, eliminating the need for multivariate methods to identify chemical components. The significant increase in spatiochemical resolution allowed identification of an unanticipated API phase that was missed by the spontaneous wide-field method and bulk Raman spectroscopy. We confirmed the presence of the unanticipated API phase using confocal spontaneous Raman, which provided spatiochemical resolution similar to BCARS but at 100× slower acquisition times.

  1. Piezoelectric Ceramics of the (1 − x)Bi0.50Na0.50TiO3–xBa0.90Ca0.10TiO3 Lead-Free Solid Solution: Chemical Shift of the Morphotropic Phase Boundary, a Case Study for x = 0.06

    Vivar-Ocampo, Rodrigo; Pardo, Lorena; Ávila, David; Morán, Emilio; González, Amador M.; Bucio, Lauro; Villafuerte-Castrejón, María-Elena


    Research and development of lead-free piezoelectric materials are still the hottest topics in the field of piezoelectricity. One of the most promising lead-free family of compounds to replace lead zirconate–titanate for actuators is that of Bi0.50Na0.50TiO3 (BNT) based solid solutions. The pseudo-binary (1 − x)Bi0.50Na0.50TiO3–xBa1 − yCayTiO3 system has been proposed for high temperature capacitors and not yet fully explored as piezoelectric material. In this work, the solid solution with x = 0.06 and y = 0.10 was obtained by two different synthesis routes: solid state and Pechini, aiming at using reduced temperatures, both in synthesis (<800 °C) and sintering (<1150 °C), while maintaining appropriated piezoelectric performance. Crystal structure, ceramic grain size, and morphology depend on the synthesis route and were analyzed by X-ray diffraction, together with scanning and transmission electron microscopy. The effects of processing and ceramic microstructure on the structural, dielectric, ferroelectric, and piezoelectric properties were discussed in terms of a shift of the Morphotropic Phase Boundary, chemically induced by the synthesis route. PMID:28773096

  2. Studies in Solid Phase Peptide Synthesis: A Personal Perspective

    Mitchell, A R


    By the early 1970s it had became apparent that the solid phase synthesis of ribonuclease A could not be generalized. Consequently, virtually every aspect of solid phase peptide synthesis (SPPS) was reexamined and improved during the decade of the 1970s. The sensitive detection and elimination of possible side reactions (amino acid insertion, N{sup {alpha}}-trifluoroacetylation, N{sup {alpha}{var_epsilon}}-alkylation) was examined. The quantitation of coupling efficiency in SPPS as a function of chain length was studied. A new and improved support for SPPS, the 'PAM-resin', was prepared and evaluated. These and many other studies from the Merrifield laboratory and elsewhere increased the general acceptance of SPPS leading to the 1984 Nobel Prize in Chemistry for Bruce Merrifield.

  3. Entransy dissipation minimization for liquid-solid phase change processes


    The liquid-solid phase change process of a simple one-dimensional slab is studied in this paper.By taking entransy dissipation minimization as optimization objective,the optimal external reservoir temperature profiles are derived by using optimal control theory under the condition of a fixed freezing or melting time.The entransy dissipation corresponding to the optimal heat exchange strategies of minimum entransy dissipation is 8/9 of that corresponding to constant reservoir temperature operations,which is independent of all system parameters.The obtained results for entransy dissipation minimization are also compared with those obtained for the optimal heat exchange strategies of minimum entropy generation and constant reservoir temperature operations by numerical examples.The obtained results can provide some theoretical guidelines for the choice of optimal cooling or heating strategy in practical liquid-solid phase change processes.

  4. Semi-automated microwave assisted solid-phase peptide synthesis

    Pedersen, Søren Ljungberg

    with microwaves for SPPS has gained in popularity as it for many syntheses has provided significant improvement in terms of speed, purity, and yields, maybe especially in the synthesis of long and "difficult" peptides. Thus, precise microwave heating has emerged as one new parameter for SPPS, in addition...... to coupling reagents, resins, solvents etc. We have previously reported on microwave heating to promote a range of solid-phase reactions in SPPS. Here we present a new, flexible semi-automated instrument for the application of precise microwave heating in solid-phase synthesis. It combines a slightly modified...... Biotage Initiator microwave instrument, which is available in many laboratories, with a modified semi-automated peptide synthesizer from MultiSynTech. A custom-made reaction vessel is placed permanently in the microwave oven, thus the reactor does not have to be moved between steps. Mixing is achieved...

  5. Hyperdoping silicon with selenium: solid vs. liquid phase epitaxy

    Zhou, Shengqiang; Liu, Fang; Prucnal, S.; Gao, Kun; Khalid, M.; Baehtz, C.; Posselt, M.; Skorupa, W.; Helm, M


    Chalcogen-hyperdoped silicon shows potential applications in silicon-based infrared photodetectors and intermediate band solar cells. Due to the low solid solubility limits of chalcogen elements in silicon, these materials were previously realized by femtosecond or nanosecond laser annealing of implanted silicon or bare silicon in certain background gases. The high energy density deposited on the silicon surface leads to a liquid phase and the fast recrystallization velocity allows trapping o...

  6. Chromatography, solid-phase extraction, and capillary electrochromatography with MIPs.

    Tóth, Blanka; Horvai, George


    Most analytical applications of molecularly imprinted polymers are based on their selective adsorption properties towards the template or its analogs. In chromatography, solid phase extraction and electrochromatography this adsorption is a dynamic process. The dynamic process combined with the nonlinear adsorption isotherm of the polymers and other factors results in complications which have limited the success of imprinted polymers. This chapter explains these problems and shows many examples of successful applications overcoming or avoiding the problems.

  7. Simulating confined swirling gas-solid two phase jet

    金晗辉; 夏钧; 樊建人; 岑可法


    A k-ε-kp multi-fluid model was used to simulate confined swirling gas-solid two phase jet comprised of particle-laden flow from a center tube and a swirling air stream entering the test section from the coaxial annular. After considering the drag force between the two phases and gravity, a series of numerical simulations of the two-phase flow of 30μm, 45μm, 60μm diameter particles were performed on a x×r=50×50 mesh grid respectively. The results showed that the k-ε-kp multi-fluid model can be applied to predict moderate swirling multi-phase flow. When the particle diameter is large, the collision of the particles with the wall will influence the prediction accuracy. The bigger the diameter of the particles, the stronger the collision with the wall, and the more obvious the difference between measured and calculated results.

  8. Novel functionalized polymeric fabric and fiber material as solid support for solid-phase synthesis and biomedical applications

    Xiang, Bei

    The aim of the research is to develop novel polymer solid support by modifying or fabricating polymeric fibrous materials for peptide synthesis and biomedical applications. Originally chemical inert isotactic polypropylene (iPP) fabric was utilized and modified to serve as a functional flexible planar solid support for solid phase peptide synthesis. The modification was achieved through thermal initiated radical grafting polymerization using acrylic acid, poly (ethylene glycol) diacrylate as monomers, and benzoyl peroxide as radical initiator. The iPP fabric was successfully functionalized and possessing as high as 0.7mmol/g carboxylic acid groups. Peptide ligand LHPQF was successfully synthesized on the new functional planar support. Specific enzyme immobilization was fulfilled on the functional iPP fabric support. A commercially available ethylene-acrylic acid copolymer was made into ultrafine copolymer fiber bundles which are composed of nanofibers with diameters ranging from 200nm to 800nm. Various mixing ratios of copolymer/matrix materials were utilized to explore the effect on the final nanofiber physical properties including morphology and stability in solvents. The surface carboxylic acid groups were further converted to amino groups before the functional nanofibers can be applied in solid phase peptide synthesis. Two peptide ligands, LHPQF and HWRGWV, were also successfully synthesized on the nanofiber bundles. Streptavidin and human immunoglobulin G specific binding with the corresponding ligand which was anchored on the nanofibers was conducted successfully to illustrate the potential applications of the nanofiber materials in biomedical field. Further study on the dispersion of the ethylene-acrylic acid nanofiber bundles was pursued to take advantage of the super high active surface area of functional nanofibers. To manipulate the polymer nanofibers during synthesis and bio-assays, a technique was developed to controllably assemble and disperse the

  9. A two-phase restricted equilibrium model for combustion of metalized solid propellants

    Sabnis, J. S.; Dejong, F. J.; Gibeling, H. J.


    An Eulerian-Lagrangian two-phase approach was adopted to model the multi-phase reacting internal flow in a solid rocket with a metalized propellant. An Eulerian description was used to analyze the motion of the continuous phase which includes the gas as well as the small (micron-sized) particulates, while a Lagrangian description is used for the analysis of the discrete phase which consists of the larger particulates in the motor chamber. The particulates consist of Al and Al2O3 such that the particulate composition is 100 percent Al at injection from the propellant surface with Al2O3 fraction increasing due to combustion along the particle trajectory. An empirical model is used to compute the combustion rate for agglomerates while the continuous phase chemistry is treated using chemical equilibrium. The computer code was used to simulate the reacting flow in a solid rocket motor with an AP/HTPB/Al propellant. The computed results show the existence of an extended combustion zone in the chamber rather than a thin reaction region. The presence of the extended combustion zone results in the chamber flow field and chemical being far from isothermal (as would be predicted by a surface combustion assumption). The temperature in the chamber increases from about 2600 K at the propellant surface to about 3350 K in the core. Similarly the chemical composition and the density of the propellant gas also show spatially non-uniform distribution in the chamber. The analysis developed under the present effort provides a more sophisticated tool for solid rocket internal flow predictions than is presently available, and can be useful in studying apparent anomalies and improving the simple correlations currently in use. The code can be used in the analysis of combustion efficiency, thermal load in the internal insulation, plume radiation, etc.

  10. A two-fluid model for reactive dilute solid-liquid mixtures with phase changes

    Reis, Martina Costa; Wang, Yongqi


    Based on the Eulerian spatial averaging theory and the Müller-Liu entropy principle, a two-fluid model for reactive dilute solid-liquid mixtures is presented. Initially, some averaging theorems and properties of average quantities are discussed and, then, averaged balance equations including interfacial source terms are postulated. Moreover, constitutive equations are proposed for a reactive dilute solid-liquid mixture, where the formation of the solid phase is due to a precipitation chemical reaction that involves ions dissolved in the liquid phase. To this end, principles of constitutive theory are used to propose linearized constitutive equations that account for diffusion, heat conduction, viscous and drag effects, and interfacial deformations. A particularity of the model is that the mass interfacial source term is regarded as an independent constitutive variable. The obtained results show that the inclusion of the mass interfacial source term into the set of independent constitutive variables permits to easily describe the phase changes associated with precipitation chemical reactions.

  11. A two-fluid model for reactive dilute solid-liquid mixtures with phase changes

    Reis, Martina Costa; Wang, Yongqi


    Based on the Eulerian spatial averaging theory and the Müller-Liu entropy principle, a two-fluid model for reactive dilute solid-liquid mixtures is presented. Initially, some averaging theorems and properties of average quantities are discussed and, then, averaged balance equations including interfacial source terms are postulated. Moreover, constitutive equations are proposed for a reactive dilute solid-liquid mixture, where the formation of the solid phase is due to a precipitation chemical reaction that involves ions dissolved in the liquid phase. To this end, principles of constitutive theory are used to propose linearized constitutive equations that account for diffusion, heat conduction, viscous and drag effects, and interfacial deformations. A particularity of the model is that the mass interfacial source term is regarded as an independent constitutive variable. The obtained results show that the inclusion of the mass interfacial source term into the set of independent constitutive variables permits to easily describe the phase changes associated with precipitation chemical reactions.

  12. Liquid-solid extraction coupled with magnetic solid-phase extraction for determination of pyrethroid residues in vegetable samples by ultra fast liquid chromatography.

    Jiang, Chunzhu; Sun, Ying; Yu, Xi; Gao, Yan; Zhang, Lei; Wang, Yuanpeng; Zhang, Hanqi; Song, Daqian


    In this study, liquid-solid extraction coupled with magnetic solid-phase extraction was successfully developed for the extraction of pyrethroid residues in vegetable samples. The analytes were determined by ultra fast liquid chromatography. The pyrethroids were extracted by liquid-solid extraction and then adsorbed onto magnetic adsorbent. Magnetic adsorbent, C18-functionalized ultrafine magnetic silica nanoparticles, was synthesized by chemical coprecipitation, silanization and alkylation. The analytes adsorbed onto the magnetic adsorbent can be simply and rapidly isolated from sample solution with a strong magnet on the bottom of the extraction vessel. The extraction parameters, such as liquid-solid extraction solvent, liquid-solid extraction time, the amount of magnetic adsorbent, magnetic solid-phase extraction time and magnetic solid-phase extraction desorption solvent, were optimized to improve the extraction efficiency. The analytical performances of this method, including linear range, detection limit, precision, and recovery were evaluated. The limits of detection for pyrethroid were between 0.63 and 1.2 ng g(-1). Recoveries obtained by analyzing the four spiked vegetable samples were between 76.0% and 99.5%. The results showed that the present method was a simple, accurate and high efficient approach for the determination of pyrethroids in the vegetable samples.

  13. Two phase continuous digestion of solid manure on-farm

    Schaefer, W.; Lehto, M. [MTT Agrifood Research Finland, Vihti (Finland). Animal Production Research; Evers, L.; Granstedt, A. [Biodynamic Research Inst., Jaerna (Sweden)


    Present commercially available biogas plants are mainly suitable for slurry and co-substrates. Cattle, horse and poultry farms using a solid manure chain experience a crucial competitive disadvantage, because conversion to slurry technology requires additional investments. Based on the technological progress of anaerobic digestion of municipal solid waste, so called 'dry fermentation' prototype plants were developed for anaerobic digestion of organic material containing 15-50% total solids (Hoffman, 2001). These plants show added advantages compared to slurry digestion plants: Less reactor volume, less process energy, less transport capacity, less odour emissions. On-farm research (Gronauer and Aschmann, 2004; Kusch and Oechsner, 2004) and prototype research (Linke, 2004) on dry fermentation in batch reactors show that loading and discharging of batch reactors remains difficult and/or time-consuming compared to slurry reactors. Additionally a constant level of gas generation requires offset operation of several batch reactors. Baserga et al. (1994) developed a pilot plant of 9.6 m{sup 3} capacity for continuous digestion of solid beef cattle manure on-farm. However, on-farm dry fermentation plants are not common and rarely commercially available. We assume that lack of tested technical solutions and scarceness of on-farm research results are the main reason for low acceptance of dry fermentation technology on-farm. We report about an innovative two phase farm-scale biogas plant. The plant continuously digests dairy cattle manure and organic residues of the farm and the surrounding food processing units. The two phase reactor technology was chosen for two reasons: first it offers the separation of a liquid fraction and a solid fraction for composting after hydrolysis and secondly the methanation of the liquid fraction using fixed film technology results in a very short hydraulic retention time, reduction in reactor volume, and higher methane content of the

  14. Direct MD simulation of liquid-solid phase equilibria for three-component plasma

    Hughto, J; Schneider, A S; Medin, Zach; Cumming, Andrew; Berry, D K


    The neutron rich isotope 22Ne may be a significant impurity in carbon and oxygen white dwarfs and could impact how the stars freeze. We perform molecular dynamics simulations to determine the influence of 22Ne in carbon-oxygen-neon systems on liquid-solid phase equilibria. Both liquid and solid phases are present simultaneously in our simulation volumes. We identify liquid, solid, and interface regions in our simulations using a bond angle metric. In general we find good agreement for the composition of liquid and solid phases between our MD simulations and the semi analytic model of Medin and Cumming. The trace presence of a third component, neon, does not appear to strongly impact the chemical separation found previously for two component carbon and oxygen systems. This suggests that small amounts of 22Ne may not qualitatively change how the material in white dwarf stars freezes. However, we do find systematically lower melting temperatures (higher Gamma) in our MD simulations compared to the semi analytic ...

  15. Phase field modeling and simulation of three-phase flow on solid surfaces

    Zhang, Qian; Wang, Xiao-Ping


    Phase field models are widely used to describe the two-phase system. The evolution of the phase field variables is usually driven by the gradient flow of a total free energy functional. The generalization of the approach to an N phase (N ≥ 3) system requires some extra consistency conditions on the free energy functional in order for the model to give physically relevant results. A projection approach is proposed for the derivation of a consistent free energy functional for the three-phase Cahn-Hilliard equations. The system is then coupled with the Navier-Stokes equations to describe the three-phase flow on solid surfaces with moving contact line. An energy stable scheme is developed for the three-phase flow system. The discrete energy law of the numerical scheme is proved which ensures the stability of the scheme. We also show some numerical results for the dynamics of triple junctions and four phase contact lines.

  16. The synthesis and properties of the phases obtained by solid-solid reactions

    Blonska-Tabero A.


    Full Text Available The presented work encompasses the subject of the studies and the results obtained over the last years by the research workers of the Department of Inorganic Chemistry. They include mainly the studies on the reactivity of metal oxides, searching for new phases in binary and ternary systems of metal oxides as well as describing phase relations establishing in such systems. They also encompass works on the extensive characteristics of physico-chemical properties of the newly obtained compounds.

  17. Silica-Based Solid Phase Extraction of DNA on a Microchip

    陈晓芳; 沈科跃; 刘鹏; 郭旻; 程京; 周玉祥


    Micro total analysis systems for chemical and biological analysis have attracted much attention.However,microchips for sample preparation and especially DNA purification are still underdeveloped.This work describes a solid phase extraction chip for purifying DNA from biological samples based on the adsorption of DNA on bare silica beads prepacked in a microchannel.The chip was fabricated with poly-dimethylsiloxane.The silica beads were packed in the channel on the chip with a tapered microchannel to form the packed bed.Fluorescence detection was used to evaluate the DNA adsorbing efficiency of the solid phase.The polymerase chain reaction was used to evaluate the quality of the purified DNA for further use.The extraction efficiency for the DNA extraction chip is approximately 50% with a 150-nL extraction volume.Successful amplification of DNA extracted from human whole blood indicates that this method is compatible with the polymerase chain reaction.

  18. Studies on solid-solid phase transitions of polyols by infrared spectroscopy

    Feng, H.; Liu, X.; He, S.; Wu, K.; Zhang, J. [Department of Chemistry, Hebei Normal University, Shijiazhuang (China)


    This paper chiefly deals with the properties of polyols - a kind of energy storage material, by IR spectra. A series of infrared spectra at various temperatures were obtained for pentaerythritol (PE), pentaglycerine (PG), neopentylglycol (NPG) and their mixture NPG/PG. The experimental results (the shifts of -OH absorption band in IR spectra) support the solid-solid phase transition mechanism, which involves the reversible breaking of nearest-neighbor hydrogen bonds in the molecular crystals at transformation temperature. The correlation between the wave number shifts and the temperatures of phase transition is proposed in this paper. Finally, by means of infrared spectroscopy experiments, it is shown that aging has a great influence on the thermal properties of polyol mixtures.

  19. Chemically modified solid state nanopores for high throughput nanoparticle separation

    Prabhu, Anmiv S; Kim, Min Jun [School of Biomedical Engineering and Health Science, Drexel University, Philadelphia, PA 19104 (United States); Jubery, Talukder Zaki N; Dutta, Prashanta [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 (United States); Freedman, Kevin J; Mulero, Rafael, E-mail: mkim@coe.drexel.ed [Department of Mechanical Engineering and Mechanics, Drexel University, Philadelphia, PA 19104 (United States)


    The separation of biomolecules and other nanoparticles is a vital step in several analytical and diagnostic techniques. Towards this end we present a solid state nanopore-based set-up as an efficient separation platform. The translocation of charged particles through a nanopore was first modeled mathematically using the multi-ion model and the surface charge density of the nanopore membrane was identified as a critical parameter that determines the selectivity of the membrane and the throughput of the separation process. Drawing from these simulations a single 150 nm pore was fabricated in a 50 nm thick free-standing silicon nitride membrane by focused-ion-beam milling and was chemically modified with (3-aminopropyl)triethoxysilane to change its surface charge density. This chemically modified membrane was then used to separate 22 and 58 nm polystyrene nanoparticles in solution. Once optimized, this approach can readily be scaled up to nanopore arrays which would function as a key component of next-generation nanosieving systems.

  20. Mechanical and chemical recycling of solid plastic waste.

    Ragaert, Kim; Delva, Laurens; Van Geem, Kevin


    This review presents a comprehensive description of the current pathways for recycling of polymers, via both mechanical and chemical recycling. The principles of these recycling pathways are framed against current-day industrial reality, by discussing predominant industrial technologies, design strategies and recycling examples of specific waste streams. Starting with an overview on types of solid plastic waste (SPW) and their origins, the manuscript continues with a discussion on the different valorisation options for SPW. The section on mechanical recycling contains an overview of current sorting technologies, specific challenges for mechanical recycling such as thermo-mechanical or lifetime degradation and the immiscibility of polymer blends. It also includes some industrial examples such as polyethylene terephthalate (PET) recycling, and SPW from post-consumer packaging, end-of-life vehicles or electr(on)ic devices. A separate section is dedicated to the relationship between design and recycling, emphasizing the role of concepts such as Design from Recycling. The section on chemical recycling collects a state-of-the-art on techniques such as chemolysis, pyrolysis, fluid catalytic cracking, hydrogen techniques and gasification. Additionally, this review discusses the main challenges (and some potential remedies) to these recycling strategies and ground them in the relevant polymer science, thus providing an academic angle as well as an applied one. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Solid-Phase Preparation and Characterization of Chitosan

    GaoLe-ping; DuYu-min; ZhangDao-bin; ShiXiao-wen; ZhanHuai-yu; SongWen-hua


    Chitosan was prepared with stressing method by blending chitin and solid alkali in a single-screw extruder at given temperature and characterized by potentiometric titration, gel permeation chromatography (GPC), infrared spectrum (IR) and carborr13 magnetic resonance sperctroscopy (13C NMR). Chitosan with a deacetylation degree (DD) of 76. 1% was obtained at a mass ratio 0.2 : 1 : 1 for H20/chitin/NaOH at 160℃ for 12 mirL Compared to conventional solution method(usually 1 : 10 for chitin/NaOH), the alkali assumption greatly decreased. Molecular weight of chitosan obtained by solid-phase method(S3,M. 1.54 X 10s ) was lower than that obtained by suspension method(Y2,Mw3. 34×105). During deacetylation, molecular weight decreased with high reaction temperature and long reaction time but remained same at different initial ratios of NaOH/chitirL It might be concluded that degradation of chitosan was caused by breakout of the main chain of the oxidized chitosan catalyzed by alkali during the deactylation. IR and 13C NMR showed that structures of chitosans prepared by solid-phase method were not changed.

  2. Thermodynamic phase behavior of API/polymer solid dispersions.

    Prudic, Anke; Ji, Yuanhui; Sadowski, Gabriele


    To improve the bioavailability of poorly soluble active pharmaceutical ingredients (APIs), these materials are often integrated into a polymer matrix that acts as a carrier. The resulting mixture is called a solid dispersion. In this work, the phase behaviors of solid dispersions were investigated as a function of the API as well as of the type and molecular weight of the carrier polymer. Specifically, the solubility of artemisinin and indomethacin was measured in different poly(ethylene glycol)s (PEG 400, PEG 6000, and PEG 35000). The measured solubility data and the solubility of sulfonamides in poly(vinylpyrrolidone) (PVP) K10 and PEG 35000 were modeled using the perturbed-chain statistical associating fluid theory (PC-SAFT). The results show that PC-SAFT predictions are in a good accordance with the experimental data, and PC-SAFT can be used to predict the whole phase diagram of an API/polymer solid dispersion as a function of the kind of API and polymer and of the polymer's molecular weight. This remarkably simplifies the screening process for suitable API/polymer combinations.

  3. Detection of Giardia lamblia Antigens in Human Fecal Specimens by a Solid-Phase Qualitative Immunochromatographic Assay▿

    Garcia, Lynne S.; Garcia, John Paul


    The SIMPLE-READ Giardia rapid assay (Medical Chemical Corporation) is a solid-phase qualitative immunochromatographic assay that detects Giardia lamblia in aqueous extracts of human fecal specimens. Testing 106 Giardia-positive and 104 Giardia-negative stool specimens yielded a sensitivity of 97.2% and a specificity of 100% for the SIMPLE-READ Giardia rapid assay.


    Three types of solid phase chemical exposure sampling media: cellulose, polyurethane foam (PUF) and XAD-2, were analyzed for 2,4-D and the amine salts of 2,4-D. Individual samples were extracted into acidified methanol and the extracts were analyzed via LC/MS/MS using electrospra...

  5. Novel solidsolid phase change material based on polyethylene glycol and cellulose used for temperature stabilisation

    Wojda Marta


    Full Text Available Thermal management is one of crucial issues in the development of modern electronic devices. In the recent years interest in phase change materials (PCMs as alternative cooling possibility has increased significantly. Preliminary results concerning the research into possibility of the use of solid-solid phase change materials (S-S PCMs for stabilisation temperature of electronic devices has been presented in the paper. Novel solid-solid phase change material based on polyethylene glycol and cellulose has been synthesized. Attempt to improve its thermal conductivity has been taken. Material has been synthesized for the purpose of stabilisation of temperature of electronic devices.

  6. Used solid catalysts from chemical and petrochemical industries; Les catalyseurs solides uses de l`industrie chimique et du raffinage petrolier



    A comprehensive survey of the solid catalysts used in the chemical and petrochemical industries is presented; information on solid catalyst market demand prospective for 1998, the nature of solid catalysts used in the various industrial sectors and for the various chemical products production, the european catalysts manufacturers, solid catalyst poisons and inhibitors according to the various types of chemical reactions, mean compositions of used solid catalysts, an assessment of the volume of used solid catalysts generated by chemical and petrochemical industries, the various ways of solid catalyst regeneration and disposal, the potential for off-site regeneration of used catalysts, and French and European regulations, is presented

  7. Deformability of adsorbents during adsorption and principles of the thermodynamics of solid-phase systems

    Tovbin, Yu. K.


    A microscopic theory of adsorption, based on a discrete continuum lattice gas model for noninert (including deformable) adsorbents that change their lattice parameters during adsorption, is presented. Cases of the complete and partial equilibrium states of the adsorbent are considered. In the former, the adsorbent consists of coexisting solid and vapor phases of adsorbent components, and the adsorbate is a mobile component of the vapor phase with an arbitrary density (up to that of the liquid adsorbate phase). The adsorptive transitioning to the bound state changes the state of the near-surface region of the adsorbent. In the latter, there are no equilibrium components of the adsorbent between the solid and vapor phases. The adsorbent state is shown to be determined by its prehistory, rather than set by chemical potentials of vapor of its components. Relations between the microscopic theory and thermodynamic interpretations are discussed: (1) adsorption on an open surface, (2) two-dimensional stratification of the adsorbate mobile phase on an open homogeneous surface, (3) small microcrystals in vacuum and the gas phase, and (4) adsorption in porous systems.

  8. Phase Equilibria of Stored Chemical Energy Reactants.


    The reaction of lithium aluminum alloy with water at high temperature is considered in terms of phase equilibria in the system Li-A1-0-H. A...thermodynamic analysis of the system reveals the potential importance of lithium hydride as a reaction product. Major needs for experimental phase equilibria data

  9. Crystallization: A phase transition process driving by chemical potential decrease

    Sun, Congting; Xue, Dongfeng


    A chemical bonding model is established to describe the chemical potential decrease during crystallization. In the nucleation stage, in situ molecular vibration spectroscopy shows the increased vibration energy of constituent groups, indicating the shortened chemical bonding and the decreased chemical potential towards the formation of nuclei. Starting from the Gibbs free energy formula, the chemical potential decrease during crystallization is scaled, which depends on the released chemical bonding energy per unit phase transition zone. In the crystal growth, the direction-dependent growth rate of inorganic single crystals can be quantitatively determined, their anisotropic thermodynamic morphology can thus be constructed on the basis of relative growth rates.

  10. Solid Phase Peptide Synthesis of Fusukang for AIDS

    甘一如; 戴琦; 张雪竹; 高晨昊


    A 36-residue peptide is designed to cure acquired immunodeficiency syndrome(AIDS), and is synthesized by the manual solid phase peptide synthesis technique. Different reaction conditions of the synthesis process were discussed. Stirring efficiency of mechanics and nitrogen was compared. The mechanical method displays a predominant performance. Although the coupling efficiencies of diisopropylcarbodiimide(DIC) and dicyclohexylcarbodiimide(DCC) are virtually identical, DIC offers several advantages over DCC in practice due to different physical characters. Wash conditions after deprotection and coupling were investigated to monitor washing efficiency. 0.369 2 g crude peptide was obtained.

  11. Solid-phase colorimetric method for the quantification of fucoidan.

    Lee, Jung Min; Shin, Z-U; Mavlonov, Gafurjon T; Abdurakhmonov, Ibrokhim Y; Yi, Tae-Hoo


    We described the simple, selective, and rapid method for determination of fucoidans using methylene blue staining of sulfated polysaccharides, immobilized into filter paper and consequent optic density (at A (663) nm) measurement of the eluted dye from filter paper. This solid-phase method allows selective determination of 1-20 μg fucoidan in presence of potentially interfering compounds (alginic acid, DNA, salts, proteins, and detergents). Further, we demonstrated the alternative way of using image processing software for fucoidan quantification without extraction of methylene blue dye from stained spots of fucoidan-dye complex.


    E.Q. Xie; W.W. Wang; N. Jiang; D.Y. He


    Manganese silicide MnSi2-x thin films have been prepared on n-type silicon substratesthrough solid phase reaction. The heterostructures were analyzed by X-ray diffraction,Rutherford backscattering spectroscopy, Fourier transform infrared transmittance spec-troscopy and the four-point probe technique. The results show that two manganese sili-cides have been formed sequentially via the reaction of thin layer Mn with Si substrateat different irradiation annealing stages, i.e., MnSi at 450℃ and MnSi1.73 at 550℃.MnSi1.73 phase exhibits preferred growth after irradiation with infrared. In situ four-point probe measurements of sheet resistance during infrared irradiation annealingshow that nucleation of MnSi and phase transformation of MnSi to MnSi1. 73 occur at410℃ and 530℃, respectively; the MnSi phase shows metallic behavior, while MnSi1.73exhibits semiconducting behavior. Characteristic phonon bands of MnSi2-x silicides,which can be used for phase identification along with conventional XRD techniques,have been observed by FTIR spectroscopy.

  13. Solid phase extraction and metabolic profiling of exudates from living copepods

    Selander, Erik; Heuschele, Jan; Nylund, Göran M.


    Copepods are ubiquitous in aquatic habitats. They exude bioactive compounds that mediate mate finding or induce defensive traits in prey organisms. However, little is known about the chemical nature of the copepod exometabolome that contributes to the chemical landscape in pelagic habitats. Here we...... describe the development of a closed loop solid phase extraction setup that allows for extraction of exuded metabolites from live copepods. We captured exudates from male and female Temora longicornis and analyzed the content with high resolution LC-MS. Chemometric methods revealed 87 compounds...... that constitute a specific chemical pattern either qualitatively or quantitatively indicating copepod presence. The majority of the compounds were present in both female and male exudates, but nine compounds were mainly or exclusively present in female exudates and hence potential pheromone candidates...

  14. Carbonyl Diisocyanate CO(NCO)2: Synthesis and Structures in Solid State and Gas Phase.

    Klapötke, Thomas M; Krumm, Burkhard; Rest, Sebastian; Scharf, Regina; Schwabedissen, Jan; Stammler, Hans-Georg; Mitzel, Norbert W


    A modified synthesis for carbonyl diisocyanate, CO(NCO)2, starting from trichloroisocyanuric acid and diphosgene is described. In addition to the previously reported (13)C NMR resonances, the (15)N NMR shift is determined for the first time. The structure in the solid state was determined by X-ray diffraction (XRD) on in situ grown crystals, that in the gas phase was experimentally determined by electron diffraction (GED) and for single molecules theoretically by quantum-chemical calculations. The structures are compared and discussed with related systems. Quantum-chemical calculations as well as GED and XRD prove syn-syn to be the conformation of lowest energy. In quantum-chemical calculations and GED the presence of a syn-anti conformer was confirmed and the structure of this conformer was determined.

  15. Electrostatic levitation studies of supercooled liquids and metastable solid phases

    Rustan, Gustav Errol

    been carried out to study the metastable phase formation in an Fe83B17 near eutectic alloy. Initial supercooling measurements using the ISU-ESL identified the formation of three metastable phases: a precipitate phase that shows stable coexistence with the deeply supercooled liquid, and two distinct bulk solidification phases. To identify the structure of the metastable phases, the Washington University Beamline ESL (WU-BESL) has been used to perform in-situ high energy x-ray diffraction measurements of the metastable phases. Based on the x-ray results, the precipitate phase has been identified as bcc-Fe, and the more commonly occurring bulk solidification product has been found to be a two-phase mixture of Fe23B6 plus fcc-Fe, which appears, upon cooling, to transform into a three phase mixture of Fe23B6, bcc-Fe, and an as-yet unidentified phase, with the transformation occurring at approximately the expected fcc-to-bcc transformation temperature of pure Fe. To further characterize the multi-phase metastable alloy, the ISU-ESL has been used to perform measurements of volume thermal expansion via the videographic technique, as well as RF susceptibility via the TDO technique. The results of the thermal expansion and susceptibility data have been found to be sensitive indicators of additional structural changes that may be occurring in the metastable solid at temperatures below 1000 K, and the susceptibility data has revealed that three distinct ferromagnetic phase transitions take place within the multi-phase mixture. Based on these results, it has been hypothesized that there may be an additional transformation taking place that leads to the formation of either bct- or o-Fe3B in addition to the Fe23B6 phase, although further work is required to test this hypothesis.

  16. Nucleation of the diamond phase in aluminium-solid solutions

    Hornbogen, E.; Mukhopadhyay, A. K.; Starke, E. A., Jr.


    Precipitation was studied from fcc solid solutions with silicon, germanium, copper and magnesium. Of all these elements only silicon and germanium form diamond cubic (DC) precipitates in fcc Al. Nucleation of the DC structure is enhanced if both types of atom are dissolved in the fcc lattice. This is interpreted as due to atomic size effects in the prenucleation stage. There are two modes of interference of fourth elements with nucleation of the DC phase in Al + Si, Ge. The formation of the DC phase is hardly affected if the atoms (for example, copper) are rejected from the (Si, Ge)-rich clusters. If additional types of atom are attracted by silicon and/or germanium, DC nuclei are replaced by intermetallic compounds (for example Mg2Si).

  17. Powder metallurgy: Solid and liquid phase sintering of copper

    Sheldon, Rex; Weiser, Martin W.


    Basic powder metallurgy (P/M) principles and techniques are presented in this laboratory experiment. A copper based system is used since it is relatively easy to work with and is commercially important. In addition to standard solid state sintering, small quantities of low melting metals such as tin, zinc, lead, and aluminum can be added to demonstrate liquid phase sintering and alloy formation. The Taguchi Method of experimental design was used to study the effect of particle size, pressing force, sintering temperature, and sintering time. These parameters can be easily changed to incorporate liquid phase sintering effects and some guidelines for such substitutions are presented. The experiment is typically carried out over a period of three weeks.

  18. Carbon nanotubes as solid-phase extraction sorbents prior to atomic spectrometric determination of metal species: A review

    Herrero Latorre, C., E-mail: [Universidad de Santiago de Compostela, Dpto. Quimica Analitica, Nutricion y Bromatologia, Facultad de Ciencias, Alfonso X el Sabio s/n, 27002 Lugo (Spain); Alvarez Mendez, J.; Barciela Garcia, J.; Garcia Martin, S.; Pena Crecente, R.M. [Universidad de Santiago de Compostela, Dpto. Quimica Analitica, Nutricion y Bromatologia, Facultad de Ciencias, Alfonso X el Sabio s/n, 27002 Lugo (Spain)


    Highlights: Black-Right-Pointing-Pointer The use of CNTs as sorbent for metal species in solid phase extraction has been described. Black-Right-Pointing-Pointer Physical and chemical strategies for functionalization of carbon nanotubes have been discussed. Black-Right-Pointing-Pointer Published analytical methods concerning solid phase extraction and atomic spectrometric determination have been reviewed. - Abstract: New materials have significant impact on the development of new methods and instrumentation for chemical analysis. From the discovery of carbon nanotubes in 1991, single and multi-walled carbon nanotubes - due to their high adsorption and desorption capacities - have been employed as sorption substrates in solid-phase extraction for the preconcentration of metal species from diverse matrices. Looking for successive improvements in sensitivity and selectivity, in the past few years, carbon nanotubes have been utilized as sorbents for solid phase extraction in three different ways: like as-grown, oxidized and functionalized nanotubes. In the present paper, an overview of the recent trends in the use of carbon nanotubes for solid phase extraction of metal species in environmental, biological and food samples is presented. The determination procedures involved the adsorption of metals on the nanotube surface, their quantitative desorption and subsequent measurement by means of atomic spectrometric techniques such as flame atomic absorption spectrometry, electrothermal atomic absorption spectrometry or inductively coupled plasma atomic emission spectrometry/mass spectrometry, among others. Synthesis, purification and types of carbon nanotubes, as well as the diverse chemical and physical strategies for their functionalization are described. Based on 140 references, the performance and general properties of the applications of solid phase extraction based on carbon nanotubes for metal species atomic spectrometric determination are discussed.

  19. DNA display III. Solid-phase organic synthesis on unprotected DNA.

    David R Halpin


    Full Text Available DNA-directed synthesis represents a powerful new tool for molecular discovery. Its ultimate utility, however, hinges upon the diversity of chemical reactions that can be executed in the presence of unprotected DNA. We present a solid-phase reaction format that makes possible the use of standard organic reaction conditions and common reagents to facilitate chemical transformations on unprotected DNA supports. We demonstrate the feasibility of this strategy by comprehensively adapting solid-phase 9-fluorenylmethyoxycarbonyl-based peptide synthesis to be DNA-compatible, and we describe a set of tools for the adaptation of other chemistries. Efficient peptide coupling to DNA was observed for all 33 amino acids tested, and polypeptides as long as 12 amino acids were synthesized on DNA supports. Beyond the direct implications for synthesis of peptide-DNA conjugates, the methods described offer a general strategy for organic synthesis on unprotected DNA. Their employment can facilitate the generation of chemically diverse DNA-encoded molecular populations amenable to in vitro evolution and genetic manipulation.

  20. Analysis of solids remaining following chemical cleaning in tank 6F

    Poirier, Michael R. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Fondeur, Fernando F. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Missimer, David M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Summer, Michael E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Fink, Samuel D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)


    Following chemical cleaning, a solid sample was collected and submitted to Savannah River National Laboratory (SRNL) for analysis. SRNL analyzed this sample by X-ray Diffraction (XRD) and scanning electron microscopy (SEM) to determine the composition of the solids remaining in Tank 6F and to assess the effectiveness of the chemical cleaning process.

  1. Phase mineralogy studies of solid waste products from coal burning at some Bulgarian themoelectric power plants

    Vassilev, S.V. (Bulgarian Academy of Sciences, Sofia (Bulgaria). Institute of Applied Mineralogy)


    A combination of methods, including separation, crystallo-optical techniques, SEM, TEM, X-ray, etc., were used to characterize the phase mineralogy, chemical composition, microstructure and some genetic phase peculiarities in solid waste products from coal burning. Fly ashes, bottom ashes and lagooned ashes from the burning of Bobov Dol and East Maritza coal at Bobov Dol and East Maritza thermoelectric power plants, respectively, were studied. These wastes comprise inorganic and organic constituents. The inorganic part consists mainly of non-crystalline (amorphous) components (glass spheres, spheroids and angular particles) and lesser amounts of crystalline components represented by various major (quartz, magnetite, hematite, mullite, feldspar, gypsum, anhydrite, kaolinite-metakaolinite), minor (mica, free CaO, calcite, olivine) and accessory (rutile, svanbergite, iron carbide, chloritoid, zincite, pyrolusite, cuprite, zircon, etc.) mineral phases. The organic constituent consists of unburnt coal components represented by slightly changed, semicoked and coked coal particles. The genesis of the solid phases could be: primary, contained in coal and having undergone no phase transitions (quartz, kaolinite, mica, feldspar, volcanic glass, coal particles); secondary, formed during burning (magnetite, hematite, metakaolinite; mullite, anhydrite, free CaO, glass, semicoke, coke); or tertiary, formed during the transport and storage of fly ashes and bottom ashes (gypsum, calcite, hematite, limonite). 21 refs., 4 figs., 4 tabs.

  2. The contribution of solid-state chemistry in the determination of multicomponent phase diagrams

    Jean Claude Tedenac; Franck Gascoin; Didier Ravot


    For a long period of time, the determination of phase diagrams was only supported by experiments related to thermal effects or thermodynamic measurements: thermal analysis, calorimetric measurements, vapor pressures, and EMF measurements. As a matter of fact, solid-solid transformations were not so accurately determined and could not be taken into account in the system's analysis. First, X-ray diffraction methods were used as a support for the thermal analysis. Sec ond, the implementation of novel tools in structural analysis (for example, the Rietveld method) has permitted to increase the knowledge of phase stability. Finally, modeling the phases using a Calphad method needed increasingly more structural results to determine and better understand the phase diagrams. On the other hand, the Calphad method has been widely developed for metallic systems, for oxide systems, and in the past 10 years, for some semi-conductor systems, for example,gallium arsenide, cadmium telluride, and lead telluride systems. In such applications, it is very important to bring point defects in the modeling of the phases to map the defects as a function of the chemical composition. Owing to its complexity,this characteristic, the knowledge of which is crucial for the understanding and the control of potential physical applications, was ignored in the previous assessment of semi-conductor systems.

  3. Studies on solid phase synthesis,characterization and fluorescent property of the new rare earth complexes

    Jianwei SHI


    Full Text Available Rare earth-β-diketone ligand complex luminescent material has stable chemical properties and excellent luminous property. Using europium oxide and (γ-NTA as raw materials, novel rare earth-β-dione complexes are synthesized by solid state coordination chemistry. The synthesis temperature and milling time are discussed for optimization. Experimental results show that the suitable reaction situation is at 50 ℃ and 20 h for solid-phase synthesis. The compositions and structures of the complexes are characterized by means of elemental analysis, UV-Vis and FTIR methods, and the phase stability of the complex is determined by using TG-DTA technique. It is proved that preparation of waterless binary rare earth complexes by the solid phase reaction method results in a higher product yield. The fluorescence spectra show that between Eu (Ⅲ and γ-NTA, there exists efficient energy transfer, and the rare earth complexes synthesis is an excellent red bright light-emitting material with excellent UV excited luminescence properties.

  4. Solid-gaseous phase transformation of elemental contaminants during the gasification of biomass.

    Jiang, Ying; Ameh, Abiba; Lei, Mei; Duan, Lunbo; Longhurst, Philip


    Disposal of plant biomass removed from heavy metal contaminated land via gasification achieves significant volume reduction and can recover energy. However, these biomass often contain high concentrations of heavy metals leading to hot-corrosion of gasification facilities and toxic gaseous emissions. Therefore, it is of significant interest to gain a further understanding of the solid-gas phase transition of metal(loid)s during gasification. Detailed elemental analyses (C, H, O, N and key metal/metalloid elements) were performed on five plant species collected from a contaminated site. Using multi-phase equilibria modelling software (MTDATA), the analytical data allows modelling of the solid/gas transformation of metal(loid)s during gasification. Thermodynamic modelling based on chemical equilibrium calculations was carried out in this study to predict the fate of metal(loid) elements during typical gasification conditions and to show how these are influenced by metal(loid) composition in the biomass and operational conditions. As, Cd, Zn and Pb tend to transform to their gaseous forms at relatively low temperatures (1200°C). Simulation of pressurised gasification conditions shows that higher pressures increase the temperature at which solid-to-gaseous phase transformations takes place.

  5. Solid phase speciation of Zn and Cd in zinc smelter effluent-irrigated soils

    Prasenjit Ray


    Full Text Available Solubility of metal in contaminated soils is a key factor which controls the phytoavailability and toxic effects of metals on soil environment. The chemical equilibria of metal ions between soil solution and solid phases govern the solubility of metals in soil. Hence, an attempt was made to identify the probable solid phases (minerals, which govern the solubility of Zn2+ and Cd2+ in zinc smelter effluent-irrigated soils. Estimation of free ion activities of Zn2+ (pZn2+ and Cd2+ (pCd2+ by Baker soil test indicated that metal ion activities were higher in smelter effluent-irrigated soils as compared to that in tubewell water-irrigated soils. Identification of solid phases further reveals that free ion activity of Zn2+ and Cd2+ in soil highly contaminated with Zn and Cd due to long-term irrigation with zinc smelter effluent is limited by the solubility of willemite (Zn2SiO4 in equilibrium with quartz and octavite (CdCO3, respectively. However, in case of tubewell water-irrigated soil, franklinite (ZnFe2O4 in equilibrium with soil-Fe and exchangeable Cd are likely to govern the activity of Zn2+ and Cd2+ in soil solution, respectively. Formation of highly soluble minerals namely, willemite and octavite indicates the potential ecological risk of Zn and Cd, respectively in smelter effluent irrigated soil.

  6. Hyperdoping silicon with selenium: solid vs. liquid phase epitaxy.

    Zhou, Shengqiang; Liu, Fang; Prucnal, S; Gao, Kun; Khalid, M; Baehtz, C; Posselt, M; Skorupa, W; Helm, M


    Chalcogen-hyperdoped silicon shows potential applications in silicon-based infrared photodetectors and intermediate band solar cells. Due to the low solid solubility limits of chalcogen elements in silicon, these materials were previously realized by femtosecond or nanosecond laser annealing of implanted silicon or bare silicon in certain background gases. The high energy density deposited on the silicon surface leads to a liquid phase and the fast recrystallization velocity allows trapping of chalcogen into the silicon matrix. However, this method encounters the problem of surface segregation. In this paper, we propose a solid phase processing by flash-lamp annealing in the millisecond range, which is in between the conventional rapid thermal annealing and pulsed laser annealing. Flash lamp annealed selenium-implanted silicon shows a substitutional fraction of ~ 70% with an implanted concentration up to 2.3%. The resistivity is lower and the carrier mobility is higher than those of nanosecond pulsed laser annealed samples. Our results show that flash-lamp annealing is superior to laser annealing in preventing surface segregation and in allowing scalability.

  7. Solid-Phase Purification of Synthetic DNA Sequences.

    Grajkowski, Andrzej; Cieslak, Jacek; Beaucage, Serge L


    Although high-throughput methods for solid-phase synthesis of DNA sequences are currently available for synthetic biology applications and technologies for large-scale production of nucleic acid-based drugs have been exploited for various therapeutic indications, little has been done to develop high-throughput procedures for the purification of synthetic nucleic acid sequences. An efficient process for purification of phosphorothioate and native DNA sequences is described herein. This process consists of functionalizing commercial aminopropylated silica gel with aminooxyalkyl functions to enable capture of DNA sequences carrying a 5'-siloxyl ether linker with a "keto" function through an oximation reaction. Deoxyribonucleoside phosphoramidites functionalized with the 5'-siloxyl ether linker were prepared in yields of 75-83% and incorporated last into the solid-phase assembly of DNA sequences. Capture of nucleobase- and phosphate-deprotected DNA sequences released from the synthesis support is demonstrated to proceed near quantitatively. After shorter than full-length DNA sequences were washed from the capture support, the purified DNA sequences were released from this support upon treatment with tetra-n-butylammonium fluoride in dry DMSO. The purity of released DNA sequences exceeds 98%. The scalability and high-throughput features of the purification process are demonstrated without sacrificing purity of the DNA sequences.

  8. Receptors useful for gas phase chemical sensing

    Jaworski, Justyn W; Lee, Seung-Wuk; Majumdar, Arunava; Raorane, Digvijay A


    The invention provides for a receptor, capable of binding to a target molecule, linked to a hygroscopic polymer or hydrogel; and the use of this receptor in a device for detecting the target molecule in a gaseous and/or liquid phase. The invention also provides for a method for detecting the presence of a target molecule in the gas phase using the device. In particular, the receptor can be a peptide capable of binding a 2,4,6-trinitrotoluene (TNT) or 2,4,-dinitrotoluene (DNT).

  9. Solid Phase Characterization of Tank 241-AY-102 Annulus Space Particulate

    Cooke, G. A.


    The Special Analytical Studies Group at the 222-S Laboratory (222-S) examined the particulate recovered from a series of samples from the annular space of tank 241-AY-102 (AY-102) using solid phase characterization (SPC) methods. These include scanning electron microscopy (SEM) using the ASPEX®1 scanning electron microscope, X-ray diffraction (XRD) using the Rigaku®2 MiniFlex X-ray diffractometer, and polarized light microscopy (PLM) using the Nikon®3 Eclipse Pol optical microscope. The SEM is equipped with an energy dispersive X-ray spectrometer (EDS) to provide chemical information.

  10. Studies of phase transitions in the aripiprazole solid dosage form.

    Łaszcz, Marta; Witkowska, Anna


    Studies of the phase transitions in an active substance contained in a solid dosage form are very complicated but essential, especially if an active substance is classified as a BCS Class IV drug. The purpose of this work was the development of sensitive methods for the detection of the phase transitions in the aripiprazole tablets containing initially its form III. Aripiprazole exhibits polymorphism and pseudopolymorphism. Powder diffraction, Raman spectroscopy and differential scanning calorimetry methods were developed for the detection of the polymorphic transition between forms III and I as well as the phase transition of form III into aripiprazole monohydrate in tablets. The study involved the initial 10 mg and 30 mg tablets, as well as those stored in Al/Al blisters, a triplex blister pack and HDPE bottles (with and without desiccant) under accelerated and long term conditions. The polymorphic transition was not observed in the initial and stored tablets but it was visible on the DSC curve of the Abilify(®) 10 mg reference tablets. The formation of the monohydrate was observed in the diffractograms and Raman spectra in the tablets stored under accelerated conditions. The monohydrate phase was not detected in the tablets stored in the Al/Al blisters under long term conditions. The results showed that the Al/Al blisters can be recommended as the packaging of the aripiprazole tablets containing form III.

  11. Thermodynamic Model Formulations for Inhomogeneous Solids with Application to Non-isothermal Phase Field Modelling

    Gladkov, Svyatoslav; Kochmann, Julian; Reese, Stefanie; Hütter, Markus; Svendsen, Bob


    The purpose of the current work is the comparison of thermodynamic model formulations for chemically and structurally inhomogeneous solids at finite deformation based on "standard" non-equilibrium thermodynamics [SNET: e. g. S. de Groot and P. Mazur, Non-equilibrium Thermodynamics, North Holland, 1962] and the general equation for non-equilibrium reversible-irreversible coupling (GENERIC) [H. C. Öttinger, Beyond Equilibrium Thermodynamics, Wiley Interscience, 2005]. In the process, non-isothermal generalizations of standard isothermal conservative [e. g. J. W. Cahn and J. E. Hilliard, Free energy of a non-uniform system. I. Interfacial energy. J. Chem. Phys. 28 (1958), 258-267] and non-conservative [e. g. S. M. Allen and J. W. Cahn, A macroscopic theory for antiphase boundary motion and its application to antiphase domain coarsening. Acta Metall. 27 (1979), 1085-1095; A. G. Khachaturyan, Theory of Structural Transformations in Solids, Wiley, New York, 1983] diffuse interface or "phase-field" models [e. g. P. C. Hohenberg and B. I. Halperin, Theory of dynamic critical phenomena, Rev. Modern Phys. 49 (1977), 435-479; N. Provatas and K. Elder, Phase Field Methods in Material Science and Engineering, Wiley-VCH, 2010.] for solids are obtained. The current treatment is consistent with, and includes, previous works [e. g. O. Penrose and P. C. Fife, Thermodynamically consistent models of phase-field type for the kinetics of phase transitions, Phys. D 43 (1990), 44-62; O. Penrose and P. C. Fife, On the relation between the standard phase-field model and a "thermodynamically consistent" phase-field model. Phys. D 69 (1993), 107-113] on non-isothermal systems as a special case. In the context of no-flux boundary conditions, the SNET- and GENERIC-based approaches are shown to be completely consistent with each other and result in equivalent temperature evolution relations.

  12. Numerical study of light-induced phase behavior of smectic solids

    Chung, Hayoung; Park, Jaesung; Cho, Maenghyo


    By the chemical cross-linking of rigid molecules, liquid crystal polymer (LCP) has been envisaged as a novel heterogeneous material due to the fact that various optical and geometric states of the liquid crystalline (LC) phases are projected onto the polymeric constituents. The phase behavior, which refers to the macroscopic shape change of LCP under thermotropic phase change, is a compelling example of such optical-mechanical coupling. In this study, the photomechanical behavior, which broadly refers to the thermal- or light-induced actuation of smectic solids, is investigated using three-dimensional nonlinear finite element analysis (FEA). First, the various phases of LC are considered as well as their relation to polymeric conformation defined by the strain energy of the smectic polymer; a comprehensive constitutive equation that bridges the strong, optomechanical coupling is then derived. Such photomechanical coupling is incorporated in the FEA considering geometric nonlinearity, which is vital to understanding the large-scale light-induced bending behavior of the smectic solid.To demonstrate the simulation capability of the present model, numerous examples of photomechanical deformations are investigated parametrically, either by changing the operating conditions such as stimuli (postsynthesis) or the intrinsic properties (presynthesis). When compared to nematic solids, distinguished behaviors due to smectic substances are found herein and discussed through experiments. The quasisoftness that bidirectionally couples microscopic variables to mechanical behavior is also explained, while considering the effect of nonlinearity. In addition to providing a comprehensive measure that could deepen the knowledge of photomechanical coupling, the use of the proposed finite element framework offers an insight into the design of light-responsive actuating systems made of smectic solids.

  13. The solid phase extraction of some metal ions using palladium nanoparticles attached to silica gel chemically bonded by silica-bonded N-propylmorpholine as new sorbent prior to their determination by flame atomic absorption spectroscopy.

    Ghaedi, M; Rezakhani, M; Khodadoust, S; Niknam, K; Soylak, M


    In this research at first palladium nanoparticle attached to a new chemically bonded silica gel has been synthesized and has been characterized with different techniques such as X-ray diffraction (XRD), fourier transform infrared (FT-IR), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). Then, this new sorbent (chemically modified silica gel with N-propylmorpholine (PNP-SBNPM)) was efficiently used for preconcentration of some metal ions in various food samples. The influence of effective variables including mass of sorbent, flow rate, pH of sample solutions and condition of eluent such as volume, type and concentration on the recoveries of understudy metal ions were investigated. Following the optimization of variables, the interfering effects of some foreign ions on the preconcentration and determination of the investigated metal ions described. At optimum values of variables, all investigated metal ions were efficiently recovered with efficiency more than 95%, relative standard deviation (RSD) between 2.4 and 2.8, and detection limit in the range of 1.4-2.7 ng mL⁻¹. The present method is simple and rapidly applicable for the determination of the understudied metal ions (ng mL⁻¹) in different natural food samples.

  14. The Solid Phase Extraction of Some Metal Ions Using Palladium Nanoparticles Attached to Silica Gel Chemically Bonded by Silica-Bonded N-Propylmorpholine as New Sorbent prior to Their Determination by Flame Atomic Absorption Spectroscopy

    M. Ghaedi


    Full Text Available In this research at first palladium nanoparticle attached to a new chemically bonded silica gel has been synthesized and has been characterized with different techniques such as X-ray diffraction (XRD, fourier transform infrared (FT-IR, transmission electron microscopy (TEM, and scanning electron microscopy (SEM. Then, this new sorbent (chemically modified silica gel with N-propylmorpholine (PNP-SBNPM was efficiently used for preconcentration of some metal ions in various food samples. The influence of effective variables including mass of sorbent, flow rate, pH of sample solutions and condition of eluent such as volume, type and concentration on the recoveries of understudy metal ions were investigated. Following the optimization of variables, the interfering effects of some foreign ions on the preconcentration and determination of the investigated metal ions described. At optimum values of variables, all investigated metal ions were efficiently recovered with efficiency more than 95%, relative standard deviation (RSD between 2.4 and 2.8, and detection limit in the range of 1.4–2.7 ng mL−1. The present method is simple and rapidly applicable for the determination of the understudied metal ions (ng mL−1 in different natural food samples.

  15. Holographic phase transitions at finite chemical potential

    Mateos, David; Myers, Robert C; Thomson, Rowan M


    Recently holographic techniques have been used to study the thermal properties of N=2 SYM theory, with gauge group SU(Nc) and coupled to Nf Nc Mq there is no phase transition as a function of the temperature and the baryon density is always nonzero. We also compare the present results for the grand canonical ensemble with those for canonical ensemble in which the baryon density is held fixed [1].

  16. Recent developments in automatic solid-phase extraction with renewable surfaces exploiting flow-based approaches

    Miró, Manuel; Hartwell, Supaporn Kradtap; Jakmunee, Jaroon


    Solid-phase extraction (SPE) is the most versatile sample-processing method for removal of interfering species and/or analyte enrichment. Although significant advances have been made over the past two decades in automating the entire analytical protocol involving SPE via flow-injection approaches......,on-line SPE assays performed in permanent mode lack sufficient reliability as a consequence of progressively tighter packing of the bead reactor, contamination of the solid surfaces and potential leakage of functional moieties. This article overviews the current state-of-the-art of an appealing tool...... chemical-derivatization reactions, and it pinpoints the most common instrumental detection techniques utilized. We present and discuss in detail relevant environmental and bioanalytical applications reported in the past few years....

  17. Chemical synthesis and modification of target phases of chalcogenide nanomaterials

    Sines, Ian T.

    Inorganic nanoparticles have been at the forefront of materials research in recent years due to their utility in modern technological processes. Chalcogenide nanomaterials are of particular interest because of their wide range of desirable properties for semiconductors, magnetic devices, and energy industries. Primary factors that dictate the properties of the material are the elemental composition, crystal structure, stoichiometry, crystallite size, and particle morphology. One of the most common approaches to synthesize these materials is through solution mediated routes. This approach offers unique advantages in controlling the morphology and particle size that other methods lack. This dissertation describes our recent work on exploiting solution chemical routes to control the crystal structure and composition of chalcogenide nanomaterials. We will start by discussing solution chemistry routes to synthesize non-equilibrium phases of chaclogenide nanomaterials. By using low-temperature bottom-up techniques it is possible to trap kinetically stable phases that cannot be accessed using traditional high-temperature techniques. We used solution chemistry to synthesize and characterize, for the first time, wurtzite-type MnSe. Wurtzite-type MnSe is the end-member of the highly investigated ZnxMn1-xSe solid solution, a classic magnetic semiconductor system. We will then discuss PbO-type FeS, another non-equilibrium phase that is isostructural with the superconducting phase of FeSe. We synthesized phase-pure PbO-type FeS using a low-temperature solvothermal route. We will then discuss the post-synthetic modification of chalcogenides nanomaterials. By exploiting the solubility of Se and S in tri-n-octylphosphine we can selectively extract the chalcogen from preformed chalcogenide nanomaterials. This gives chemists a technique for purification and phase-targeting of particular chalcogenide phases. This method can be modified to facilitate anion exchange. When Te is

  18. Phase nucleation and evolution mechanisms in heterogeneous solids

    Udupa, Anirudh

    Phase nucleation and evolution is a problem of critical importance in many applications. As the length scales are reduced, it becomes increasingly important to consider interfacial and micro-structural effects that can be safely ignored at larger length scales owing to randomness. The theory of phase nucleation has been addressed usually by the classical nucleation theory, which was originally derived for single component fluid systems, after making an assumption of equilibrium. The criterion has not been rigorously derived for solids, which are far from equilibrium due to dissipation by multiple physical drivers. In this thesis, a thermodynamically sound nucleation criterion is derived for systems with multiple interacting physical phenomena and multiple dissipating mechanisms. This is done, using the tools of continuum mechanics, by determining the change in free energy upon the introduction of a new nucleus into the system. The developed theory is demonstrated to be a generalization of the classical nucleation theory (CNT). The developed theory is then applied to the problem of electromigration driven void nucleation, a serious reliability concern for the microelectronics industry. The void grows and eventually severs the line making the chip nonfunctional. There are two classes of theories at present in the electromigration literature to address the problem of void nucleation, the vacancy supersaturation theory and the entropic dissipation theory, both of which are empirical and based on intuition developed from experimental observations. When the developed theory was applied to the problem of electromigration, it was found to be consistent with the vacancy supersaturation theory, but provided the correct energetic quantity, the chemical potential, which has contribution from both the vacancy concentration as well as the hydrostatic stress. An experiment, consisting of electromigration tests on serpentine lines, was developed to validate the developed

  19. Density functional theory study of phase IV of solid hydrogen

    Pickard, Chris J.; Martinez-Canales, Miguel; Needs, Richard J.


    We have studied solid hydrogen up to pressures of 300 GPa and temperatures of 350 K using density functional theory methods and have found “mixed structures” that are more stable than those predicted earlier. Mixed structures consist of alternate layers of strongly bonded molecules and weakly bonded graphene-like sheets. Quasiharmonic vibrational calculations show that mixed structures are the most stable at room temperature over the pressure range 250-295 GPa. These structures are stabilized with respect to strongly bonded molecular phases at room temperature by the presence of lower frequency vibrational modes arising from the graphene-like sheets. Our results for the mixed structures are consistent with the experimental Raman data [M. I. Eremets and I. A. Troyan, Nat. Mater.1476-112210.1038/nmat3175 10, 927 (2011) and R. T. Howie , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.108.125501 108, 125501 (2012)]. We find that mixed phases are reasonable structural models for phase IV of hydrogen.

  20. Vapour phase synthesis of salol over solid acids via transesterification

    S Z Mohamed Shamshuddin; N Nagaraju


    The transesterification of methyl salicylate with phenol has been studied in vapour phase over solid acid catalysts such as ZrO2, MoO3 and SO$^{2-}_{4}$ or Mo(VI) ions modified zirconia. The catalytic materials were prepared and characterized for their total surface acidity, BET surface area and powder XRD patterns. The effect of mole-ratio of the reactants, catalyst bed temperature, catalyst weight, flowrate of reactants, WHSV and time-on-stream on the conversion (%) of phenol and selectivity (%) of salol has been investigated. A good yield (up to 70%) of salol with 90% selectivity was observed when the reactions were carried out at a catalyst bed temperature of 200°C and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst. The results have been interpreted based on the variation of acidic properties and powder XRD phases of zirconia on incorporation of SO$^{2-}_{4}$ or Mo(VI) ions. The effect of poisoning of acid sites of SO$^{2-}_{4}$ or Mo(VI) ions modified zirconia on total surface acidity, powder XRD phases and catalytic activity was also studied. Possible reaction mechanisms for the formation of salol and diphenyl ether over acid sites are proposed.

  1. Solid phase epitaxial regrowth of (001) anatase titanium dioxide

    Barlaz, David Eitan; Seebauer, Edmund G., E-mail: [Department of Chemical and Biomolecular Engineering, University of Illinois, 600 S Mathews Ave., Urbana, Illinois 61801 (United States)


    The growing interest in metal oxide based semiconductor technologies has driven the need to produce high quality epitaxial films of one metal oxide upon another. Largely unrecognized in synthetic efforts is that some metal oxides offer strongly polar surfaces and interfaces that require electrostatic stabilization to avoid a physically implausible divergence in the potential. The present work examines these issues for epitaxial growth of anatase TiO{sub 2} on strontium titanate (001). Solid phase epitaxial regrowth yields only the (001) facet, while direct crystalline growth by atomic layer deposition yields both the (112) and (001). The presence of amorphous TiO{sub 2} during regrowth may provide preferential stabilization for formation of the (001) facet.

  2. Nanoscale doping of compound semiconductors by solid phase dopant diffusion

    Ahn, Jaehyun, E-mail:; Koh, Donghyi; Roy, Anupam; Banerjee, Sanjay K., E-mail: [Department of Electrical and Computer Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States); Chou, Harry [Materials Science and Engineering Program, University of Texas at Austin, Austin, Texas 78712 (United States); Kim, Taegon [Department of Electrical and Computer Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States); Semiconductor R& D Center, Samsung Electronics Corporation, 1 Samsungjeonja-ro, Hwasung, Kyounggi 445-330 (Korea, Republic of); Song, Jonghan [Advanced Analysis Center, Korea Institute of Science and Technology, Cheongryang, P.O. Box 131, Seoul 130-650 (Korea, Republic of)


    Achieving damage-free, uniform, abrupt, ultra-shallow junctions while simultaneously controlling the doping concentration on the nanoscale is an ongoing challenge to the scaling down of electronic device dimensions. Here, we demonstrate a simple method of effectively doping ΙΙΙ-V compound semiconductors, specifically InGaAs, by a solid phase doping source. This method is based on the in-diffusion of oxygen and/or silicon from a deposited non-stoichiometric silicon dioxide (SiO{sub x}) film on InGaAs, which then acts as donors upon activation by annealing. The dopant profile and concentration can be controlled by the deposited film thickness and thermal annealing parameters, giving active carrier concentration of 1.4 × 10{sup 18 }cm{sup −3}. Our results also indicate that conventional silicon based processes must be carefully reviewed for compound semiconductor device fabrication to prevent unintended doping.

  3. A rapid easy—to—perform solid phase digoxin radioimmunoassay

    LiBin; ZhouMei-Ying; 等


    A solid-phase-radioimmunoassay(SPRIA) for the monitoring of blood digoxin level has been developed,in which a secondary antibody-coated polystyrene tubes are used.This noval method seems to be simple to use and only takes about an half hour.The standard curve is linear from 0.25to 4μg/L.The sensitivity of the detection is 0.1μg/L.Reproducibility studies with 3 control sera of 0.5-2.5μg/L give intraassay CV<5% and interassay CV<10%.The specimens are measured and compared with those of the conventional radioimmunoassay and the values are well correlated(r=0.96,Y=1.022X+0.04μg/L)。

  4. Chemical looping coal gasification with calcium ferrite and barium ferrite via solid--solid reactions

    Siriwardane, Ranjani [U.S. Department of Energy/NETL; Riley, Jarrett [Oak Ridge Inst. for Science and Education (ORISE), Oak Ridge, TN (United States); Tian, Hanjing [West Virginia Univ., Morgantown, WV (United States); Richards, George [U.S. Department of Energy/NETL


    Coal gasification to produce synthesis gas by chemical looping was investigated with two oxygen carriers, barium ferrite (BaFe2O4) and calcium ferrite (CaFe2O4). Thermo-gravimetric analysis (TGA) and fixed-bed flow reactor data indicated that a solid–solid interaction occurred between oxygen carriers and coal to produce synthesis gas. Both thermodynamic analysis and experimental data indicated that BaFe2O4 and CaFe2O4 have high reactivity with coal but have a low reactivity with synthesis gas, which makes them very attractive for the coal gasification process. Adding steam increased the production of hydrogen (H2) and carbon monoxide (CO), but carbon dioxide (CO2) remained low because these oxygen carriers have minimal reactivity with H2 and CO. Therefore, the combined steam–oxygen carrier produced the highest quantity of synthesis gas. It appeared that neither the water–gas shift reaction nor the water splitting reaction promoted additional H2 formation with the oxygen carriers when steam was present. Wyodak coal, which is a sub-bituminous coal, had the best gasification yield with oxygen carrier–steam while Illinois #6 coal had the lowest. The rate of gasification and selectivity for synthesis gas production was significantly higher when these oxygen carriers were present during steam gasification of coal. The rates and synthesis gas yields during the temperature ramps of coal–steam with oxygen carriers were better than with gaseous oxygen.

  5. Solid Phase Extraction Disk Procedure to Determine 239Pu in Soils

    ZHANG Ji-qiao;ZHAO Ya-ping;DING You-qian;ZHANG Sheng-dong;YANG Jin-ling


    Full Text Available 239Pu in many soil samples should be analyzed to survey radioactive pollution level in nuclear facilities and its affinity environment efficiently. In order to input the opt conditions for column experiment, the experiments of the static adsorption coefficient of 239Pu to solid phase extraction disk with different contact time, concentration of HNO3 and different temperature were carried out. The chemical procedure for the rapid separation and determination of 239Pu in soils had been formulated, which using solid phase extraction disk (EmporeTM Anion Exchange-SR as extraction material and liquid scintillation spectrometry counting as measurement. In the procedure, soil sample usage was 10 g, and were leached by 8 mol/L HNO3, the chemical recovery of the procedure was about 78.9%, and the minimum detectable concentration was 3.7 Bq/kg. It took less than 3 hours once and the presence of 137Cs, 90Sr-90Y and natural uranium, 241Am, 99Tc did not interfere with the procedure, owning high DF of them. The procedure can be used extensively in determination of 239Pu in soils.

  6. An extrapolation scheme for solid-state NMR chemical shift calculations

    Nakajima, Takahito


    Conventional quantum chemical and solid-state physical approaches include several problems to accurately calculate solid-state nuclear magnetic resonance (NMR) properties. We propose a reliable computational scheme for solid-state NMR chemical shifts using an extrapolation scheme that retains the advantages of these approaches but reduces their disadvantages. Our scheme can satisfactorily yield solid-state NMR magnetic shielding constants. The estimated values have only a small dependence on the low-level density functional theory calculation with the extrapolation scheme. Thus, our approach is efficient because the rough calculation can be performed in the extrapolation scheme.

  7. New methods and materials for solid phase extraction and high performance liquid chromatography

    Dumont, Philip John [Iowa State Univ., Ames, IA (United States)


    This paper describes methods for solid phase extraction and high performance liquid chromatography (HPLC). The following are described: Effects of Resin Sulfonation on the Retention of Polar Organic Compounds in Solid Phase Extraction; Ion-Chromatographic Separation of Alkali Metals In Non-Aqueous Solvents; Cation-Exchange Chromatography in Non-Aqueous Solvents; and Silicalite As a Stationary Phase For HPLC.

  8. Comparative solution and solid-phase glycosylations toward a disaccharide library

    Agoston, K.; Kröger, Lars; Agoston, Agnes


    A comparative study on solution-phase and solid-phase oligosaccharide synthesis was performed. A 16-member library containing all regioisomers of Glc-Glc, Glc-Gal, Gal-Glc, and Gal-Gal disaccharides was synthesized both in solution and on solid phase. The various reaction conditions for different...

  9. Steady-state diffusion regime in solid-phase micro extraction kinetics

    Benhabib, K.; Laak, ter T.L.; Leeuwen, van H.P.


    The temporal evolution of diffusion-controlled analyte accumulation in solid-phase microextraction (SPME) is critically discussed in terms of the various aspects of steady-state diffusion in the two phases under conditions of fast exchange of the analyte at the solid phase film/water interface. For

  10. Solid-Phase Organic Chemistry: Synthesis of 2β-(HeterocyclylthiomethylPenam Derivatives on Solid Support

    Ernesto G. Mata


    Full Text Available The synthesis of 2β-(heterocyclylthiomethylpenam derivatives on solid support has been developed. Compounds are obtained in good to high yields (based on loading of the original resin. The key step is the solid-phase double rearrangement of the corresponding penicillin sulfoxide.

  11. Solid-state NMR analysis of a complex crystalline phase of ronacaleret hydrochloride.

    Vogt, Frederick G; Williams, Glenn R; Strohmeier, Mark; Johnson, Matthew N; Copley, Royston C B


    A crystalline phase of the pharmaceutical compound ronacaleret hydrochloride is studied by solid-state nuclear magnetic resonance (SSNMR) spectroscopy and single-crystal X-ray diffraction. The crystal structure is determined to contain two independent cationic molecules and chloride anions in the asymmetric unit, which combine with the covalent structure of the molecule to yield complex SSNMR spectra. Experimental approaches based on dipolar correlation, chemical shift tensor analysis, and quadrupolar interaction analysis are employed to obtain detailed information about this phase. Density functional theory (DFT) calculations are used to predict chemical shielding and electric field gradient (EFG) parameters for comparison with experiment. (1)H SSNMR experiments performed at 16.4 T using magic-angle spinning (MAS) and homonuclear dipolar decoupling provide information about hydrogen bonding and molecular connectivity that can be related to the crystal structure. (19)F and (13)C assignments for the Z' = 2 structure are obtained using DFT calculations, (19)F homonuclear dipolar correlation, and (13)C-(19)F heteronuclear dipolar correlation experiments. (35)Cl MAS experiments at 16.4 T observe two chlorine sites that are assigned using calculated chemical shielding and EFG parameters. SSNMR dipolar correlation experiments are used to extract (1)H-(13)C, (1)H-(15)N, (1)H-(19)F, (13)C-(19)F, and (1)H-(35)Cl through-space connectivity information for many positions of interest. The results allow for the evaluation of the performance of a suite of SSNMR experiments and computational approaches as applied to a complex but typical pharmaceutical solid phase.

  12. Phase diagrams and kinetics of solid-liquid phase transitions in crystalline polymer blends

    Matkar, Rushikesh A.

    A free energy functional has been formulated based on an order parameter approach to describe the competition between liquid-liquid phase separation and solid-liquid phase separation. In the free energy description, the assumption of complete solvent rejection from the crystalline phase that is inherent in the Flory diluent theory was removed as solvent has been found to reside in the crystalline phase in the form of intercalates. Using this approach, we have calculated various phase diagrams in binary blends of crystalline and amorphous polymers that show upper or lower critical solution temperature. Also, the discrepancy in the chi values obtained from different experimental methods reported in the literature for the polymer blend of poly(vinylidenefluoride) and poly(methylmethacrylate) has been discussed in the context of the present model. Experimental phase diagram for the polymer blend of poly(caprolactone) and polystyrene has also been calculated. Of particular importance is that the crystalline phase concentration as a function of temperature has been calculated using free energy minimization methods instead of assuming it to be pure. In the limit of complete immiscibility of the solvent in the crystalline phase, the Flory diluent theory is recovered. The model is extended to binary crystalline blends and the formation of eutectic, peritectic and azeotrope phase diagrams has been explained on the basis of departure from ideal solid solution behavior. Experimental eutectic phase diagram from literature of a binary blend of crystalline polymer poly(caprolactone) and trioxane were recalculated using the aforementioned approach. Furthermore, simulations on the spatio temporal dynamics of crystallization in blends of crystalline and amorphous polymers were carried out using the Ginzburg-Landau approach. These simulations have provided insight into the distribution of the amorphous polymer in the blends during the crystallization process. The simulated results

  13. Solid Phase Formylation of N-Terminus Peptides

    Anna Lucia Tornesello


    Full Text Available Formylation of amino groups is a critical reaction involved in several biological processes including post-translational modification of histones. The addition of a formyl group (CHO to the N-terminal end of a peptide chain generates biologically active molecules. N-formyl-peptides can be produced by different methods. We performed the N-formylation of two chemotactic hexapetides, Met1-Leu2-Lys3-Leu4-Ile5-Val6 and Met1-Met2-Tyr3-Ala4-Leu5-Phe6, carrying out the reaction directly on peptidyl-resin following pre-activation of formic acid with N,N-dicyclohexylcarbodiimmide (DCC in liquid phase. The overnight incubation at 4 °C resulted in a significant increase in production yields of formylated peptides compared to the reaction performed at room temperature. The method is consistently effective, rapid, and inexpensive. Moreover, the synthetic strategy can be applied for the formylation of all primary amines at N-terminus of peptide chains or amino groups of lysine side-chains in solid phase.

  14. In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries

    Nandasiri, Manjula I.; Camacho-Forero, Luis E.; Schwarz, Ashleigh M.; Shutthanandan, Vaithiyalingam; Thevuthasan, Suntharampillai; Balbuena, Perla B.; Mueller, Karl T.; Murugesan, Vijayakumar


    Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li-S) batteries lead to the for-mation of solid electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and oth-er electrolyte components are still unclear. We report an in-situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li-S batteries. A multi-modal approach in-volving AIMD modeling and in-situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li2S, LiF, Li2O etc); and formation of a secondary matrix type phase due to cross interaction between reaction products and elec-trolyte components, which is followed by a highly dynamic mono-anionic polysulfide (i.e. LiS5) fouling process. These new molecular-level insights into the SEI layer evolution on Li- anodes are crucial for delineating effective strategies for the development of Li–S batteries.

  15. Insights into Nano- and Micron-Scale Phase Separation in Amorphous Solid Dispersions Using Fluorescence-Based Techniques in Combination with Solid State Nuclear Magnetic Resonance Spectroscopy.

    Purohit, Hitesh S; Ormes, James D; Saboo, Sugandha; Su, Yongchao; Lamm, Matthew S; Mann, Amanda K P; Taylor, Lynne S


    Miscibility between the drug and the polymer in an amorphous solid dispersion (ASD) is considered to be one of the most important factors impacting the solid state stability and dissolution performance of the active pharmaceutical ingredient (API). The research described herein utilizes emerging fluorescence-based methodologies to probe (im)miscibility of itraconazole (ITZ)-hydroxypropyl methylcellulose (HPMC) ASDs. The ASDs were prepared by solvent evaporation with varying evaporation rates and were characterized by steady-state fluorescence spectroscopy, confocal imaging, differential scanning calorimetry (DSC), and solid state nuclear magnetic resonance (ssNMR) spectroscopy. The size of the phase separated domains for the ITZ-HPMC ASDs was affected by the solvent evaporation rate. Smaller domains (30 nm) were found in ASDs prepared using slower evaporation rates. Confocal imaging provided visual confirmation of phase separation along with chemical specificity, achieved by selectively staining drug-rich and polymer-rich phases. ssNMR confirmed the results of fluorescence-based techniques and provided information on the size of phase separated domains. The fluorescence-based methodologies proved to be sensitive and rapid in detecting phase separation, even at the nanoscale, in the ITZ-HPMC ASDs. Fluorescence-based methods thus show promise for miscibility evaluation of spray-dried ASDs.

  16. Immunochemical cross-reactivity between albumin and solid-phase adsorbed histamine

    Poulsen, L K; Nolte, H; Søndergaard, I


    For production of an antibody against histamine, this was coupled to human serum albumin (HSA) and used for immunization of rabbits. To test the antiserum, an immunoradiometric assay was developed comprising solid-phase bound histamine, antisera and radiolabelled protein A. Titration and inhibition...... experiments revealed that histamine adsorbed onto a solid-phase could bind the antiserum. However, neither free histamine nor histamine coupled to unrelated carriers could inhibit the binding of antiserum to the solid-phase histamine. Cross-reactivity was demonstrated between HSA and solid-phase bound...

  17. Size Dependence of a Temperature-Induced Solid-Solid Phase Transition in Copper(I) Sulfide

    Rivest, Jessy B; Fong, Lam-Kiu; Jain, Prashant K; Toney, Michael F; Alivisatos, A Paul


    Determination of the phase diagrams for the nanocrystalline forms of materials is crucial for our understanding of nanostructures and the design of functional materials using nanoscale building blocks. The ability to study such transformations in nanomaterials with controlled shape offers further insight into transition mechanisms and the influence of particular facets. Here we present an investigation of the size-dependent, temperature-induced solid-solid phase transition in copper sulfide nanorods from low- to high-chalcocite. We find the transition temperature to be substantially reduced, with the high chalcocite phase appearing in the smallest nanocrystals at temperatures so low that they are typical of photovoltaic operation. Size dependence in phase trans- formations suggests the possibility of accessing morphologies that are not found in bulk solids at ambient conditions. These other- wise-inaccessible crystal phases could enable higher-performing materials in a range of applications, including sensing, switching, lighting, and photovoltaics.

  18. From Polymer to Small Organic Molecules: A Tight Relationship between Radical Chemistry and Solid-Phase Organic Synthesis

    Danilo Mirizzi


    Full Text Available Since Gomberg’s discovery of radicals as chemical entities, the interest around them has increased through the years. Nowadays, radical chemistry is used in the synthesis of 75% of all polymers, inevitably establishing a close relationship with Solid-Phase Organic Synthesis. More recently, the interest of organic chemists has shifted towards the application of usual “in-solution” radical chemistry to the solid-phase, ranging from the use of supported reagents for radical reactions, to the development of methodologies for the synthesis of small molecules or potential libraries. The aim of this review is to put in perspective radical chemistry, moving it away from its origin as a synthetic means for solid supports, to becoming a useful tool for the synthesis of small molecules.

  19. From polymer to small organic molecules: a tight relationship between radical chemistry and solid-phase organic synthesis.

    Mirizzi, Danilo; Pulici, Maurizio


    Since Gomberg's discovery of radicals as chemical entities, the interest around them has increased through the years. Nowadays, radical chemistry is used in the synthesis of 75% of all polymers, inevitably establishing a close relationship with Solid-Phase Organic Synthesis. More recently, the interest of organic chemists has shifted towards the application of usual "in-solution" radical chemistry to the solid-phase, ranging from the use of supported reagents for radical reactions, to the development of methodologies for the synthesis of small molecules or potential libraries. The aim of this review is to put in perspective radical chemistry, moving it away from its origin as a synthetic means for solid supports, to becoming a useful tool for the synthesis of small molecules.

  20. Application of Photocured Polymer Ion Selective Membranes for Solid-State Chemical Sensors

    Natalia Abramova


    Full Text Available Application of conducting polymers with additional functional groups for a solid contact formation and photocurable membranes as sensitive elements of solid-state chemical sensors is discussed. Problems associated with application of UV-curable polymers for sensors are analyzed. A method of sensor fabrication using copolymerized conductive layer and sensitive membrane is presented and the proof of concept is confirmed by two examples of solid-contact electrodes for Ca ions and pH.

  1. Shortcut access to peptidosteroid conjugates: building blocks for solid-phase bile acid scaffold decoration by convergent ligation.

    Verzele, Dieter; Figaroli, Sara; Madder, Annemieke


    We present three versatile solid-supported scaffold building blocks based on the (deoxy)cholic acid framework and decorated with handles for further derivatization by modern ligation techniques such as click chemistry, Staudinger ligation or native chemical ligation. Straightforward procedures are presented for the synthesis and analysis of the steroid constructs. These building blocks offer a new, facile and shorter access route to bile acid-peptide conjugates on solid-phase with emphasis on heterodipodal conjugates with defined spatial arrangements. As such, we provide versatile new synthons to the toolbox for bile acid decoration.

  2. Shortcut Access to Peptidosteroid Conjugates: Building Blocks for Solid-Phase Bile Acid Scaffold Decoration by Convergent Ligation

    Sara Figaroli


    Full Text Available We present three versatile solid-supported scaffold building blocks based on the (deoxycholic acid framework and decorated with handles for further derivatization by modern ligation techniques such as click chemistry, Staudinger ligation or native chemical ligation. Straightforward procedures are presented for the synthesis and analysis of the steroid constructs. These building blocks offer a new, facile and shorter access route to bile acid-peptide conjugates on solid-phase with emphasis on heterodipodal conjugates with defined spatial arrangements. As such, we provide versatile new synthons to the toolbox for bile acid decoration.

  3. Advanced Multi-Phase Flow CFD Model Development for Solid Rocket Motor Flowfield Analysis

    Liaw, Paul; Chen, Y. S.; Shang, H. M.; Doran, Denise


    It is known that the simulations of solid rocket motor internal flow field with AL-based propellants require complex multi-phase turbulent flow model. The objective of this study is to develop an advanced particulate multi-phase flow model which includes the effects of particle dynamics, chemical reaction and hot gas flow turbulence. The inclusion of particle agglomeration, particle/gas reaction and mass transfer, particle collision, coalescence and breakup mechanisms in modeling the particle dynamics will allow the proposed model to realistically simulate the flowfield inside a solid rocket motor. The Finite Difference Navier-Stokes numerical code FDNS is used to simulate the steady-state multi-phase particulate flow field for a 3-zone 2-D axisymmetric ASRM model and a 6-zone 3-D ASRM model at launch conditions. The 2-D model includes aft-end cavity and submerged nozzle. The 3-D model represents the whole ASRM geometry, including additional grain port area in the gas cavity and two inhibitors. FDNS is a pressure based finite difference Navier-Stokes flow solver with time-accurate adaptive second-order upwind schemes, standard and extended k-epsilon models with compressibility corrections, multi zone body-fitted formulations, and turbulence particle interaction model. Eulerian/Lagrangian multi-phase solution method is applied for multi-zone mesh. To simulate the chemical reaction, penalty function corrected efficient finite-rate chemistry integration method is used in FDNS. For the AL particle combustion rate, the Hermsen correlation is employed. To simulate the turbulent dispersion of particles, the Gaussian probability distribution with standard deviation equal to (2k/3)(exp 1/2) is used for the random turbulent velocity components. The computational results reveal that the flow field near the juncture of aft-end cavity and the submerged nozzle is very complex. The effects of the turbulent particles affect the flow field significantly and provide better

  4. Modeling the solid-liquid phase transition in saturated triglycerides

    Pink, David A.; Hanna, Charles B.; Sandt, Christophe; MacDonald, Adam J.; MacEachern, Ronald; Corkery, Robert; Rousseau, Dérick


    We investigated theoretically two competing published scenarios for the melting transition of the triglyceride trilaurin (TL): those of (1) Corkery et al. [Langmuir 23, 7241 (2007)], in which the average state of each TL molecule in the liquid phase is a discotic "Y" conformer whose three chains are dynamically twisted, with an average angle of ˜120° between them, and those of (2) Cebula et al. [J. Am. Oil Chem. Soc. 69, 130 (1992)], in which the liquid-state conformation of the TL molecule in the liquid phase is a nematic h∗-conformer whose three chains are in a modified "chair" conformation. We developed two competing models for the two scenarios, in which TL molecules are in a nematic compact-chair (or "h") conformation, with extended, possibly all-trans, chains at low-temperatures, and in either a Y conformation or an h∗ conformation in the liquid state at temperatures higher than the phase-transition temperature, T∗=319 K. We defined an h-Y model as a realization of the proposal of Corkery et al. [Langmuir 23, 7241 (2007)], and explored its predictions by mapping it onto an Ising model in a temperature-dependent field, performing a mean-field approximation, and calculating the transition enthalpy ΔH. We found that the most plausible realization of the h-Y model, as applied to the solid-liquid phase transition in TL, and likely to all saturated triglycerides, gave a value of ΔH in reasonable agreement with the experiment. We then defined an alternative h-h∗ model as a realization of the proposal of Cebula et al. [J. Am. Oil Chem. Soc. 69, 130 (1992)], in which the liquid phase exhibits an average symmetry breaking similar to an h conformation, but with twisted chains, to see whether it could describe the TL phase transition. The h-h∗ model gave a value of ΔH that was too small by a factor of ˜3-4. We also predicted the temperature dependence of the 1132 cm-1 Raman band for both models, and performed measurements of the ratios of three TL Raman

  5. Education: Chemical Research Council Gains Solid Financial Footing.

    Kiefer, David


    Conceived three years ago, the Council for Chemical Research (CCR) is meeting its goal to expedite technological transfer between universities and industry. Although funding is still a problem, membership is growing (37 industries and 128 universities). CCR encourages industrial grants to chemistry/chemical engineering departments and the Chemical…

  6. "Meshed-Bag Gathered-Bunch" method for solid-phase synthesis of small molecular diverse compounds.

    Zhang, Suo-De; Liu, Gang; Xia, Shu-Quan; Wu, Ping; Zhang, Liang


    A new "Meshed-Bag Gathered-Bunch" technology for the solid-phase synthesis of chemical libraries was developed. Using such technology, we synthesized muramyl dipeptide mimetics including derivatives at the N- and C-terminus, cyclic muramyl dipeptide mimetics, muramyl dipeptide and Tuftsin's analogue conjugates. The advantages of such a method include ease of manufacture, low unit cost of production, the physical encoding method, and the compatibility with both parallel and "split-mix" approaches.

  7. Preparation of Pt/C Catalyst with Solid Phase Reaction Method


    The Pt/C catalyst was prepared with solid phase reaction method (Pt/C(S)) for the first time. Its performances were compared with that prepared by the traditional liquid phase reaction method. The results demonstrate that the electrocatalytic activity of Pt/C catalyst with solid phase reaction method for methanol oxidation is higher than that with liquid phase reaction method. XRD and TEM measurements indicate that the Pt/C(S) possesses low crystalline extent and small particle size.


    Yuliya Modna


    Full Text Available The acute destructive pneumonias (ADP occupy up to 80% of the total number of pneumonias. They require constant improvement of treatment strategy. Nowadays the use of surfactants is a part of most treatment protocols. The aim was to study the features of the solid phase bronchoalveolar lavage in children with the ADPs in the dynamics of complex treatment with exogenous surfactant.Material and methods: We examined 39 patients of contaminated surgery. We identified 2 groups of patients. The patients of first group (n=27 had pulmonary pleural form of ADP, the second group (n=12 had pulmonary form of ADP. All patients got classical treatment and the earlier draining of pleural cavity. We used as an antiseptic reamberin 1.5% by 10 ml/kg and endobronchially injected exogenous surfactant Bl in dose12 mg/kg body weight a day, 6 mg/kg every 12 hours. All the children were made a bronchoscopy to obtain BAL to study the crystallization properties. The solid phase of BAL was studied by method of cuneal dehydration.Results: All facies before treatment were divided into two groups according to classification of facies of biological fluids. Only the facies of the second and the third types were detected there. It was revealed that the sizes of the zones of the facies were different in the comparison groups before treatment and after. And the level of crystalline structures and amorphous aggregates were different in the groups with different degrees of inflammation.Conclusion: So, we can assume that the change in surfactant system is characterized by changes in the morphological structure of solids phases of BAL. And the morphological structure of BAL depends on the chemical composition of BAL.

  9. Molecularly imprinted solid phase extraction of fluconazole from pharmaceutical formulations.

    Manzoor, S; Buffon, R; Rossi, A V


    This work encompasses a direct and coherent strategy to synthesise a molecularly imprinted polymer (MIP) capable of extracting fluconazole from its sample. The MIP was successfully prepared from methacrylic acid (functional monomer), ethyleneglycoldimethacrylate (crosslinker) and acetonitrile (porogenic solvent) in the presence of fluconazole as the template molecule through a non-covalent approach. The non-imprinted polymer (NIP) was prepared following the same synthetic scheme, but in the absence of the template. The data obtained from scanning electronic microscopy, infrared spectroscopy, thermogravimetric and nitrogen Brunauer-Emmett-Teller plot helped to elucidate the structural as well as the morphological characteristics of the MIP and NIP. The application of MIP as a sorbent was demonstrated by packing it in solid phase extraction cartridges to extract fluconazole from commercial capsule samples through an offline analytical procedure. The quantification of fluconazole was accomplished through UPLC-MS, which resulted in LOD≤1.63×10(-10) mM. Furthermore, a high percentage recovery of 91±10% (n=9) was obtained. The ability of the MIP for selective recognition of fluconazole was evaluated by comparison with the structural analogues, miconazole, tioconazole and secnidazole, resulting in percentage recoveries of 51, 35 and 32%, respectively.

  10. Automated Solid-Phase Radiofluorination Using Polymer-Supported Phosphazenes

    Bente Mathiessen


    Full Text Available The polymer supported phosphazene bases PS-P2tBu and the novel PS-P2PEG allowed for efficient extraction of [18F]F− from proton irradiated [18O]H2O and subsequent radiofluorination of a broad range of substrates directly on the resin. The highest radiochemical yields were obtained with aliphatic sulfonates (69% and bromides (42%; the total radiosynthesis time was 35–45 min. The multivariate analysis showed that the radiochemical yields and purities were controlled by the resin load, reaction temperature, and column packing effects. The resins could be reused several times with the same or different substrates. The fully automated on-column radiofluorination methodology was applied to the radiosynthesis of the important PET radiotracers [18F]FLT and [18F]FDG. The latter was produced with 40% yield on a 120 GBq scale and passed GMP-regulated quality control required for commercial production of [18F]FDG. The combination of compact form factor, simplicity of [18F]F− recovery and processing, and column reusability can make solid phase radiofluorination an attractive radiochemistry platform for the emerging dose-on-demand instruments for bedside production of PET radiotracers.

  11. Binding of properdin to solid-phase immune complexes

    Junker, A; Baatrup, G; Svehag, S E


    The capacity of serum to support deposition of C3, properdin and factor B was studied by enzyme-linked immunosorbent assay using solid-phase immune complexes (IC) for activation of complement. Deposition of C3 and properdin occurred in fairly dilute normal human serum (NHS), but factor B uptake...... was hardly detectable. Alternative pathway-mediated deposition of C3 with slow kinetics was demonstrated in C2-deficient serum and in NHS depleted of C1q, factor D and properdin (C1qDP-depleted serum) after reconstitution with factor D and properdin. Efficient uptake of properdin required a functional...... classical pathway, in the presence of which C3 and properdin were rapidly deposited onto the IC. Judging from findings in C3-deficient serum, factor I-deficient serum, and C1qDPB-depleted serum, the uptake of properdin was strictly C3-dependent, and did not require the presence of factors B and D. Thus, C3b...

  12. Microwave heating in solid-phase peptide synthesis.

    Pedersen, Søren L; Tofteng, A Pernille; Malik, Leila; Jensen, Knud J


    The highly refined organic chemistry in solid-phase synthesis has made it the method of choice not only to assemble peptides but also small proteins - mainly on a laboratory scale but increasingly also on an industrial scale. While conductive heating occasionally has been applied to peptide synthesis, precise microwave irradiation to heat the reaction mixture during coupling and N(α)-deprotection has become increasingly popular. It has often provided dramatic reductions in synthesis times, accompanied by an increase in the crude peptide purity. Microwave heating has been proven especially relevant for sequences which might form β-sheet type structures and for sterically difficult couplings. The beneficial effect of microwave heating appears so far to be due to the precise nature of this type of heating, rather than a peptide-specific microwave effect. However, microwave heating as such is not a panacea for all difficulties in peptide syntheses and the conditions may need to be adjusted for the incorporation of Cys, His and Asp in peptides, and for the synthesis of, for example, phosphopeptides, glycopeptides, and N-methylated peptides. Here we provide a comprehensive overview of the advances in microwave heating for peptide synthesis, with a focus on systematic studies and general protocols, as well as important applications. The assembly of β-peptides, peptoids and pseudopeptides are also evaluated in this critical review (254 references).

  13. Solid-phase microextraction and the human fecal VOC metabolome.

    Emma Dixon

    Full Text Available The diagnostic potential and health implications of volatile organic compounds (VOCs present in human feces has begun to receive considerable attention. Headspace solid-phase microextraction (SPME has greatly facilitated the isolation and analysis of VOCs from human feces. Pioneering human fecal VOC metabolomic investigations have utilized a single SPME fiber type for analyte extraction and analysis. However, we hypothesized that the multifarious nature of metabolites present in human feces dictates the use of several diverse SPME fiber coatings for more comprehensive metabolomic coverage. We report here an evaluation of eight different commercially available SPME fibers, in combination with both GC-MS and GC-FID, and identify the 50/30 µm CAR-DVB-PDMS, 85 µm CAR-PDMS, 65 µm DVB-PDMS, 7 µm PDMS, and 60 µm PEG SPME fibers as a minimal set of fibers appropriate for human fecal VOC metabolomics, collectively isolating approximately 90% of the total metabolites obtained when using all eight fibers. We also evaluate the effect of extraction duration on metabolite isolation and illustrate that ex vivo enteric microbial fermentation has no effect on metabolite composition during prolonged extractions if the SPME is performed as described herein.

  14. Phase I studies of porfiromycin (NSC--56410) in solid tumors.

    Grage, T B; Weiss, A J; Wilson, W; Reynolds, V


    Porfiromycin was given to a group of patients with a variety of solid tumors. Of 114 patients admitted to the study, 103 yielded evaluable data. The following dosage schedules were used to determine the toxicity of porfiromycin when given in multiple doses by intravenous injection: 0.2 mg/kg x 5 days, 0.3 mg/kg x 5 days, 0.35 mg/kg x 5 days, 0.4 mg/kg x 5 days, 0.24 mg/kg x 10 days and 0.6 mg/kg weekly. Toxic effects noted were mainly leukopenia, thrombocytopenia, and, when injected paravenously, local tissue necrosis. Biological effects were noted at all dosage levels and were more severe at the higher dosages. The data suggest that profiromycin administered intravenously at a dose of 0.35 mg/kg daily for 5 days results in moderate hermatological toxicity and clinical evaluation in a Phase II study at this dosage level is indicated.

  15. Headspace solid-phase microextraction for wine volatile analysis.

    Azzi-Achkouty, Samar; Estephan, Nathalie; Ouaini, Naïm; Rutledge, Douglas N


    The most commonly used technique to prepare samples for the analysis of wine volatile is the headspace solid-phase microextraction (HS-SPME). This method has gained popularity in last few years, as it is a unique solventless preparation technique. In this paper, a summary of recently published studies using HS-SPME for the analysis of wine aromas, with special emphasis on the method developed, has been compiled. Several papers are discussed in detail, mainly with respect to the SPME conditions used. A brief summary of the reviews related to HS-SPME analysis is given and discussed. Several parameters affecting the HS-SPME, such as the salt concentration and the agitation conditions, are used in the same way as used in several papers. The HS-SPME extraction proved to be sufficiently sensitive to satisfy legislative requirements related to low detection and quantification limits as well as method accuracy and precision requirements. However, in order to achieve the best performance and precision, the protocol needs to be optimized for each case. The effect of different parameters must be well characterized to ensure correct extraction and desorption to ensure the transfer of extracted compounds into the analytical system. The operating parameters, such as time, temperature, and agitation, must then be kept constant for all the samples.

  16. Chemical imaging and solid state analysis at compact surfaces using UV imaging

    Wu, Jian X.; Rehder, Sönke; van den Berg, Frans


    Fast non-destructive multi-wavelength UV imaging together with multivariate image analysis was utilized to visualize distribution of chemical components and their solid state form at compact surfaces. Amorphous and crystalline solid forms of the antidiabetic compound glibenclamide...... and excipients in a non-invasive way, as well as mapping the glibenclamide solid state form. An exploratory data analysis supported the critical evaluation of the mapping results and the selection of model parameters for the chemical mapping. The present study demonstrated that the multi-wavelength UV imaging...

  17. Quantitative Infrared Spectra of Vapor Phase Chemical Agents

    Sharpe, Steven W.; Johnson, Timothy J.; Chu, P M.; Kleimeyer, J; Rowland, Brad; Gardner, Patrick J.


    Quantitative high resolution (0.1 cm -1) infrared spectra have been acquired for a number of pressure broadened (101.3 KPa N2), vapor phase chemicals including: Sarin (GB), Soman (GD), Tabun (GA), Cyclosarin (GF), VX, nitrogen mustard (HN3), sulfur mustard (HD) and Lewisite (L).

  18. Summer Research Institute Interfacial and Condensed Phase Chemical Physics

    Barlow, Stephan E.


    Pacific Northwest National Laboratory (PNNL) hosted its first annual Summer Research Institute in Interfacial and Condensed Phase Chemical Physics from May through September 2004. During this period, fourteen PNNL scientists hosted sixteen young scientists from eleven different universities. Of the sixteen participants, fourteen were graduate students; one was transitioning to graduate school; and one was a university faculty member.

  19. An acid-stable tert-butyldiarylsilyl (TBDAS) linker for solid-phase organic synthesis.

    Diblasi, Christine M; Macks, Daniel E; Tan, Derek S


    [reaction: see text] A new, robust tert-butyldiarylsilyl (TBDAS) linker has been developed for solid-phase organic synthesis. This linker is stable to both protic and Lewis acidic reaction conditions, overcoming a significant limitation of previously reported silyl linkers. Solid-phase acetal deprotection, olefination, asymmetric allylation, and silyl protecting group deblocking reactions have been demonstrated with TBDAS-linked substrates.

  20. 40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.


    ... MATERIALS Definitions § 227.32 Liquid, suspended particulate, and solid phases of a material. (a) For the... 40 Protection of Environment 24 2010-07-01 2010-07-01 false Liquid, suspended particulate, and solid phases of a material. 227.32 Section 227.32 Protection of Environment ENVIRONMENTAL...


    A. R. Koohpaei ، S. J. Shahtaheri ، M. R. Ganjali ، A. Rahimi Forushani


    Full Text Available Solid phase extraction is one of the major applications of molecularly imprinted polymers fields for clean-up of environmental and biological samples namely molecularly imprinted solid-phase extraction. In this study, solid phase extraction using the imprinted polymer has been optimized with the experimental design approach for a triazine herbicide, named atrazine with regard to the critical factors which influence the molecular imprinted solid phase extraction efficiency such as sample pH, concentration, flow-rate, volume, elution solvent, washing solvent and sorbent mass. Optimization methods that involve changing one factor at a time can be laborious. A novel approach for the optimization of imprinted solid-phase extraction using chemometrics is described. The factors were evaluated statistically and also validated with spiked water samples and showed a good reproducibility over six consecutive days as well as six within-day experiments. Also, in order to the evaluate efficiency of the optimized molecularly imprinted solid-phase extraction protocols, enrichment capacity, reusability and cross-reactivity of cartridges have been also evaluated. Finally, selective molecularly imprinted solid-phase extraction of atrazine was successfully demonstrated with a recovery above 90% for spiked drinking water samples. It was concluded that the chemometrics is frequently employed for analytical method optimization and based on the obtained results, it is believed that the central composite design could prove beneficial for aiding the molecularly imprinted polymer and molecularly imprinted solid-phase extraction development.

  2. Facile synthesis of aliphatic isothiocyanates and thioureas on solid phase using peptide coupling reagents

    Boas, Ulrik; Andersen, Heidi Gertz; Christensen, Jørn B.;


    Peptide coupling reagents can be used as versatile reagents for the formation of aliphatic isothiocyanates and thioureas on solid phase from the corresponding solid-phase anchored aliphatic primary amines. The formation of the thioureas is fast and highly chemoselective, and proceeds via formation...

  3. The Iron-Iron Carbide Phase Diagram: A Practical Guide to Some Descriptive Solid State Chemistry.

    Long, Gary J.; Leighly, H. P., Jr.


    Discusses the solid state chemistry of iron and steel in terms of the iron-iron carbide phase diagram. Suggests that this is an excellent way of introducing the phase diagram (equilibrium diagram) to undergraduate students while at the same time introducing the descriptive solid state chemistry of iron and steel. (Author/JN)

  4. Complement fixation by solid phase immune complexes. Reduced capacity in SLE sera

    Baatrup, G; Jonsson, H; Sjöholm, A


    We describe an ELISA for assessment of complement function based on the capacity of serum to support fixation of complement components to solid phase immune complexes (IC). Microplates were coated with aggregated bovine serum albumin (BSA) followed by rabbit anti-BSA IgG. The solid phase IC were ...

  5. Solid-state retrodirective phased array concepts for microwave power transmission from Solar Power Satellite

    Schroeder, K. G.; Petroff, I. K.


    Two prototype solid-state phased array systems concepts for potential use in the Solar Power Satellite are described. In both concepts, the beam is centered on the rectenna by means of phase conjugation of a pilot signal emanating from the ground. Also discussed is on-going solid-state amplifier development.

  6. A coupled theory for chemically active and deformable solids with mass diffusion and heat conduction

    Zhang, Xiaolong; Zhong, Zheng


    To analyse the frequently encountered thermo-chemo-mechanical problems in chemically active material applications, we develop a thermodynamically-consistent continuum theory of coupled deformation, mass diffusion, heat conduction and chemical reaction. Basic balance equations of force, mass and energy are presented at first, and then fully coupled constitutive laws interpreting multi-field interactions and evolving equations governing irreversible fluxes are constructed according to the energy dissipation inequality and the chemical kinetics. To consider the essential distinction between mass diffusion and chemical reactions in affecting free energy and dissipations of a highly coupled system, we regard both the concentrations of diffusive species and the extent of reaction as independent state variables. This new formulation then distinguishes between the energy contribution from the diffusive species entering the solid and that from the subsequent chemical reactions occurring among these species and the host solid, which not only interact with stresses or strains in different manners and on different time scales, but also induce different variations of solid microstructures and material properties. Taking advantage of this new description, we further establish a specialized isothermal model to predict precisely the transient chemo-mechanical response of a swelling solid with a proposed volumetric constraint that accounts for material incompressibility. Coupled kinetics is incorporated to capture the volumetric swelling of the solid caused by imbibition of external species and the simultaneous dilation arised from chemical reactions between the diffusing species and the solid. The model is then exemplified with two numerical examples of transient swelling accompanied by chemical reaction. Various ratios of characteristic times of diffusion and chemical reaction are taken into account to shed light on the dependency on kinetic time scales of evolution patterns for

  7. Solid-Phase Organic Synthesis and Catalysis: Some Recent Strategies Using Alumina, Silica, and Polyionic Resins

    Basudeb Basu; Susmita Paul


    Solid-phase organic synthesis (SPOS) and catalysis have gained impetus after the seminal discovery of Merrifield’s solid-phase peptide synthesis and also because of wide applicability in combinatorial and high throughput chemistry. A large number of organic, inorganic, or organic-inorganic hybrid materials have been employed as polymeric solid supports to promote or catalyze various organic reactions. This review article provides a concise account on our approaches involving the use of (i) al...

  8. Nahoon: Time-dependent gas-phase chemical model

    Wakelam, V.


    Nahoon is a gas-phase chemical model that computes the chemical evolution in a 1D temperature and density structure. It uses chemical networks downloaded from the KInetic Database for Astrochemistry (KIDA) but the model can be adapted to any network. The program is written in Fortran 90 and uses the DLSODES (double precision) solver from the ODEPACK package to solve the coupled stiff differential equations. The solver computes the chemical evolution of gas-phase species at a fixed temperature and density and can be used in one dimension (1D) if a grid of temperature, density, and visual extinction is provided. Grains, both neutral and negatively charged, and electrons are considered as chemical species and their concentrations are computed at the same time as those of the other species. Nahoon contains a test to check the temperature range of the validity of the rate coefficients and avoid extrapolations outside this range. A test is also included to check for duplication of chemical reactions, defined over complementary ranges of temperature.

  9. Local Gas Phase Flow Characteristics of a Gas—Liquid—Solid Three—Phase Reversed Flow Jet Loop Reactor

    WENJianping; ChenYunlin; 等


    The local gas-phase flow characteristics such as local gas holdup (εg), local bubble velocity (Vb) and local bubble mean diameter(db) at a specified point in a gas-liquid-solid three-phase reversed flow jet loop reactor was experimentally investigated by a five-point conductivity probe. The effects of gas jet flow rate, liquid jet flow rate, solid loading, nozzle diameter and axial position on the local εg,Vb and db profiles were discussed. The presence of solids at low solid concentrations not only increased the local εg and Vb, but also decreased the local db. The optimum solid olading for the maximum local εg and Vb together with the minimum local db was 0.16×10-3m3, corresponding to a solid volume fraction,εS=2.5%.

  10. Improved detection limits for phthalates by selective solid-phase micro-extraction

    Zia, Asif I.


    Presented research reports on an improved method and enhanced limits of detection for phthalates; a hazardous additive used in the production of plastics by solid-phase micro-extraction (SPME) polymer in comparison to molecularly imprinted solid-phase extraction (MISPE) polymer. The polymers were functionalized on an interdigital capacitive sensor for selective binding of phthalate molecules from a complex mixture of chemicals. Both polymers owned predetermined selectivity by formation of valuable molecular recognition sites for Bis (2-ethylhexyl) phthalate (DEHP). Polymers were immobilized on planar electrochemical sensor fabricated on a single crystal silicon substrate with 500 nm sputtered gold electrodes fabricated using MEMS fabrication techniques. Impedance spectra were obtained using electrochemical impedance spectroscopy (EIS) to determine sample conductance for evaluation of phthalate concentration in the spiked sample solutions with various phthalate concentrations. Experimental results revealed that the ability of SPME polymer to adsorb target molecules on the sensing surface is better than that of MISPE polymer for phthalates in the sensing system. Testing the extracted samples using high performance liquid chromatography with photodiode array detectors validated the results.

  11. Determination of perfluorinated compounds (PFCs) in solid and liquid phase river water samples in Chao Phraya River, Thailand.

    Kunacheva, Chinagarn; Tanaka, Shuhei; Fujii, Shigeo; Boontanon, Suwanna Kitpati; Musirat, Chanatip; Wongwattana, Thana


    Perfluorinated compounds (PFCs), especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are fully fluorinated organic compounds, which have been used in many industrial applications. These chemicals have contaminated surface water all over the world even in developing countries like Thailand. The previous study showed the contamination in Chao Phraya River in 2006 and 2007. The purposes of this field study were to determine the solid and liquid phase of PFCs contamination in Chao Phraya River and to compare the changes of PFC concentration in 2008. Surveys were conducted in the lower reach of Chao Phraya River in the industrialized area. A solid phase extraction (SPE) coupled with HPLC-ESI-MS/MS were used for the analysis for ten PFCs. Ten PFCs were analyzed to identify the contamination in both solid and liquid phases. PFCs were detected in both the solid and liquid phase in every sample. PFOA was the most dominant PFC while PFPA and PFOS were also highly detected in most samples. The average loadings of PFPA, PFOA and PFOS in Chao Phraya River were 94.3, 284.6 and 93.4 g/d, respectively. PFOS concentrations did not show differences between 2006 and 2008. However, PFOA concentrations were higher in 2008/5/26, while comparing other samplings. The ratio of solid:liquid PFPA (2.1:1.0) [(ng/g)/(ng/L)] was lower than PFOA (13.9:1.0) [(ng/g)/(ng/L)] and PFOS (17.6:1.0) [(ng/g)/(ng/L)]. The shorter chain (more hydrophilic) PFC was better to dissolve in water rather than adsorb onto suspended solids. PFOS also showed more potential to attach in the suspended solids than PFOA.

  12. Novel materials and methods for solid-phase extraction and liquid chromatography

    Ambrose, Diana [Iowa State Univ., Ames, IA (United States)


    This report contains a general introduction which discusses solid-phase extraction and solid-phase micro-extraction as sample preparation techniques for high-performance liquid chromatography, which is also evaluated in the study. This report also contains the Conclusions section. Four sections have been removed and processed separately: silicalite as a sorbent for solid-phase extraction; a new, high-capacity carboxylic acid functionalized resin for solid-phase extraction; semi-micro solid-phase extraction of organic compounds from aqueous and biological samples; and the high-performance liquid chromatographic determination of drugs and metabolites in human serum and urine using direct injection and a unique molecular sieve.

  13. Microcosm experiments to study the interaction of solid and solute phases during initial soil development

    Zimmermann, C.; Chabbi, S.; Schaaf, W.


    During the initial phase of soil formation mineral weathering, interactions between the solid and liquid phases as well as accumulation of organic matter play an important role for the development of soil properties and for the establishment of vegetation and the colonization of soil biota. Our study is part of the Transregional Collaborative Research Centre (SFB/TRR 38) ‘Patterns and processes of initial ecosystem development in an artificial catchment' funded by the Deutsche Forschungsgemeinschaft (DFG). The catchment ´Chicken Creeḱ close to Cottbus (Germany) has a size of 6 ha and is composed of a 3-4 m layer of Quaternary loamy to sandy sediments overlying a 1-2 m clay layer. To connect interactions between the soil solid phase and soil solution at the micro-scale with observed processes at the catchment scale we perform microcosm experiments with soil samples from the catchment under controlled laboratory conditions. The microcosm experiments are carried out in a climate chamber at constant 10 °C corresponding to the mean annual temperature of the region. In total 48 soil columns with a diameter of 14.4 cm and height of 30 cm were filled with substrates of two textural compositions reflecting the gradients observed at the catchment and a bulk density of 1.4-1.5 g*cm3. Within the microcosms it is possible to control the gaseous phase and the water fluxes by artificial irrigation. The irrigation runs automated and quasi-continuously four times a day with 6.6 ml each (in total 600 mm*yr-1). Irrigation amount and chemical composition of the artificial rainwater are based on the annual mean at the field site. Litter of two different plant species occurring at the catchment site (Lotus corniculatus, Calamagrostis epigejos) labelled with stable isotopes (δ13C; δ15N) is used for the experiments. All treatments including a control run with four replicates. The gaseous phase in the headspace of the microcosms is analysed continuously for CO2 and N2O contents

  14. Mechanochemical spinodal decomposition: a phenomenological theory of phase transformations in multi-component, crystalline solids

    Rudraraju, Shiva; van der Ven, Anton; Garikipati, Krishna


    We present a phenomenological treatment of diffusion-driven martensitic phase transformations in multi-component crystalline solids that arise from non-convex free energies in mechanical and chemical variables. The treatment describes diffusional phase transformations that are accompanied by symmetry-breaking structural changes of the crystal unit cell and reveals the importance of a mechanochemical spinodal, defined as the region in strain-composition space, where the free-energy density function is non-convex. The approach is relevant to phase transformations wherein the structural order parameters can be expressed as linear combinations of strains relative to a high-symmetry reference crystal. The governing equations describing mechanochemical spinodal decomposition are variationally derived from a free-energy density function that accounts for interfacial energy via gradients of the rapidly varying strain and composition fields. A robust computational framework for treating the coupled, higher-order diffusion and nonlinear strain gradient elasticity problems is presented. Because the local strains in an inhomogeneous, transforming microstructure can be finite, the elasticity problem must account for geometric nonlinearity. An evaluation of available experimental phase diagrams and first-principles free energies suggests that mechanochemical spinodal decomposition should occur in metal hydrides such as ZrH2-2c. The rich physics that ensues is explored in several numerical examples in two and three dimensions, and the relevance of the mechanism is discussed in the context of important electrode materials for Li-ion batteries and high-temperature ceramics.

  15. Chemically Collapsible Mandrel for Solid Rocket Motor Processing

    Dey,Abhijit; Kumar, Arvind; Sikder,Arun K; Gupta, Manoj


    ABSTRACT: Composite propellant mainly consists of two parts, binder matrix (prepolymer, plasticizer, cross linker, antioxidant and curative etc.) and solid ingredients (oxidizer, metal fuel, burn rate modifier, combustion stabilizer etc.). Its processing involves several stages like ingredient preparation (grinding, 1.1 Hazard Division - 1.1 HD), mixing (1.1 HD), casting (1.1 HD), curing (1.3 HD) and extraction (1.3 HD). Each and every process is very hazardous. Removal of any of the mentione...

  16. Chemical analysis of solid residue from liquid and solid fuel combustion: Method development and validation

    Trkmic, M. [University of Zagreb, Faculty of Mechanical Engineering and Naval Architecturek Zagreb (Croatia); Curkovic, L. [University of Zagreb, Faculty of Chemical Engineering and Technology, Zagreb (Croatia); Asperger, D. [HEP-Proizvodnja, Thermal Power Plant Department, Zagreb (Croatia)


    This paper deals with the development and validation of methods for identifying the composition of solid residue after liquid and solid fuel combustion in thermal power plant furnaces. The methods were developed for energy dispersive X-ray fluorescence (EDXRF) spectrometer analysis. Due to the fuels used, the different composition and the location of creation of solid residue, it was necessary to develop two methods. The first method is used for identifying solid residue composition after fuel oil combustion (Method 1), while the second method is used for identifying solid residue composition after the combustion of solid fuels, i. e. coal (Method 2). Method calibration was performed on sets of 12 (Method 1) and 6 (Method 2) certified reference materials (CRM). CRMs and analysis test samples were prepared in pellet form using hydraulic press. For the purpose of method validation the linearity, accuracy, precision and specificity were determined, and the measurement uncertainty of methods for each analyte separately was assessed. The methods were applied in the analysis of real furnace residue samples. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Distinguishing solid bitumens formed by thermochemical sulfate reduction and thermal chemical alteration

    Kelemen, S.R.; Walters, C.C.; Kwiatek, P.J.; Afeworki, M.; Sansone, M.; Freund, H.; Pottorf, R.J.; Machel, H.G.; Zhang, T.; Ellis, G.S.; Tang, Y.; Peters, K.E.


    Insoluble solid bitumens are organic residues that can form by the thermal chemical alteration (TCA) or thermochemical sulfate reduction (TSR) of migrated petroleum. TCA may actually encompass several low temperature processes, such as biodegradation and asphaltene precipitation, followed by thermal alteration. TSR is an abiotic redox reaction where petroleum is oxidized by sulfate. It is difficult to distinguish solid bitumens associated with TCA of petroleum from those associated with TSR when both processes occur at relatively high temperature. The focus of the present work was to characterize solid bitumen samples associated with TCA or TSR using X-ray photoelectron spectroscopy (XPS). XPS is a surface analysis conducted on either isolated or in situ (>25 ??m diameter) solid bitumen that can provide the relative abundance and chemical speciation of carbon, organic and inorganic heteroatoms (NSO). In this study, naturally occurring solid bitumens from three locations, Nisku Fm. Brazeau River area (TSR-related), LaBarge Field Madison Fm. (TSR-related), and the Alaskan Brooks range (TCA-related), are compared to organic solids generated during laboratory simulation of the TSR and TCA processes. The abundance and chemical nature of organic nitrogen and sulfur in solid bitumens can be understood in terms of the nature of (1) petroleum precursor molecules, (2) the concentration of nitrogen by way of thermal stress and (3) the mode of sulfur incorporation. TCA solid bitumens originate from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. Organic sulfur in TCA organic solids remains fairly constant with increasing maturation (3.5 to ???17 sulfur per 100 carbons) into aromatic structures and to the low levels of nitrogen in their hydrocarbon precursors. Hence, XPS results provide organic chemical composition information that helps to

  18. A thermodynamical formulation for chemically active multi-phase turbulent flows

    Ahmadi, G.; Cao, J.


    A generalized thermodynamics for chemically active multiphase solid-fluid mixtures in turbulent state of motion is formulated. The global equations of balance for each phase are ensemble averaged and the local conservation laws for the mean motions are derived. The averaged and the local conservation laws for the mean motions are derived. The averaged form of the Clausius-Duhem inequality is used and the thermodynamics of the chemically active mixtures in turbulent motion is studied. Particular attention is given to the species concentration and chemical reaction effects, in addition to transport and interaction of the phasic fluctuation energies. Based on the averaged entropy inequality, constitutive equations for the stresses, energy, heat and mass fluxes of various species are developed. The explicit governing equations of motion are derived and discussed.

  19. Chemical associations and mobilization of heavy metals in fly ash from municipal solid waste incineration.

    Weibel, Gisela; Eggenberger, Urs; Schlumberger, Stefan; Mäder, Urs K


    This study focusses on chemical and mineralogical characterization of fly ash and leached filter cake and on the determination of parameters influencing metal mobilization by leaching. Three different leaching processes of fly ash from municipal solid waste incineration (MSWI) plants in Switzerland comprise neutral, acidic and optimized acidic (+ oxidizing agent) fly ash leaching have been investigated. Fly ash is characterized by refractory particles (Al-foil, unburnt carbon, quartz, feldspar) and newly formed high-temperature phases (glass, gehlenite, wollastonite) surrounded by characteristic dust rims. Metals are carried along with the flue gas (Fe-oxides, brass) and are enriched in mineral aggregates (quartz, feldspar, wollastonite, glass) or vaporized and condensed as chlorides or sulphates. Parameters controlling the mobilization of neutral and acidic fly ash leaching are pH and redox conditions, liquid to solid ratio, extraction time and temperature. Almost no depletion for Zn, Pb, Cu and Cd is achieved by performing neutral leaching. Acidic fly ash leaching results in depletion factors of 40% for Zn, 53% for Cd, 8% for Pb and 6% for Cu. The extraction of Pb and Cu are mainly limited due to a cementation process and the formation of a PbCu(0)-alloy-phase and to a minor degree due to secondary precipitation (PbCl2). The addition of hydrogen peroxide during acidic fly ash leaching (optimized acidic leaching) prevents this reduction through oxidation of metallic components and thus significantly higher depletion factors for Pb (57%), Cu (30%) and Cd (92%) are achieved. The elevated metal depletion using acidic leaching in combination with hydrogen peroxide justifies the extra effort not only by reduced metal loads to the environment but also by reduced deposition costs.

  20. Pressure Effects on Solid State Phase Transformation of Aluminium Bronze in Cooling Process

    WANG Hai-Yan; CHEN Yan; LIU Yu-Wen; LI Fei; LIU Jian-Hua; PENG Gui-Rong; WANG Wen-Kui


    Effects of high pressure (6 GPa) on the solid state phase transformation kinetic parameters of aluminum bronze during the cooling process are investigated, based on the measurement and calculation of its solid state phase transformation temperature, duration and activation energy and the observation of its microstructures. The results show that high pressure treatment can reduce the solid phase transformation temperature and activation energy in the cooling process and can shorten the phase transformation duration, which is favorable when forming fine-grained aluminum bronze.

  1. The importance of screening solid-state phases of a racemic modification of a chiral drug: thermodynamic and structural characterization of solid-state phases of etiracetam.

    Herman, Christelle; Vermylen, Valérie; Norberg, Bernadette; Wouters, Johan; Leyssens, Tom


    In this contribution different solid-state forms of the racemic compound (RS)-2-(2-oxo-pyrrolidin-1yl)-butyramide are studied from a structural and thermal point of view. Three different solid-state phases were identified, including two polymorphs and one hydrate phase. Comparison is made with the structure of the (S)-enantiomer, for which only one solid-state phase is known. The basic structural motif found in both polymorphs of the racemic compound is similar, but the basic motif observed for the hydrate differs. These synthons could in principle be used in future polymorph prediction studies to screen for possible alternative forms of the enantiopure compound. Based on the structure of the hydrate, further efforts should therefore be made in order to identify a hydrate structure of the enantiopure compound. Studying the different phases of a racemic compound can therefore help to guide polymorphic screening of an enantiopure compound.

  2. Solid and liquid phase equilibria and solid-hydrate formation in binary mixtures of water with amines

    车冠全; 彭文烈; 黄良恩; 古喜兰; 车飙


    Solid and liquid phase diagrams have been constructed for {water+triethylamine,or+N,N-dimethylformamide(DMF) or+N,N-dimethlacetamide (DMA)} Solid-hydrates form with the empirical formulae N(C2H5)3 3H2O,DMF 3H2O,DMF 2H2O,DMA 3H2O and (DMA)2 3H2O.All are congruently melting except the first which melts incongruently.The solid-hydrate formation is attributed to hydrogen bond.The results are compared with the references

  3. Solid phase epitaxial regrowth of (100)GaAs

    Almonte, Marlene Isabel [California Univ., Berkeley, CA (United States). Dept. of Materials Science and Mineral Engineering


    This thesis showed that low temperature (250°C) SPE of stoichiometrically balanced ion implanted GaAs layers can yield good epitaxial recovery for doses near the amorphization threshold. For 250°C anneals, most of the regrowth occurred in the first 10 min. HRTEM revealed much lower stacking fault density in the co-implanted sample than in the As-only and Ga-only samples with comparable doses. After low temp annealing, the nonstoichiometric samples had a large number of residual defects. For higher dose implants, very high temperatures (700°C) were needed to remove residual defects for all samples. The stoichiometrically balanced layer did not regrow better than the Ga-only and As-only samples. The co-implanted sample exhibited a thinner amorphous layer and a room temperature (RT) annealing effect. The amorphous layer regrew about 5 nm, suggesting that stoichiometrically balanced amorphous layers can regrow even at RT. Mechanisms for solid phase crystallization in (100)GasAs is discussed: nucleation and growth of randomly oriented crystallites and SPE. These two mechanisms compete in compound semiconductors at much lower temperatures than in Si. For the low dose As-only and Ga-only samples with low-temp anneals, both mechanisms are active. For this amorphization threshold dose, crystallites remain in the amorphous layer for all as-implants. 250°C annealing showed recrystallization from the surface and bulk for these samples; for the co-implant, the mechanism is not evident.

  4. Application of solid phase microextraction on dental composite resin analysis.

    Wang, Ven-Shing; Chang, Ta-Yuan; Lai, Chien-Chen; Chen, San-Yue; Huang, Long-Chen; Chao, Keh-Ping


    A direct immersion solid phase microextraction (DI-SPME) method was developed for the analysis of dentin monomers in saliva. Dentine monomers, such as triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA) and 2,2-bis-[4-(2-hydroxy-3-methacryloyloxypropoxy) phenyl]-propane (Bis-GMA), have a high molecular weight and a low vapor pressure. The polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber with a medium polarity was employed for DI-SPME, and 215 nm of detection wavelength was found to be optimum in the chromatogram of HPLC measurement. The calibration range for DI-SPME was 0.30-300 μg/mL with correlation coefficients (r) greater than 0.998 for each analyte. The DI-SPME method achieved good accuracy (recovery 96.1-101.2%) and precision (2.30-8.15% CV) for both intra- and inter-day assays of quality control samples for three target compounds. Method validation was performed on standards dissolved in blank saliva, and there was no significant difference (p>0.2) between the DI-SPME method and the liquid injection method. However, the detection limit of DI-SPME was as low as 0.03, 0.27 and 0.06 μg/mL for TEGDMA, UDMA and Bis-GMA, respectively. Real sample analyses were performed on commercial dentin products after curing for the leaching measurement. In summary, DI-SPME is a more sensitive method that requires less sample pretreatment procedures to measure the resin materials leached in saliva.

  5. Porous, High Capacity Coatings for Solid Phase Microextraction by Sputtering.

    Diwan, Anubhav; Singh, Bhupinder; Roychowdhury, Tuhin; Yan, DanDan; Tedone, Laura; Nesterenko, Pavel N; Paull, Brett; Sevy, Eric T; Shellie, Robert A; Kaykhaii, Massoud; Linford, Matthew R


    We describe a new process for preparing porous solid phase microextraction (SPME) coatings by the sputtering of silicon onto silica fibers. The microstructure of these coatings is a function of the substrate geometry and mean free path of the silicon atoms, and the coating thickness is controlled by the sputtering time. Sputtered silicon structures on silica fibers were treated with piranha solution (a mixture of concd H2SO4 and 30% H2O2) to increase the concentration of silanol groups on their surfaces, and the nanostructures were silanized with octadecyldimethylmethoxysilane in the gas phase. The attachment of this hydrophobic ligand was confirmed by X-ray photoelectron spectroscopy and contact angle goniometry on model, planar silicon substrates. Sputtered silicon coatings adhered strongly to their surfaces, as they were able to pass the Scotch tape adhesion test. The extraction time and temperature for headspace extraction of mixtures of alkanes and alcohols on the sputtered fibers were optimized (5 min and 40 °C), and the extraction performances of SPME fibers with 1.0 or 2.0 μm of sputtered silicon were compared to those from a commercial 7 μm poly(dimethylsiloxane) (PDMS) fiber. For mixtures of alcohols, aldehydes, amines, and esters, the 2.0 μm sputtered silicon fiber yielded signals that were 3-9, 3-5, 2.5-4.5, and 1.5-2 times higher, respectively, than those of the commercial fiber. For the heavier alkanes (undecane-hexadecane), the 2.0 μm sputtered fiber yielded signals that were approximately 1.0-1.5 times higher than the commercial fiber. The sputtered fibers extracted low molecular weight analytes that were not detectable with the commercial fiber. The selectivity of the sputtered fibers appears to favor analytes that have both a hydrophobic component and hydrogen-bonding capabilities. No detectable carryover between runs was noted for the sputtered fibers. The repeatability (RSD%) for a fiber (n = 3) was less than 10% for all analytes tested

  6. Solid rocket motor fire tests: Phases 1 and 2

    Chang, Yale; Hunter, Lawrence W.; Han, David K.; Thomas, Michael E.; Cain, Russell P.; Lennon, Andrew M.


    JHU/APL conducted a series of open-air burns of small blocks (3 to 10 kg) of solid rocket motor (SRM) propellant at the Thiokol Elkton MD facility to elucidate the thermal environment under burning propellant. The propellant was TP-H-3340A for the STAR 48 motor, with a weight ratio of 71/18/11 for the ammonium perchlorate, aluminum, and HTPB binder. Combustion inhibitor applied on the blocks allowed burning on the bottom and/or sides only. Burns were conducted on sand and concrete to simulate near-launch pad surfaces, and on graphite to simulate a low-recession surface. Unique test fixturing allowed propellant self-levitation while constraining lateral motion. Optics instrumentation consisted of a longwave infrared imaging pyrometer, a midwave spectroradiometer, and a UV/visible spectroradiometer. In-situ instrumentation consisted of rod calorimeters, Gardon gauges, elevated thermocouples, flush thermocouples, a two-color pyrometer, and Knudsen cells. Witness materials consisted of yttria, ceria, alumina, tungsten, iridium, and platinum/rhodium. Objectives of the tests were to determine propellant burn characteristics such as burn rate and self-levitation, to determine heat fluxes and temperatures, and to carry out materials analyses. A summary of qualitative results: alumina coated almost all surfaces, the concrete spalled, sand moisture content matters, the propellant self-levitated, the test fixtures worked as designed, and bottom-burning propellant does not self-extinguish. A summary of quantitative results: burn rate averaged 1.15 mm/s, thermocouples peaked at 2070 C, pyrometer readings matched MWIR data at about 2400 C, the volume-averaged plume temperatures were 2300-2400 C with peaks of 2400-2600 C, and the heat fluxes peaked at 125 W/cm2. These results are higher than other researchers' measurements of top-burning propellant in chimneys, and will be used, along with Phase 3 test results, to analyze hardware response to these environments, including General

  7. Chemical reactions on solid surfaces using molecular beam techniques

    Palmer, R. L.


    Thermal energy molecular beams have been used to study chemical interactions with metal surfaces. Chemisorption of simple molecules such as H2, O2, CH4, C2Hx and CO was investigated on single and polycrystalline surfaces of Pt, Ni, Co, and Ag. Kinetic parameters and reaction mechanisms were determined for model catalytic reactions including CO and C2Hx oxidation and methanation from H2/CO mixtures. Chemical reactions of NOx with CO and D2 on Pt(111) and other surfaces have been surveyed and the kinetics of NO and O2 chemisorption have been measured. The theory of adsorption/desorption kinetics is reviewed and certain deficiencies identified.

  8. Observation of Solid-Solid Phase Transitions in Ramp-Compressed Aluminum

    Polsin, D. N.; Boehly, T. R.; Delettrez, J. A.; Gregor, M. C.; McCoy, C. A.; Henderson, B.; Fratanduono, D. E.; Smith, R.; Kraus, R.; Eggert, J. H.; Collins, R.; Coppari, F.; Celliers, P. M.


    We present results of experiments using x-ray diffraction to study the crystalline structure of solid aluminum compressed up to 500 GPa. Aluminum is of interest because it is frequently used as a standard material in high-pressure compression experiments. At ambient pressure and temperature, Al is a face-centered cubic close-packed crystal and has been observed to transform to hexagonal close-packed (hcp) when compressed to 200GPa in a diamond anvil cell. It is predicted to transform from hcp to body-centered cubic when compressed to 315GPa. Laser-driven ramp waves will be used to compress Al to various constant-pressure states. The goal is to investigate the Al phase diagram along its isentrope, i.e., at temperatures 1000K and pressures ranging from 200 to 500 GPa. X-ray diffraction will be used to measure the crystalline structure of the compressed Al and observe the transformations that occur at various pressures. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

  9. Boron fullerenes B(32+8k) with four-membered rings and B32 solid phases: geometrical structures and electronic properties.

    Sheng, Xian-Lei; Yan, Qing-Bo; Zheng, Qing-Rong; Su, Gang


    Based on ab initio calculations, we have studied the geometrical, electronic properties and chemical bonding of boron fullerenes B(32+8k) (0 cubic (sc), face-centered cubic (fcc), body-centered cubic (bcc), and body-centered tetragonal (bct) structures, where the bct phase is observed to be the most stable. Electronic structure calculations reveal that the sc, fcc and bcc phases of B(32) solids are metallic, but the bct phase is a semimetal.

  10. Some Chemical and Electronic Considerations of Solid State Semiconductor Crystals.

    Hinitz, Herman J.


    Describes the trend toward the use of electronic instrumentation to monitor and measure various parameters in chemical reactions. Stresses that a knowledge of the operational relationships involved in such instruments is essential for students beginning in science. Discusses electrostatic charges, semiconductor crystals, electronic conductors,…

  11. Silver Solid Amalgam Electrodes as Sensors for Chemical Carcinogens

    Bogdan Yosypchuk


    Full Text Available The applicability of differential pulse voltammetry (DPV and adsorptivestripping voltammetry (AdSV at a non-toxic meniscus-modified silver solid amalgamelectrode (m-AgSAE for the determination of trace amounts of genotoxic substances wasdemonstrated on the determination of micromolar and submicromolar concentrations of3-nitrofluoranthene using methanol - 0.01 mol L-1 NaOH (9:1 mixture as a base electrolyteand of Ostazine Orange using 0.01 mol L-1 NaOH as a base electrolyte.

  12. Efficient chemical potential evaluation with kinetic Monte Carlo method and non-uniform external potential: Lennard-Jones fluid, liquid, and solid

    Ustinov, E. A.


    The aim of this paper is to present a method of a direct evaluation of the chemical potential of fluid, liquid, and solid with kinetic Monte Carlo simulation. The method is illustrated with the 12-6 Lennard-Jones (LJ) system over a wide range of density and temperature. A distinctive feature of the methodology used in the present study is imposing an external potential on the elongated simulation box to split the system into two equilibrium phases, one of which is substantially diluted. This technique provides a reliable direct evaluation of the chemical potential of the whole non-uniform system (including that of the uniformly distributed dense phase in the central zone of the box), which, for example, is impossible in simulation of the uniform crystalline phase. The parameters of the vapor-liquid, liquid-solid, and fluid-solid transitions have been reliably determined. The chemical potential and the pressure are defined as thermodynamically consistent functions of density and temperature separately for the liquid and the solid (FCC) phases. It has been shown that in two-phase systems separated by a flat interface, the crystal melting always occurs at equilibrium conditions. It is also proved that in the limit of zero temperature, the specific heat capacity of an LJ crystal at constant volume is exactly 3Rg (where Rg is the gas constant) without resorting to harmonic oscillators.

  13. Proposed method for controlling turbid particles in solid-phase bioluminescent toxicity measurement.

    Yeo, Seul-Ki; Park, Jun-Boum; Ahn, Joo-Sung; Han, Young-Soo


    In the recent half century, numerous methods have been developed to assess ecological toxicity. However, the presence of solid-particle turbidity sometimes causes such tests to end with questionable results. Many researchers focused on controlling this arbitrary turbidity effect when using the Microtox® solid-phase toxicity system, but there is not yet a standard method. In this study, we examined four solid-phase sample test methods recommended in the Microtox® manual, or proposed from the literature, and compared the existing methods with our proposed method (centrifuged basic solid-phase test, c-BSPT). Four existing methods use the following strategies to control turbid particles: complete separation of liquid and solid using 0.45-μm filtration before contacting solid samples and bacteria, natural settlement, moderate separation of large particles using coarser pore size filtration, and exclusion of light loss in the toxicity calculation caused by turbidity after full disturbance of samples. Our proposed method uses moderate centrifugation to separate out the heavier soil particles from the lighter bacteria after direct contact between them. Among the solid-phase methods tested, in which the bacteria and solid particles were in direct contact (i.e., the three existing methods and the newly proposed one, c-BSPT), no single method could be recommended as optimal for samples over a range of turbidity. Instead, a simple screening strategy for selecting a sample-dependent solid-phase test method was suggested, depending on the turbidity of the solid suspension. The results of this study highlight the importance of considering solid particles, and the necessity for optimal selection of test method to reduce errors in the measurement of solid-phase toxicity.

  14. Microwave spectroscopic observation of distinct electron solid phases in wide quantum wells.

    Hatke, A T; Liu, Yang; Magill, B A; Moon, B H; Engel, L W; Shayegan, M; Pfeiffer, L N; West, K W; Baldwin, K W


    In high magnetic fields, two-dimensional electron systems can form a number of phases in which interelectron repulsion plays the central role, since the kinetic energy is frozen out by Landau quantization. These phases include the well-known liquids of the fractional quantum Hall effect, as well as solid phases with broken spatial symmetry and crystalline order. Solids can occur at the low Landau-filling termination of the fractional quantum Hall effect series but also within integer quantum Hall effects. Here we present microwave spectroscopy studies of wide quantum wells that clearly reveal two distinct solid phases, hidden within what in d.c. transport would be the zero diagonal conductivity of an integer quantum-Hall-effect state. Explanation of these solids is not possible with the simple picture of a Wigner solid of ordinary (quasi) electrons or holes.

  15. Phase interface effects in the total enthalpy-based lattice Boltzmann model for solid-liquid phase change

    Huang, Rongzong; Wu, Huiying


    In this paper, phase interface effects, including the differences in thermophysical properties between solid and liquid phases and the numerical diffusion across phase interface, are investigated for the recently developed total enthalpy-based lattice Boltzmann model for solid-liquid phase change, which has high computational efficiency by avoiding iteration procedure and linear equation system solving. For the differences in thermophysical properties (thermal conductivity and specific heat) between solid and liquid phases, a novel reference specific heat is introduced to improve the total enthalpy-based lattice Boltzmann model, which makes the thermal conductivity and specific heat decoupled. Therefore, the differences in thermal conductivity and specific heat can be handled by the dimensionless relaxation time and equilibrium distribution function, respectively. As for the numerical diffusion across phase interface, it is revealed for the first time and found to be induced by solid-liquid phase change. To reduce such numerical diffusion, multiple-relaxation-time collision scheme is exploited, and a special value (one fourth) for the so-called "magic" parameter, a combination of two relaxation parameters, is found. Numerical tests show that the differences in thermophysical properties can be correctly handled and the numerical diffusion across phase interface can be dramatically reduced. Finally, theoretical analyses are carried out to offer insights into the roles of the reference specific heat and "magic" parameter in the treatments of phase interface effects.

  16. Solid phase extraction and determination of carbamate pesticides in water samples by reverse-phase HPLC

    Moreno-Tovar, J.; Santos-Delgado, M.J. [Departamento de Quimica Analitica, Facultad de ciencias Quimicas, Universidad Complutense de Madrid (Spain)


    Solid phase extraction. SPE. using C{sub 1}8 bonded silica cartridges for trace amounts determination of carbaryl, propoxur, thiram, propham and methiocarb in water samples was studied and the breakthrough volume of the cartridges was established. The high enrichment factor and large injection volume admissible in the isocratic reverse-phase HPLC system allows pesticides determination with UV detection at 22o nm even at a concentration lower than 0.05 mug/L. Purified tap natural and underground water samples were spiked with carbamate pesticides in the concentration range 0.16-16.0 mug/L. Large volumes of samples (up to 2L) were passed through available C{sub 1}8, cartridges and eluted with acetonitrile. The preconcentrated samples were analyzed by HPLC using a Spherisorb ODS column with a 42.58 acetonitrile-water mobile phase. From replicate samples, recovery for the pesticides ranged from 79.0 to 103.7% except for thiran which is not retained. Tehe relative standard deviation (n=4 at 0.16 to 1.61 mug/L concetration level) range from 1.1 to 6.8%. (Author) 14 refs.

  17. Can large fermion chemical potentials suppress the electroweak phase transition ?

    Quimbay, C; Hurtado, R; Quimbay, Carlos; Morales, John; Hurtado, Rafael


    We calculate the critical temperature $(T_c$) of the electroweak phase transition in the minimal standard model considering simultaneously temperature ($T$) and fermion chemical potential ($\\mu_f$) effects over the effective potential. The calculation is performed in the one-loop approximation to the effective potential at non-zero temperature using the real time formalism of the thermal field theory. We show that it exists a fermion chemical potential critical value ($\\mu_f^c$) for which the Higgs boson condensate vanishes at T=0. If $T$ and $\\mu_f$ effects are considered simultaneously, it is shown that for $\\mu_f \\geq \\mu_f^c$ then $T_c^2 \\leq 0$, implying that the electroweak phase transition might not take place.

  18. Constraints for the QCD phase diagram from imaginary chemical potential

    Philipsen, Owe


    We present unambiguous evidence from lattice simulations of N_f=3 QCD for two tricritical points in the (T,m) phase diagram at fixed imaginary \\mu/T=i\\pi/3 mod. 2\\pi/3, one in the light and one in the heavy quark regime. Together with similar results in the literature for N_f=2 this implies the existence of a chiral and of a deconfinement tricritical line at those values of imaginary chemical potentials. These tricritical lines represent the boundaries of the analytically continued chiral and deconfinement critical surfaces, respectively, which delimit the parameter space with first order phase transitions. It is demonstrated that the shape of the deconfinement critical surface is dictated by tricritical scaling and implies the weakening of the deconfinement transition with real chemical potential. A qualitatively similar effect holds for the chiral critical surface.

  19. Analysis of Solid and Aqueous Phase Products from Hydrothermal Carbonization of Whole and Lipid-Extracted Algae

    Amber Broch


    Full Text Available Microalgae have tremendous potential as a feedstock for production of liquid biofuels, particularly biodiesel fuel via transesterification of algal lipids. However, biodiesel production results in significant amounts of algal residues, or “lipid extracted algae” (LEA. Suitable utilization of the LEA residue will improve the economics of algal biodiesel. In the present study, we evaluate the hydrothermal carbonization (HTC of whole and lipid extracted algal (Spirulina maxima feedstocks in order to produce a solid biofuel (hydrochar and value-added co-products in the aqueous phase. HTC experiments were performed using a 2-L Parr reactor (batch type at 175–215 °C with a 30-min holding time. Solid, aqueous and gaseous products were analyzed using various laboratory methods to evaluate the mass and carbon balances, and investigate the existence of high value chemicals in the aqueous phase. The HTC method is effective in creating an energy dense, solid hydrochar from both whole algae and LEA at lower temperatures as compared to lignocellulosic feedstocks, and is effective at reducing the ash content in the resulting hydrochar. However, under the treatment temperatures investigated, less than 1% of the starting dry algae mass was recovered as an identified high-value chemical in the aqueous phase.

  20. Carbon stripping - a critical process step in chemical looping combustion of solid fuels

    Kramp, M.; Thon, A.; Hartge, E.U.; Heinrich, S.; Werther, J. [Hamburg University of Technology, Institute of Solids Process Engineering and Particle Technology, Hamburg (Germany)


    In chemical looping combustion of solid fuels the well-mixed solids flow from the fuel reactor consisting of char, ash, and oxygen carrier particles cannot be completely separated into its constituents before it enters the air reactor. The slip of carbon will thus lead to char oxidation in the wrong reactor. Process simulation was applied to investigate the carbon stripping process in chemical looping combustion of solid fuels. Depending on the fuel choice, without carbon stripping CO{sub 2} capture rates below 50 % are calculated for 4 min of solids residence time in the fuel reactor. In a process with carbon stripper, however, CO{sub 2} capture rates exceeding 90 % can be achieved for both fuels investigated in this work. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. Characterization of interactions between soil solid phase and soil solution in the initial ecosystem development phase

    Zimmermann, Claudia; Schaaf, Wolfgang


    In the initial phase of soil formation interactions between solid and liquid phases and processes like mineral weathering, formation of reactive surfaces and accumulation of organic matter play a decisive role in developing soil properties. As part of the Transregional Collaborative Research Centre (SFB/TRR 38) 'Patterns and processes of initial ecosystem development' in an artificial catchment, these interactions are studied at the catchment 'Chicken Creek' (Gerwin et al. 2009). To link the interactions between soil solid phase and soil solution at the micro-scale with observed processes at the catchment scale, microcosm experiments under controlled laboratory conditions were carried out. Main objectives were to determine the transformation processes of C and N from litter decomposition within the gaseous, liquid and solid phase, the interaction with mineral surfaces and its role for the establishment of biogeochemical cycles. The microcosm experiments were established in a climate chamber at constant 10 ° C. In total 48 soil columns (diameter: 14.4 cm; height: 30 cm) were filled with two different quaternary substrates (sand and loamy sand) representing the textural variation within the catchment at a bulk density of 1.4-1.5 g*cm-3. The columns were automatically irrigated four times a day with 6.6 ml each (corresponding to 600 mm*yr-1). The gaseous phase in the headspace of the microcosms was analysed continuously for CO2 and N2O contents. C and N transformation processes were studied using 13C and 15N labelled litter of two different plant species occurring at the catchment (Lotus corniculatus, Calamagrostis epigejos) that was incorporated into the microcosm surface. All treatments including a control ran with four replicates over a period of 40 weeks. Two additional microcosms act as pure litter controls where substrate was replaced by glass pearls. Litter and substrate were analysed before and after the experiment. Percolate was continuously collected and

  2. A solid-phase extraction approach for the identification of pharmaceutical-sludge adsorption mechanisms

    Laurence Berthod; Gary Roberts; Graham A. Mills


    It is important to understand the adsorption mechanism of chemicals and active pharmaceu-tical ingredients (API) on sewage sludge since wastewater treatment plants are the last barrier before the release of these compounds to the environment. Adsorption models were developed considering mostly hydrophobic API-sludge interaction. They have poor predictive ability, especially with ionisable compounds. This work proposes a solid-phase extraction (SPE) approach to estimate rapidly the API-sludge interaction. Sludge-filled SPE cartridges could not be percolated with API spiked mobile phases so different powders were tested as SPE sludge supports. Polytetrafluoroethylene (PTFE) was selected and tested at different PTFE/sludge ratios under eight different adsorption conditions with three API ionisable compounds. The PTFE/sludge mixtures with 50% or less sludge could be used in SPE mode for API sorption studies with methanol/water liquid phases. The results gave insights into API-sludge interactions. It was found that π-π, hydrogen-bonding and charge-charge interactions were as important as hydrophobicity in the adsorption mechanism of charged APIs on sludge.

  3. Solid phase precipitates in (Zr,Th)-OH-(oxalate, malonate) ternary aqueous system

    Kobayashi, T.; Sasaki, T.; Takagi, I.; Moriyama, H. [Kyoto Univ. (Japan). Dept. of Nuclear Engineering


    The solubility-limiting solid phases in the ternary aqueous systems of Zr(IV)/OH/oxalate, Zr(IV)/OH/malonate, Th(IV)/OH/oxalate and Th(IV)/OH/malonate were characterized by elemental analysis, X-ray diffraction, thermogravimetric analysis and differential thermal analysis. The ternary solid phase of M(IV)/OH/carboxylate was observed to form, even under acidic conditions, depending on the pH and the concentration of carboxylate ligand. In the presence of a large excess of carboxylic acid, however; the binary M(IV)-carboxylate solid phase formed. (orig.)

  4. Design and Synthesis of a Dual Linker for Solid Phase Synthesis of Oleanolic Acid Derivatives

    Shaorong Wang


    Full Text Available A hydrophilic amino-terminated poly(ethylene glycol-type dual linker for solid phase synthesis of oleanolic acid derivatives using trityl chloride resin was designed and synthesized for the first time. Model reactions in both liquid and solid phase were performed to show the feasibility of its selective cleavage at two different sites. The biological assay results indicated that the long and flexible alkyl ether functionality in the linker is less likely to be critical for the binding event. Following the successful solid-phase synthesis of model compounds, the potential of this dual linker in reaction monitoring and target identification is deemed worthy of further study.

  5. Solid-fluid and solid-solid equilibrium in hard sphere united atom models of n-alkanes: rotator phase stability.

    Cao, M; Monson, P A


    We present a study of the phase behavior for models of n-alkanes with chain lengths up to C(21) based on hard sphere united atom models of methyl and methylene groups, with fixed bond lengths and C-C-C bond angles. We extend earlier work on such models of shorter alkanes by allowing for gauche conformations in the chains. We focus particularly on the orientational order about the chain axes in the solid phase near the melting point, and our model shows how the loss of this orientational order leads to the formation of rotator phases. We have made extensive calculations of the thermodynamic properties of the models as well as order parameters for tracking the degree of orientational order around the chain axis. Depending on the chain length and whether the carbon number is even or odd, the model exhibits both a rotator phase and a more orientationally ordered solid phase in addition to the fluid phase. Our results indicate that the transition between the two solid phases is first-order with a small density change. The results are qualitatively similar to those seen experimentally and show that rotator phases can appear in models of alkanes without explicit treatment of attractive forces or explicit treatment of the hydrogen atoms in the chains.

  6. Evaluation of Chemical Interactions between Small Molecules in the Gas Phase Using Chemical Force Microscopy.

    Lee, Jieun; Ju, Soomi; Kim, In Tae; Jung, Sun-Hwa; Min, Sun-Joon; Kim, Chulki; Sim, Sang Jun; Kim, Sang Kyung


    Chemical force microscopy analyzes the interactions between various chemical/biochemical moieties in situ. In this work we examined force-distance curves and lateral force to measure the interaction between modified AFM tips and differently functionalized molecular monolayers. Especially for the measurements in gas phase, we investigated the effect of humidity on the analysis of force-distance curves and the images in lateral force mode. Flat chemical patterns composed of different functional groups were made through micro-contact printing and lateral force mode provided more resolved analysis of the chemical patterns. From the images of 1-octadecanethiol/11-mercapto-1-undecanoic acid patterns, the amine group functionalized tip brought out higher contrast of the patterns than an intact silicon nitride tip owing to the additional chemical interaction between carboxyl and amine groups. For more complex chemical interactions, relative chemical affinities toward specific peptides were assessed on the pattern of 1-octadecanethiol/phenyl-terminated alkanethiol. The lateral image of chemical force microscopy reflected specific preference of a peptide to phenyl group as well as the hydrophobic interaction.

  7. Convergent solid-phase and solution approaches in the synthesis of the cysteine-rich Mdm2 RING finger domain.

    Vasileiou, Zoe; Barlos, Kostas; Gatos, Dimitrios


    The RING finger domain of the Mdm2, located at the C-terminus of the protein, is necessary for regulation of p53, a tumor suppressor protein. The 48-residues long Mdm2 peptide is an important target for studying its interaction with small anticancer drug candidates. For the chemical synthesis of the Mdm2 RING finger domain, the fragment condensation on solid-phase and the fragment condensation in solution were studied. The latter method was performed using either protected or free peptides at the C-terminus as the amino component. Best results were achieved using solution condensation where the N-component was applied with the C-terminal carboxyl group left unprotected. The developed method is well suited for large-scale synthesis of Mdm2 RING finger domain, combining the advantages of both solid-phase and solution synthesis.

  8. Graphene-Based Materials as Solid Phase Extraction Sorbent for Trace Metal Ions, Organic Compounds, and Biological Sample Preparation.

    Ibrahim, Wan Aini Wan; Nodeh, Hamid Rashidi; Sanagi, Mohd Marsin


    Graphene is a new carbon-based material that is of interest in separation science. Graphene has extraordinary properties including nano size, high surface area, thermal and chemical stability, and excellent adsorption affinity to pollutants. Its adsorption mechanisms are through non-covalent interactions (π-π stacking, electrostatic interactions, and H-bonding) for organic compounds and covalent interactions for metal ions. These properties have led to graphene-based material becoming a desirable adsorbent in a popular sample preparation technique known as solid phase extraction (SPE). Numerous studies have been published on graphene applications in recent years, but few review papers have focused on its applications in analytical chemistry. This article focuses on recent preconcentration of trace elements, organic compounds, and biological species using SPE-based graphene, graphene oxide, and their modified forms. Solid phase microextraction and micro SPE (µSPE) methods based on graphene are discussed.

  9. Liquid phase sintering, II: Computer study of skeletal settling and solid phase extrication in a microgravity environment

    Nikolić Z.S.


    Full Text Available A two-dimensional numerical method based on the Brownian motion model and on the Densification model for simulation of liquid phase sintering in microgravity environment will be developed. Both models will be based on domain topology (two-dimensional particle representation and control volume methodology and on three submodels for domain translation, solid skeleton formation and domain extrication. This method will be tested in order to conduct a study of diffusion phenomena and microgravitational effects on microstructural evolution influenced by skeletal settling combined with solid-phase extrication during liquid phase sintering of porous W-Ni system.

  10. Combinatorial Libraries on Rigid Scaffolds: Solid Phase Synthesis of Variably Substituted Pyrazoles and Isoxazoles

    Eduard R. Felder


    Full Text Available The synthesis of combinatorial compound libraries has become a powerful lead finding tool in modern drug discovery. The ability to synthesize rapidly, in high yield, new chemical entities with low molecular weight on a solid support has a recognized strategic relevance (“small molecule libraries”. We designed and validated a novel solid phase synthesis scheme, suitable to generate diversity on small heterocycles of the pyrazole and isoxazole type. Appropriate conditions were worked out for each reaction, and a variety of more or less reactive agents (building blocks was utilized for discrete conversions, in order to exploit the system’s breadth of applicability. Four sequential reaction steps were validated, including the loading of the support with an acetyl bearing moiety, a Claisen condensation, an a-alkylation and a cyclization of a b-diketone with monosubstituted hydrazines. In a second stage, the reaction sequence was applied in a split and mix approach, in order to prepare a combinatorial library built-up from 4 acetyl carboxylic acids (R1, 35 carboxylic esters (R2 and 41 hydrazines (R4 (and 1 hydroxylamine to yield a total of 11,760 compounds divided into 41 pyrazole sublibraries with 140 pairs of regioisomers and 1 isoxazole sublibrary of equal size.

  11. Regenerable mixed copper-iron-inert support oxygen carriers for solid fuel chemical looping combustion process

    Siriwardane, Ranjani V.; Tian, Hanjing


    The disclosure provides an oxygen carrier for a chemical looping cycle, such as the chemical looping combustion of solid carbonaceous fuels, such as coal, coke, coal and biomass char, and the like. The oxygen carrier is comprised of at least 24 weight % (wt %) CuO, at least 10 wt % Fe2O3, and an inert support, and is typically a calcine. The oxygen carrier exhibits a CuO crystalline structure and an absence of iron oxide crystalline structures under XRD crystallography, and provides an improved and sustained combustion reactivity in the temperature range of C. particularly for solid fuels such as carbon and coal.

  12. Single Nanoparticle Translocation Through Chemically Modified Solid Nanopore

    Tan, Shengwei; Wang, Lei; Liu, Hang; Wu, Hongwen; Liu, Quanjun


    The nanopore sensor as a high-throughput and low-cost technology can detect single nanoparticle in solution. In the present study, the silicon nitride nanopores were fabricated by focused Ga ion beam (FIB), and the surface was functionalized with 3-aminopropyltriethoxysilane to change its surface charge density. The positively charged nanopore surface attracted negatively charged nanoparticles when they were in the vicinity of the nanopore. And, nanoparticle translocation speed was slowed down to obtain a clear and deterministic signal. Compared with previous studied small nanoparticles, the electrophoretic translocation of negatively charged polystyrene (PS) nanoparticles (diameter ~100 nm) was investigated in solution using the Coulter counter principle in which the time-dependent nanopore current was recorded as the nanoparticles were driven across the nanopore. A linear dependence was found between current drop and biased voltage. An exponentially decaying function ( t d ~ e -v/v0 ) was found between the duration time and biased voltage. The interaction between the amine-functionalized nanopore wall and PS microspheres was discussed while translating PS microspheres. We explored also translocations of PS microspheres through amine-functionalized solid-state nanopores by varying the solution pH (5.4, 7.0, and 10.0) with 0.02 M potassium chloride (KCl). Surface functionalization showed to provide a useful step to fine-tune the surface property, which can selectively transport molecules or particles. This approach is likely to be applied to gene sequencing.

  13. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A


    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order.

  14. Determination of crystal violet in water by direct solid phase spectrophotometry after rotating disk sorptive extraction.

    Manzo, Valentina; Navarro, Orielle; Honda, Luis; Sánchez, Karen; Inés Toral, M; Richter, Pablo


    The microextraction of crystal violet (CV) from water samples into polydimethylsiloxane (PDMS) using the rotating disk sorptive extraction (RDSE) technique was performed. The extracting device was a small Teflon disk that had an embedded miniature magnetic stirring bar and a PDMS (560 μL) film attached to one side of the disk using double-sided tape. The extraction involves a preconcentration of CV into the PDMS, where the analyte is then directly quantified using solid phase spectrophotometry at 600 nm. Different chemical and extraction device-related variables were studied to achieve the best sensitivity for the determination. The optimum extraction was performed at pH 14 because under this condition, CV is transformed to the neutral and colorless species carbinol, which can be quantitatively transferred to the PDMS phase. Although the colorless species is the chemical form extracted in the PDMS, an intense violet coloration appeared in the phase because the -OH bond in the carbinol molecule is weakened through the formation of hydrogen bonds with the oxygen atoms of the PDMS, allowing the resonance between the three benzene rings to compensate for the charge deficit on the central carbon atom of the molecule. The accuracy and precision of the method were evaluated in river water samples spiked with 10 and 30 μg L(-1) of CV, yielding a relative standard deviation of 6.2% and 8.4% and a recovery of 98.4% and 99.4%, respectively. The method detection limit was 1.8 μg L(-1) and the limit of quantification was 5.4 μg L(-1), which can be decreased if the sample volume is increased.

  15. Method for fractional solid-waste sampling and chemical analysis

    Riber, Christian; Rodushkin, I.; Spliid, Henrik


    to repeated particle-size reduction, mixing, and mass reduction until a sufficiently small but representative sample was obtained for digestion prior to chemical analysis. The waste-fraction samples were digested according to their properties for maximum recognition of all the studied substances. By combining...... four subsampling methods and five digestion methods, paying attention to the heterogeneity and the material characteristics of the waste fractions, it was possible to determine 61 substances with low detection limits, reasonable variance, and high accuracy. For most of the substances of environmental...... concern, the waste-sample concentrations were above the detection limit (e.g. Cd gt; 0.001 mg kg-1, Cr gt; 0.01 mg kg-1, Hg gt; 0.002 mg kg-1, Pb gt; 0.005 mg kg-1). The variance was in the range of 5-100%, depending on material fraction and substance as documented by repeated sampling of two highly...

  16. Peptide-based affinity media for solid-phase extraction of Ochratoxin A from wine samples: Effect of the solid support on binding properties.

    Giovannoli, Cristina; Passini, Cinzia; Volpi, Giorgio; Di Nardo, Fabio; Anfossi, Laura; Baggiani, Claudio


    A suitable sample clean up is a key point in the development of an analytical method. Peptide-based affinity media have recently gained attention in the selective extraction of defined target analytes from complex samples. In this paper we investigated the thermodynamic and kinetic binding properties of different stationary phases (Amberlite IRC-50, Lewatit CNP105, Toyopearl CM-650 M, porous silica gel beads and micrometric glass beads) functionalized with a hexapeptide sequence binding the Ochratoxin A. The highest values of the equilibrium binding constant (Keq) and binding site concentration (Bmax) were obtained for Lewatit CNP105 (Keq: 98.1×10(6) M(-1), Bmax: 30.8 μmol/g), followed by Toyopearl and micrometric glass beads, whereas the worst performances were obtained with Amberlite IRC-50 and porous silica gel beads. Also kinetic performances show the same trend. These results highlight that the surface chemical nature has a key role in the binding properties of solid supports used as affinity media for the selective extraction of well-defined target molecules. Finally, Lewatit CNP105 was compared with Amberlite IRC-50 as solid support in SPE extraction of OTA from 14 wine samples fortified with OTA at 2 and 4 μg l(-1) levels. The extracts were analyzed by HPLC with fluorescence detection (λexc 333 nm, λem 460 nm) showing no significant matrix effects, with a LOD and LOQ of 0.45 and 1.5 μgl(-1), respectively, and good recoveries between 71% and 108% for Amberlite IRC-50 and 91% and 101% for Lewatit CNP105. While both supports showed a statistically comparable extraction accuracy, a statistically significant difference was found in terms of extraction precision, confirming that the solid phase based on Lewatit CNP105 performs better than the solid phase based on Amberlite IRC-50.

  17. Silica supported Fe(3)O(4) magnetic nanoparticles for magnetic solid-phase extraction and magnetic in-tube solid-phase microextraction: application to organophosphorous compounds.

    Moliner-Martinez, Y; Vitta, Yosmery; Prima-Garcia, Helena; González-Fuenzalida, R A; Ribera, Antonio; Campíns-Falcó, P; Coronado, Eugenio


    This work demonstrates the application of silica supported Fe3O4 nanoparticles as sorbent phase for magnetic solid-phase extraction (MSPE) and magnetic on-line in-tube solid-phase microextraction (Magnetic-IT-SPME) combined with capillary liquid chromatography-diode array detection (CapLC-DAD) to determine organophosphorous compounds (OPs) at trace level. In MSPE, magnetism is used as separation tool while in Magnetic-IT-SPME, the application of an external magnetic field gave rise to a significant improvement of the adsorption of OPs on the sorbent phase. Extraction efficiency, analysis time, reproducibility and sensitivity have been compared. This work showed that Magnetic-IT-SPME can be extended to OPs with successful results in terms of simplicity, speed, extraction efficiency and limit of detection. Finally, wastewater samples were analysed to determine OPs at nanograms per litre.

  18. Microscopic model for chemical etchability along radiation damage paths in solids

    Mukhtar Ahmed RANA


    It would be very interesting to develop a picture about removal of atoms from the radiation damaged paths or latent nuclear tracks and undamaged bulk material in track detectors. Here, theory of chemical etching is described briefly and a new model for chemical etching along radiation damaged paths in solids is developed based on basic scientific facts and valid assumptions. Dependence of chemical etching on radiation damage intensity and etching conditions is discussed. A new parameter for etching along radiation damaged paths is introduced, which is useful for investigation of relationship between chemical etchability and radiation damage in a solid. Results and discussion presented here are also useful for further development of nuclear waste immobilization.

  19. Utilizing ion-pairing hydrophilic interaction chromatography solid phase extraction for efficient glycopeptide enrichment in glycoproteomics

    Mysling, Simon; Palmisano, Giuseppe; Højrup, Peter;


    Glycopeptide enrichment is a prerequisite to enable structural characterization of protein glycosylation in glycoproteomics. Here we present an improved method for glycopeptide enrichment based on zwitter-ionic hydrophilic interaction chromatography solid phase extraction (ZIC-HILIC SPE...

  20. Study on New Sensitive Method of Determination of Phosphorus by Solid Phase Spectrophotometry


    The use of solid phase spectrophotometry for the determination of trace phosphorus in the system of phosphomolybdate-fructose is described. The adsorption of the system on anion-exchange resin is reported.

  1. Recent Application of Solid Phase Based Techniques for Extraction and Preconcentration of Cyanotoxins in Environmental Matrices.

    Mashile, Geaneth Pertunia; Nomngongo, Philiswa N


    Cyanotoxins are toxic and are found in eutrophic, municipal, and residential water supplies. For this reason, their occurrence in drinking water systems has become a global concern. Therefore, monitoring, control, risk assessment, and prevention of these contaminants in the environmental bodies are important subjects associated with public health. Thus, rapid, sensitive, selective, simple, and accurate analytical methods for the identification and determination of cyanotoxins are required. In this paper, the sampling methodologies and applications of solid phase-based sample preparation methods for the determination of cyanotoxins in environmental matrices are reviewed. The sample preparation techniques mainly include solid phase micro-extraction (SPME), solid phase extraction (SPE), and solid phase adsorption toxin tracking technology (SPATT). In addition, advantages and disadvantages and future prospects of these methods have been discussed.

  2. Design and Solid-Phase Synthesis of Multiple Muramyl Dipeptide (MMD)


    As a non-specific modulator of macrophage, multiplied muramyl dipeptide (MMD) is solid-phase synthesized by application of standard Fmoc chemistry strategy. Tam's multiple antigen system (MAS) is used as our four branched-linker on Lysine.

  3. Solid phase microextraction speciation analysis of triclosan in aqueous mediacontaining sorbing nanoparticles

    Zielinska, K.


    Solid phase microextraction (SPME) is applied in the speciation analysis of the hydrophobic compound triclosan in an aqueous medium containing sorbing SiO2 nanoparticles (NPs). It is found that these NPs, as well as their complexes with triclosan, partition between the bulk medium and the solid

  4. Solid phase microextraction speciation analysis of triclosan in aqueous mediacontaining sorbing nanoparticles

    Zielinska, K.


    Solid phase microextraction (SPME) is applied in the speciation analysis of the hydrophobic compound triclosan in an aqueous medium containing sorbing SiO2 nanoparticles (NPs). It is found that these NPs, as well as their complexes with triclosan, partition between the bulk medium and the solid phas

  5. Solid-phase micro-extraction in bioanalysis, exemplified by lidocaine determination

    de Jong, GJ; Koster, EHM


    Solid-phase micro-extraction (SPME) is a never sample preparation technique that can be used for gaseous, liquid or solid samples in conjunction with GC, HPLC or CE (e.g. [1]). The use of SPME for the analysis of drugs in biofluids is also becoming popular (e.g. [2]). The principle is that a fused s

  6. Use of semi-permeable membrane devices and solid-phase extraction for the wide-range screening of microcontaminants in surface water by GC-AED/MS

    Stee, van L.L.P.; Leonards, P.E.G.; Loon, van W.M.G.M.; Hendriks, A.J.; Maas, J.L.; Struijs, J.; Brinkman, U.A.T.


    An automated GC-MS-based screening method was developed for over 400 industrial, agrochemical and household chemicals. Extracted ion chromatograms were used and the method was aimed at creating a minimum number of false positives. The compound polarity range usually associated with solid-phase extra

  7. Use of semi-permeable membrane devices and solid-phase extraction for the wide-range screening of microcontaminants in surface water by GC-AED/MS

    Stee, van L.L.P.; Leonards, P.E.G.; Loon, van W.M.G.M.; Hendriks, A.J.; Maas, J.L.; Struijs, J.; Brinkman, U.A.T.


    An automated GC-MS-based screening method was developed for over 400 industrial, agrochemical and household chemicals. Extracted ion chromatograms were used and the method was aimed at creating a minimum number of false positives. The compound polarity range usually associated with solid-phase extra

  8. Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies.

    Kumar, Rajeev; Mago, Gaurav; Balan, Venkatesh; Wyman, Charles E


    In order to investigate changes in substrate chemical and physical features after pretreatment, several characterizations were performed on untreated (UT) corn stover and poplar and their solids resulting pretreatments by ammonia fiber expansion (AFEX), ammonia recycled percolation (ARP), controlled pH, dilute acid, flowthrough, lime, and SO(2) technologies. In addition to measuring the chemical compositions including acetyl content, physical attributes determined were biomass crystallinity, cellulose degree of polymerization, cellulase adsorption capacity of pretreated solids and enzymatically extracted lignin, copper number, FT-IR responses, scanning electron microscopy (SEM) visualizations, and surface atomic composition by electron spectroscopy of chemical analysis (ESCA). Lime pretreatment removed the most acetyl groups from both corn stover and poplar, while AFEX removed the least. Low pH pretreatments depolymerized cellulose and enhanced biomass crystallinity much more than higher pH approaches. Lime pretreated corn stover solids and flowthrough pretreated poplar solids had the highest cellulase adsorption capacity, while dilute acid pretreated corn stover solids and controlled pH pretreated poplar solids had the least. Furthermore, enzymatically extracted AFEX lignin preparations for both corn stover and poplar had the lowest cellulase adsorption capacity. ESCA results showed that SO(2) pretreated solids had the highest surface O/C ratio for poplar, but for corn stover, the highest value was observed for dilute acid pretreatment with a Parr reactor. Although dependent on pretreatment and substrate, FT-IR data showed that along with changes in cross linking and chemical changes, pretreatments may also decrystallize cellulose and change the ratio of crystalline cellulose polymorphs (Ialpha/Ibeta).

  9. Chemical characterization of agroforestry solid residues aiming its utilization as adsorbents for metals in water

    Francisco H. M. Luzardo; Fermin G. Velasco; Clemildes P. Alves; Correia,Ivea K. da S.; Cazorla,Lázaro L.


    In this work, a study of the correlation between the functional groups present in the chemical structure of the fibers of coconut shells, cocoa and eucalyptus, and their adsorption capacity of Cd+2 and Cu+2 ions from water was performed. The content of soluble solids and reactive phenols in aqueous extracts were determined. The chemical functional groups present in the fibers were examined using the IR spectra. The ads...

  10. Isostructural solid-solid phase transition in monolayers of soft core-shell particles at fluid interfaces: structure and mechanics.

    Rey, Marcel; Fernández-Rodríguez, Miguel Ángel; Steinacher, Mathias; Scheidegger, Laura; Geisel, Karen; Richtering, Walter; Squires, Todd M; Isa, Lucio


    We have studied the complete two-dimensional phase diagram of a core-shell microgel-laden fluid interface by synchronizing its compression with the deposition of the interfacial monolayer. Applying a new protocol, different positions on the substrate correspond to different values of the monolayer surface pressure and specific area. Analyzing the microstructure of the deposited monolayers, we discovered an isostructural solid-solid phase transition between two crystalline phases with the same hexagonal symmetry, but with two different lattice constants. The two phases corresponded to shell-shell and core-core inter-particle contacts, respectively; with increasing surface pressure the former mechanically failed enabling the particle cores to come into contact. In the phase-transition region, clusters of particles in core-core contacts nucleate, melting the surrounding shell-shell crystal, until the whole monolayer moves into the second phase. We furthermore measured the interfacial rheology of the monolayers as a function of the surface pressure using an interfacial microdisk rheometer. The interfaces always showed a strong elastic response, with a dip in the shear elastic modulus in correspondence with the melting of the shell-shell phase, followed by a steep increase upon the formation of a percolating network of the core-core contacts. These results demonstrate that the core-shell nature of the particles leads to a rich mechanical and structural behavior that can be externally tuned by compressing the interface, indicating new routes for applications, e.g. in surface patterning or emulsion stabilization.

  11. Solid Phase Equilibria in the Pi-Ga-As and Pt-Ga-Sb Systems


    OFFICE OF NAVAL RESEARCH Research Contract N00014-87-K-0014 R&T Code 413E026---01 AD-A 198 654 TECHNICAL REPORT No. 9 SOLID PHASE EQUILIBRIA IN THE...Classtcation) UNCLASSLFIED: Tech.Rept.#9 SOLID PHASE EQUILIBRIA IN T11: Pt-Ga-As AND Pt-Ga-Sb SYST’IS 12 PERSONAL AuTiOR(S) C.T. Tsai and R.S. Williats 13a TYPE

  12. Molecularly imprinted polymers: New molecular recognition materials for selective solid-phase extraction of organic compounds

    Martín Esteban, A.


    During the last few years molecularly imprinted polymers have appeared as new selective sorbents for solid-phase extraction of organic compounds in different samples. Molecular imprinting technology involves the preparation of a polymer with specific recognition sites for certain molecules. Once the polymer has been obtained, it can be used in solid-phase extraction protocols, where a careful selection of the most appropriate solvents to be used in the different steps (sample loading, washing...

  13. Expedient protocol for solid-phase synthesis of secondary and tertiary amines

    Olsen, Christian A; Witt, Matthias; Jaroszewski, Jerzy W


    [reaction: see text] An expedient solid-phase synthetic approach to secondary and tertiary amines was developed. The protocol employs conversion of resin-bound amino alcohols to the corresponding iodides, followed by iodide displacement with primary or secondary amines or with unprotected amino...... alcohols. This two-step procedure, affording products in good to excellent yields, is suitable for solid-phase synthesis of polyamines....

  14. Isotope effects in dense solid hydrogen - Phase transition in deuterium at 190 + or - 20 GPa

    Hemley, R. J.; Mao, H. K.


    Raman measurements of solid normal deuterium compressed in a diamond-anvil cell indicate that the material undergoes a structural phase transformation at 190 + or - 20 GPa and 77 K. Spectroscopically, the transition appears analogous to that observed in hydrogen at 145 + or - 5 GPa. The large isotope effect on the transition pressure suggests there is a significant vibrational contribution to the relative stability of the solid phases of hydrogen at very high densities.

  15. Multivariate Quantification of the Solid State Phase Composition of Co-Amorphous Naproxen-Indomethacin

    Beyer, Andreas; Grohganz, Holger; Löbmann, Korbinian


    regression approach that enables the simultaneous determination of up to four solid state fractions: crystalline naproxen, γ-indomethacin, α-indomethacin as well as co-amorphous naproxen-indomethacin. For this purpose, a calibration set that covers the whole range of possible combinations of the four...... four solid state phases, involving one co-amorphous phase, can be quantified with this XRPD data-based approach....

  16. Chemical analysis applied to the radiation sterilization of solid ketoprofen

    Colak, S.; Maquille, A.; Tilquin, B.


    The aim of this work is to investigate the feasibility of radiation sterilization of ketoprofen from a chemical point of view. Although irradiated ketoprofen has already been studied in the literature [Katusin-Razem et al., Radiat. Phys. Chem. 73 111-116 (2005)], new results, on the basis of electron spin resonance (ESR) measurements and the use of hyphenated techniques (GC-MS and LC-MS), are obtained. The ESR spectra of irradiated ketoprofen consists of four unresolved resonance peaks and the mean G-value of ketoprofen is found to be 4 +/- 0.9 nmoles/J, which is very small. HPLC-UV analyses indicate that no significant loss of ketoprofen is detected after irradiation. LC-MS-MS analyses show that the structures of the non-volatile final products are similar to ketoprofen. Benzaldehyde is detected in the irradiated samples after dynamic-extraction GC-MS. The analyses show that ketoprofen is radioresistant and therefore might be radiosterilized.

  17. Two-dimensional solid-phase extraction strategy for the selective enrichment of aminoglycosides in milk.

    Shen, Aijin; Wei, Jie; Yan, Jingyu; Jin, Gaowa; Ding, Junjie; Yang, Bingcheng; Guo, Zhimou; Zhang, Feifang; Liang, Xinmiao


    An orthogonal two-dimensional solid-phase extraction strategy was established for the selective enrichment of three aminoglycosides including spectinomycin, streptomycin, and dihydrostreptomycin in milk. A reversed-phase liquid chromatography material (C18 ) and a weak cation-exchange material (TGA) were integrated in a single solid-phase extraction cartridge. The feasibility of two-dimensional clean-up procedure that experienced two-step adsorption, two-step rinsing, and two-step elution was systematically investigated. Based on the orthogonality of reversed-phase and weak cation-exchange procedures, the two-dimensional solid-phase extraction strategy could minimize the interference from the hydrophobic matrix existing in traditional reversed-phase solid-phase extraction. In addition, high ionic strength in the extracts could be effectively removed before the second dimension of weak cation-exchange solid-phase extraction. Combined with liquid chromatography and tandem mass spectrometry, the optimized procedure was validated according to the European Union Commission directive 2002/657/EC. A good performance was achieved in terms of linearity, recovery, precision, decision limit, and detection capability in milk. Finally, the optimized two-dimensional clean-up procedure incorporated with liquid chromatography and tandem mass spectrometry was successfully applied to the rapid monitoring of aminoglycoside residues in milk. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Solid-Phase Synthesis of PEGylated Lipopeptides Using Click Chemistry

    Jølck, Rasmus Irming; Berg, Rolf Henrik; Andresen, Thomas Lars


    A versatile methodology for efficient synthesis of PEGylated lipopeptides via CuAAC “Click” conjugation between alkyne-bearing solid-supported lipopeptides and azido-functionalized PEGs is described. This new and very robust method offers a unique platform for synthesizing PEGylated lipopeptides...

  19. Solid-state nanoparticle coated emulsions for encapsulation and improving the chemical stability of all-trans-retinol.

    Ghouchi-Eskandar, Nasrin; Simovic, Spomenka; Prestidge, Clive A


    Submicron oil-in-water (o/w) emulsions stabilised with conventional surfactants and silica nanoparticles were prepared and freeze-dried to obtain free-flowing powders with good redispersibility and a three-dimensional porous matrix structure. Solid-state emulsions were characterised for visual appearance, particle size distribution, zeta potential and reconstitution properties after freeze-drying with various sugars and at a range of sugar to oil ratios. Comparative degradation kinetics of all-trans-retinol from freeze-dried and liquid emulsions was investigated as a function of storage temperatures. Optimum stability was observed for silica-coated oleylamine emulsions at 4 °C in their wet state. The half-life of all-trans-retinol was 25.66 and 22.08 weeks for silica incorporation from the oil and water phases respectively. This was ∼4 times higher compared to the equivalent solid-state emulsions with drug half-life of 6.18 and 6.06 weeks at 4 °C. Exceptionally, at a storage temperature of 40 °C, the chemical stability of the drug was 3 times higher in the solid-state compared to the wet emulsions which confirmed that freeze-drying is a promising approach to improve the chemical stability of water-labile compounds provided that the storage conditions are optimised.

  20. Graphenized pencil lead fiber: facile preparation and application in solid-phase microextraction.

    Liu, Qian; Cheng, Mengting; Long, Yanmin; Yu, Miao; Wang, Thanh; Jiang, Guibin


    Graphenized pencil lead fiber was facilely prepared by in situ chemical exfoliation of graphite in pencil lead fiber to few-layered graphene sheets via a one-pot, one-step pressurized oxidation reaction for the first time. This new fiber was characterized and demonstrated to be a highly efficient but low-cost solid-phase microextraction (SPME) fiber. The extraction performance of the fiber was evaluated with four bisphenol analogs [bisphenol A (BPA), bisphenol S (BPS), bisphenol AF (BPAF), and tetrabromobisphenol A (TBBPA)] as model analytes in direct SPME mode. Unlike commercially available fibers, the graphenized pencil lead fiber showed an excellent chemical stability in highly saline, acidic, alkaline and organic conditions due to its coating-free configuration. The fiber also showed a very long lifespan. Furthermore, high extraction efficiency and good selectivity for the analytes with a wide polarity range could be obtained due to the exceptional properties of graphene. The detection limits (LODs) for the analytes were in the range of 1.1-25ng/L. The fiber was successfully applied in the analysis of tap water and effluent samples from a waste water treatment plant with spike recoveries ranging from 68.5 to 105.1%. Therefore, the graphenized pencil lead fiber provides a high performance, cheap, robust, and reliable tool for SPME.

  1. Particulate matter chemical component concentrations and sources in settings of household solid fuel use.

    Secrest, Matthew H; Schauer, James J; Carter, Ellison; Baumgartner, Jill


    Particulate matter (PM) air pollution derives from combustion and non-combustion sources and consists of various chemical species that may differentially impact human health and climate. Previous reviews of PM chemical component concentrations and sources focus on high-income urban settings, which likely differ from the low- and middle-income settings where solid fuel (i.e., coal, biomass) is commonly burned for cooking and heating. We aimed to summarize the concentrations of PM chemical components and their contributing sources in settings where solid fuel is burned. We searched the literature for studies that reported PM component concentrations from homes, personal exposures, and direct stove emissions under uncontrolled, real-world conditions. We calculated weighted mean daily concentrations for select PM components and compared sources of PM determined by source apportionment. Our search criteria yielded 48 studies conducted in 12 countries. Weighted mean daily cooking area concentrations of elemental carbon, organic carbon, and benzo(a)pyrene were 18.8 μg m(-3) , 74.0 μg m(-3) , and 155 ng m(-3) , respectively. Solid fuel combustion explained 29% to 48% of principal component / factor analysis variance and 41% to 87% of PM mass determined by positive matrix factorization. Several indoor and outdoor sources impact PM concentrations and composition in these settings, including solid fuel burning, mobile emissions, dust, and solid waste burning. This article is protected by copyright. All rights reserved.

  2. PWR steam generator chemical cleaning, Phase I. Final report

    Rothstein, S.


    United Nuclear Industries (UNI) entered into a subcontract with Consolidated Edison Company of New York (Con Ed) on August 8, 1977, for the purpose of developing methods to chemically clean the secondary side tube to tube support crevices of the steam generators of Indian Point Nos. 1 and 2 PWR plants. This document represents the first reporting on activities performed for Phase I of this effort. Specifically, this report contains the results of a literature search performed by UNI for the purpose of determining state-of-the-art chemical solvents and methods for decontaminating nuclear reactor steam generators. The results of the search sought to accomplish two objectives: (1) identify solvents beyond those proposed at present by UNI and Con Ed for the test program, and (2) confirm the appropriateness of solvents and methods of decontamination currently in use by UNI.

  3. Determination of 8 Synthetic Food Dyes by Solid Phase Extraction ...

    The analysis was carried out on a UV detector with two optimized method settings within 17 min. ... International Pharmaceutical Abstract, Chemical Abstracts, Embase, Index Copernicus, EBSCO, ... technique is a routine qualitative method to.

  4. Solid waste disposal in the soil: effects on the physical, chemical, and organic properties of soil

    Vanessa Regina Lasaro Mangieri


    Full Text Available Currently, there is growing concern over the final destination of the solid waste generated by society. Landfills should not be considered the endpoint for substances contained or generated in solid waste. The sustainable use of natural resources, especially soil and water, has become relevant, given the increase in anthropogenic activities. Agricultural use is an alternative to solid waste (leachate, biosolid disposal, considering the hypothesis that the agricultural use of waste is promising for reducing waste treatment costs, promoting nutrient reuse and improving the physical and chemical conditions of soil. Thus, this literature review, based on previously published data, seeks to confirm or disprove the hypothesis regarding the promising use of solid waste in agriculture to decrease the environmental liability that challenges public administrators in the development of efficient management. The text below addresses the following subtopics after the introduction: current solid waste disposal and environmental issues, the use of solid waste in agriculture, and the effect on the physical and chemical properties of soil and on organic matter, ending with final considerations.

  5. Determination of particulate-bound formaldehyde from burning incense by solid phase microextraction.

    Liou, S W; Chen, C Y; Yang, T T; Lin, J M


    This work studied the feasibility of using a solid phase microextraction (SPME) fiber for sampling and analysis of gaseous formaldehyde as well as particulate-bound formaldehyde from burning Chinese incense. The SPME fiber with PDMS/DVB coating were partially coated with o-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine hydrochloride (PFBHA), and used for sampling formaldehyde. The sampling rate for formaldehyde and its dependence on temperature, relative humidity and sampling time were observed. The same PFBHA treated fibers were, in parallel, exposed to incense burning smoke with pre-filtration and without pre- filtration for 0.5-1 min. The NIOSH method 2541 using an XAD-2 tube at a flow rate of 0.1 Lpm was also applied for sampling simultaneously. The results demonstrate that commercially available PDMS/DVB fibers partially coated with PFBHA are capable of sampling the gas phase of formaldehyde as well as particulate-bound formaldehyde. The determined level of formaldehyde was close to the result obtained by the NIOSH method 2541. However, a reduction of the fiber's formaldehyde loading capacity in the aerosol sampling in comparison with gas sampling was noticed. This indicates that the particulate characteristics, and their bound chemicals other than formaldehyde may influence the maximum loading capacity of formaldehyde, and some characteristic particulates in high concentrations may even deteriorate the fiber coating.

  6. Direct MD simulation of liquid-solid phase equilibria for two-component plasmas

    Schneider, A S; Horowitz, C J; Berry, D K


    We determine the liquid-solid phase diagram for carbon-oxygen plasma mixtures using two-phase MD simulations. We identified liquid, solid, and interface regions using a bond angle metric. To study finite size effects, we perform 55296 ion simulations and compare to earlier 27648 ion results. To help monitor non-equilibrium effects, we calculate diffusion constants $D_i$. We find that $D_O$ for oxygen ions in the solid is much smaller than $D_C$ for carbon ions and that both diffusion constants are 80 or more times smaller than diffusion constants in the liquid phase. There is excellent agreement between our phase diagram and that predicted by Medin and Cumming. This suggests that errors from finite size and non-equilibrium effects are small and that the carbon-oxygen phase diagram is now accurately known.

  7. Numerical Simulation of Erosion-Corrosion in the Liquid Solid Two-Phase Flow


    Erosion-corrosion of liquid-solid two-phase flow occurring in a pipe with sudden expansion in cross section is numerically simulated in this paper. The global model for erosion-corrosion process includes three main components: the liquid-solid two-phase flow model, erosion model and corrosion model. The Euierian-Lagranglan approach is used to simulate liquid-solid two-phase flow, while the stochastic trajectory model was adopted to obtain properties of particle phase. Two-way coupling effect between the fluid and the particle phase is considered in the model. The accuracy of the models is tested by the data in the reference. The comparison shows that the model is basically correct and feasible.

  8. Influence of solvent composition on the solid phase at equilibrium with saturated solutions of quinolones in different solvent mixtures.

    Romero, Susana; Bustamante, Pilar; Escalera, Begoña; Mura, Paola; Cirri, Marzia


    The dissolution profiles and solubilities of three quinolonic drugs (oxolinic, pipemidic, and nalidixic acids) in different solvent mixtures were studied. The behavior of the solid phase, during solubility experiments was in-depth investigated with the aim of detecting possible crystalline modifications, such as polymorphic transitions or solvate formations, that might modify drug stability and/or solubility properties. In order to test the influence of both the nature and polarity of the co-solvents, aqueous and non-aqueous binary mixtures have been prepared by using Lewis base (dioxane and ethyl acetate) and amphiprotic co-solvents (ethanol and water). Differential scanning calorimetry (DSC), hot stage microscopy, IR spectroscopy and X-ray powder diffraction were used in combination with solubility and dissolution studies to characterize and investigate the solid state properties of the original powders and the corresponding ones at equilibrium with the different pure solvents and solvent mixtures examined. The solid phases of nalidixic and oxolinic acids did not show any change after equilibration with the various pure solvents or binary solvent mixtures, regardless the chemical nature of the examined solvents. On the contrary, in the case of pipemidic acid, the different analytical techniques used to characterize the drug solid state enabled identification of a solvated form at equilibrium with pure dioxane and a trihydrated form in aqueous mixtures of water with both ethanol (amphiprotic) or dioxane (Lewis base) in a concentration range from 10 to 100% water. Copyright 2004 Elsevier B.V.

  9. Phase transitions of amorphous solid acetone in confined geometry investigated by reflection absorption infrared spectroscopy.

    Shin, Sunghwan; Kang, Hani; Kim, Jun Soo; Kang, Heon


    We investigated the phase transformations of amorphous solid acetone under confined geometry by preparing acetone films trapped in amorphous solid water (ASW) or CCl4. Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to monitor the phase changes of the acetone sample with increasing temperature. An acetone film trapped in ASW shows an abrupt change in the RAIRS features of the acetone vibrational bands during heating from 80 to 100 K, which indicates the transformation of amorphous solid acetone to a molecularly aligned crystalline phase. Further heating of the sample to 140 K produces an isotropic solid phase, and eventually a fluid phase near 157 K, at which the acetone sample is probably trapped in a pressurized, superheated condition inside the ASW matrix. Inside a CCl4 matrix, amorphous solid acetone crystallizes into a different, isotropic structure at ca. 90 K. We propose that the molecularly aligned crystalline phase formed in ASW is created by heterogeneous nucleation at the acetone-water interface, with resultant crystal growth, whereas the isotropic crystalline phase in CCl4 is formed by homogeneous crystal growth starting from the bulk region of the acetone sample.

  10. Evaporation induced orientational order in soft solid phases of clays

    Lindbo Hansen, Elisabeth; Hemmen, Henrik; Dommersnes, Paul; Fossum, Jon Otto


    We demonstrate experimentally the possibility for promoting uniaxial orientational order in initially isotropic, soft solid dispersions of the synthetic clays Na-fluorohectorite and Laponite RD. We observe that strong orientational order can emerge from initially isotropic states when the samples are subjected to a slow concentration increase through evaporation of the dispersion water. During evaporation, there is a gradient in the order which, if evaporation is halted, slowly relaxes towards a uniform order throughout the samples. It is evident that the development of orientational order is not counterindicated by the viscoelastic nature of the samples, and that although the translational and likely also rotational diffusion of the particles is restricted in the soft solid state, the orientational degree of freedom can undergo a transition from a collectively random to an ordered state.

  11. Spectroscopic investigations on the effect of humic acid on the formation and solubility of secondary solid phases of Ln2(CO3)3

    Stella Antoniou; Ioannis Pashalidis; Andre Gessner; Michael U Kumke


    The formation of secondary Ln(Ⅲ) solid phases (e.g., Nd2(CO3)3 and Sm2(CO3)3) was studied as a function of the humic acid concentration in 0.1 mol/L NaClO4 aqueous solution in the neutral pH range (5-6.5). The solid phases under investigation were prepared by alkaline precipitation under 100% CO2 atmosphere and characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), time-resolved laser fluorescence spectroscopy (TRLFS), diffuse reflectance ultraviolet-visible (DR-UV-Vis), Raman spectroscopy, and solubility measurements. The spectroscopic data obtained indicated that Nd2(CO3)3 and Sm2(CO3)3 were stable and remained the solubility limiting solid phases even in the presence of increased humic acid concentration (0.5 g/L) in solution.Upon base addition in the Ln(Ⅲ)-HA system, decomplexation of the previously formed Ln(Ⅲ)-humate complexes and precipitation of two distinct phases occurred, the inorganic (Ln2(CO3)3) and the organic phase (HA), which was adsorbed on the particle surface of the former.Nevertheless, humic acid affected the particle size of the solid phases. Increasing humic acid concentration resulted in decreasing crystallite size of the Nd2(CO3)3 and increasing crystallite size of the Sm2(CO3)3 solid phase, and affected inversely the solubility of the solid phases.However, this impact on the solid phase properties was expected to be of minor relevance regarding the chemical behavior and migration of trivalent lanthanides and actinides in the geosphere.

  12. New insights in Microbial Fuel Cells: novel solid phase anolyte

    Tommasi, Tonia; Salvador, Gian Paolo; Quaglio, Marzia


    For the development of long lasting portable microbial fuel cells (MFCs) new strategies are necessary to overcome critical issues such as hydraulic pump system and the biochemical substrate retrieval overtime to sustain bacteria metabolism. The present work proposes the use of a synthetic solid anolyte (SSA), constituted by agar, carbonaceous and nitrogen sources dissolved into diluted seawater. Results of a month-test showed the potential of the new SSA-MFC as a long lasting low energy consuming system.

  13. Solid-liquid phase diagram of disubstituted benzene systems

    黑恩成; 刘国杰


    The cooling curves of different compositions of the systems of ortho-chlorotoluene/para-chlorotoluene and ortho-nitrochlorobenzene/para-nitrochlorobenzene are carefully determined by the thermal analysis method. The crystals obtained are also tested. The conclusion that both systems are of simple eutectic diagram but not the solid solution diagram with a minimum melting point is confirmed. The characteristics of the diagram are explained according to the physical and thermodynarmc properties of the components.

  14. Phase transition of solid bismuth under high pressure

    Chen, Hai-Yan; Xiang, Shi-Kai; Yan, Xiao-Zhen; Zheng, Li-Rong; Zhang, Yi; Liu, Sheng-Gang; Bi, Yan


    As a widely used pressure calibrator, the structural phase transitions of bismuth from phase I, to phase II, to phase III, and then to phase V with increasing pressure at 300 K have been widely confirmed. However, there are different structural versions for phase III, most of which are determined by x-ray diffraction (XRD) technology. Using x-ray absorption fine structure (XAFS) measurements combined with ab initio calculations, we show that the proposed incommensurate composite structure of bismuth of the three configurations is the best option. An abnormal continuous increase of the nearest-neighbor distance of phase III with elevated pressure is also observed. The electronic structure transformation from semimetal to metal is responsible for the complex behavior of structure transformation. Project supported by the National Natural Science Foundation of China (Grant Nos. 10904133, 11304294, 11274281, 11404006, and U1230201), the Development Foundation of China Academy of Engineering Physics (Grant Nos. 2015B0101004, 2013B0401062, and 2012A0101001), the Research Foundation of the Laboratory of Shock Wave and Detonation, China (Grant No. 9140C670201140C67282).

  15. Effect of shear stress in ferroelectric solid solutions with coexisting phases

    Lu, Xiaoyan; Zhang, Hangbo; Zheng, Limei; Cao, Wenwu


    One common feature of ferroelectric solid solutions with large piezoelectricity is the coexistence of two or more phases. Due to the strain mismatch among coexisting phases, adaptive structures near the interfaces or domain walls develop to maintain the atomic coherency. Shear stresses commonly exist, especially when the domain size is small. The effect of shear stresses on phase morphology in Pb(Zr1-xTix)O3 solid solutions with compositions within the morphotropic phase boundary region was studied within the framework of Landau phenomenological theory. Our results show that the coexisting rhombohedral (R) and tetragonal (T) phases can be modified to form stable or metastable R-like and/or T-like monoclinic phases under shear stresses. Large stresses may also induce first order or second order phase transitions.

  16. Temperature and phase dependence of positron lifetimes in solid cyclohexane

    Eldrup, Morten Mostgaard


    The temperature dependence of position lifetimes in both the brittle and plastic phases of cyclohaxane has been examined. Long-lived components in both phases are associated with the formation of positronium (Ps). Two long lifetimes attributable to ortho-Ps are resolvable in the plastic phase....... The longer of these (≈ 2.5 ns), which is temperature dependent, is ascribed to ortho-Ps trapped at vacancies. The shorter lifetime (≈ 0.9 ns), shows little temperature dependence. In contrast to most other plastic crystals, no sigmoidal behaviour of the average ortho-Ps lifetime is observed. A possibility...

  17. Recent progress, challenges and trends in trace determination of drug analysis using molecularly imprinted solid-phase microextraction technology.

    Ansari, Saeedeh; Karimi, Majid


    The quantification of drugs in biological samples is a significant task for determination of the physiological efficiency in evaluated drugs in the drug discovery. To analysis of the chemical compounds at the trace and ultratrace levels, adequate analytical procedures should be applied. Therefore, sample preparation method undoubtedly is the most important stage in the trace determination process. In spite of the great growth of analytical instrumentation during the recent years, sample preparation is still nowadays considered the impasse of the all analytical procedure, especially in drugs analysis. Because of the low concentration level of drugs in blood, plasma, and the diversity of the metabolites, the chosen extraction technique should be almost perfect. Solid-phase microextraction (SPME) is a powerful, simple, fast and an equilibrium-based sample preparation method that permits integration of sampling, sample clean-up, and pre-concentration in a single solvent-free step for chemical analysis. Molecularly imprinted polymers (MIPs) that provided by the presence of a template during their synthesis are the stable polymers with molecular recognition abilities and excellent materials which provide selectivity to sample preparation. Because of its characteristics such as easy preparation, high selectivity, and chemical stability, MIP is widely utilized in many analytical fields. Accordingly, the molecular imprinting and SPME methods combination would prepare a strong analytical instrumentation which comprises simplicity, flexibility, and the selectivity characteristics of both methods. This review focuses on the application of solid-phase microextraction method coupled with molecularly imprinted polymers, namely molecularly imprinted solid-phase microextraction (MISPME), for trace determination in drug analysis.

  18. Solid-liquid phase equilibria of the Gaussian core model fluid.

    Mausbach, Peter; Ahmed, Alauddin; Sadus, Richard J


    The solid-liquid phase equilibria of the Gaussian core model are determined using the GWTS [J. Ge, G.-W. Wu, B. D. Todd, and R. J. Sadus, J. Chem. Phys. 119, 11017 (2003)] algorithm, which combines equilibrium and nonequilibrium molecular dynamics simulations. This is the first reported use of the GWTS algorithm for a fluid system displaying a reentrant melting scenario. Using the GWTS algorithm, the phase envelope of the Gaussian core model can be calculated more precisely than previously possible. The results for the low-density and the high-density (reentrant melting) sides of the solid state are in good agreement with those obtained by Monte Carlo simulations in conjunction with calculations of the solid free energies. The common point on the Gaussian core envelope, where equal-density solid and liquid phases are in coexistence, could be determined with high precision.

  19. Study of solid solution strengthening of alloying element with phase structure factors


    Using the empirical electron theory of solids and molecules (EET), the phase structure factors, nA and nB, of the carbon-containing structural units with mass fraction of carbon (wC) below 0.8% and the mono-alloy structural units with wC at 0.2% in austenite and martensite are calculated. The solid solution strengthening brought by C-containing interstitial solid solution and alloy-substitutional solid solution in γ-Fe and α-Fe is discussed at electron structural level. The coefficient (s) of solid solution strengthening is advanced according to the bonding force between atoms. The study shows that when the criterion is applied to the carbonaceous or alloying element-containing solid solution the results of calculation will coincide with the experimental result very well.

  20. Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries

    Nicolaou, K C; Montagnon, T; Ulven, T


    New synthetic technologies for the preparation and elaboration of alpha-tosyloxy ketones in solution- and on solid-phase are described. Both olefins and ketones serve as precursors to these relatively stable chemical entities: olefins via a novel one-pot epoxidation, arylsulfonic acid displacement......-tosyloxy ketones are engaged by "hard" versus "soft" nucleophiles. The accessibility and site-selectivity of the chemistry demonstrated herein offer the promise of an expanded use for this moiety in solid-phase library construction, in particular, and in the field of organic synthesis, in general....

  1. A novel perovskite oxide chemically designed to show multiferroic phase boundary with room-temperature magnetoelectricity

    Fernández-Posada, Carmen M.; Castro, Alicia; Kiat, Jean-Michel; Porcher, Florence; Peña, Octavio; Algueró, Miguel; Amorín, Harvey


    There is a growing activity in the search of novel single-phase multiferroics that could finally provide distinctive magnetoelectric responses at room temperature, for they would enable a range of potentially disruptive technologies, making use of the ability of controlling polarization with a magnetic field or magnetism with an electric one (for example, voltage-tunable spintronic devices, uncooled magnetic sensors and the long-searched magnetoelectric memory). A very promising novel material concept could be to make use of phase-change phenomena at structural instabilities of a multiferroic state. Indeed, large phase-change magnetoelectric response has been anticipated by a first-principles investigation of the perovskite BiFeO3-BiCoO3 solid solution, specifically at its morphotropic phase boundary between multiferroic polymorphs of rhombohedral and tetragonal symmetries. Here, we report a novel perovskite oxide that belongs to the BiFeO3-BiMnO3-PbTiO3 ternary system, chemically designed to present such multiferroic phase boundary with enhanced ferroelectricity and canted ferromagnetism, which shows distinctive room-temperature magnetoelectric responses.

  2. Distinguishing bicontinuous lipid cubic phases from isotropic membrane morphologies using (31)P solid-state NMR spectroscopy.

    Yang, Yu; Yao, Hongwei; Hong, Mei


    Nonlamellar lipid membranes are frequently induced by proteins that fuse, bend, and cut membranes. Understanding the mechanism of action of these proteins requires the elucidation of the membrane morphologies that they induce. While hexagonal phases and lamellar phases are readily identified by their characteristic solid-state NMR line shapes, bicontinuous lipid cubic phases are more difficult to discern, since the static NMR spectra of cubic-phase lipids consist of an isotropic (31)P or (2)H peak, indistinguishable from the spectra of isotropic membrane morphologies such as micelles and small vesicles. To date, small-angle X-ray scattering is the only method to identify bicontinuous lipid cubic phases. To explore unique NMR signatures of lipid cubic phases, we first describe the orientation distribution of lipid molecules in cubic phases and simulate the static (31)P chemical shift line shapes of oriented cubic-phase membranes in the limit of slow lateral diffusion. We then show that (31)P T2 relaxation times differ significantly between isotropic micelles and cubic-phase membranes: the latter exhibit 2 orders of magnitude shorter T2 relaxation times. These differences are explained by the different time scales of lipid lateral diffusion on the cubic-phase surface versus the time scales of micelle tumbling. Using this relaxation NMR approach, we investigated a DOPE membrane containing the transmembrane domain (TMD) of a viral fusion protein. The static (31)P spectrum of DOPE shows an isotropic peak, whose T2 relaxation times correspond to that of a cubic phase. Thus, the viral fusion protein TMD induces negative Gaussian curvature, which is an intrinsic characteristic of cubic phases, to the DOPE membrane. This curvature induction has important implications to the mechanism of virus-cell fusion. This study establishes a simple NMR diagnostic probe of lipid cubic phases, which is expected to be useful for studying many protein-induced membrane remodeling phenomena

  3. Theoretical and experimental study of metastable solid solutions and phase stability within the immiscible Ag-Mo binary system

    Sarakinos, K.; Greczynski, G.; Elofsson, V.; Magnfält, D.; Högberg, H.; Alling, B.


    Metastable solid solutions are phases that are synthesized far from thermodynamic equilibrium and offer a versatile route to design materials with tailor-made functionalities. One of the most investigated classes of metastable solid solutions with widespread technological implications is vapor deposited ternary transition metal ceramic thin films (i.e., nitrides, carbides, and borides). The vapor-based synthesis of these ceramic phases involves complex and difficult to control chemical interactions of the vapor species with the growing film surface, which often makes the fundamental understanding of the composition-properties relations a challenging task. Hence, in the present study, we investigate the phase stability within an immiscible binary thin film system that offers a simpler synthesis chemistry, i.e., the Ag-Mo system. We employ magnetron co-sputtering to grow Ag1-xMox thin films over the entire composition range along with x-ray probes to investigate the films structure and bonding properties. Concurrently, we use density functional theory calculations to predict phase stability and determine the effect of chemical composition on the lattice volume and the electronic properties of Ag-Mo solid solutions. Our combined theoretical and experimental data show that Mo-rich films (x ≥ ˜0.54) form bcc Mo-Ag metastable solid solutions. Furthermore, for Ag-rich compositions (x ≤ ˜0.21), our data can be interpreted as Mo not being dissolved in the Ag fcc lattice. All in all, our data show an asymmetry with regards to the mutual solubility of Ag and Mo in the two crystal structures, i.e., Ag has a larger propensity for dissolving in the bcc-Mo lattice as compared to Mo in the fcc-Ag lattice. We explain these findings in light of isostructural short-range clustering that induces energy difference between the two (fcc and bcc) metastable phases. We also suggest that the phase stability can be explained by the larger atomic mobility of Ag atoms as compared to that

  4. Determination of Roxarsone in feeds using solid phase extraction and liquid chromatography with ultraviolet detection.

    Sapp, R E; Davidson, S


    A method is presented for detection and quantitation of Roxarsone in poultry feed by liquid chromatography. The drug is extracted by phosphate buffer and determined by solid phase extraction and reversed-phase liquid chromatography. Recoveries of the sample spikes and fortified field samples agree closely with those obtained by the standard spectrophotometric method.


    TANG Xuelin; QIAN Zhongdong; WU Yulin


    The dense solid-phase governing equations for two-phase flows are obtained by using the kinetic theory of gas molecules. Assuming that the solid-phase velocity distributions obey the Maxwell equations, the collision term for particles under dense two-phase flow conditions is also derived.In comparison with the governing equations of a dilute two-phase flow, the solid-particle's governing equations are developed for a dense turbulent solid-liquid flow by adopting some relevant terms from the dilute two-phase governing equations. Based on Cauchy-Helmholtz theorem and Smagorinsky model,a second-order dynamic sub-grid-scale (SGS) model, in which the sub-grid-scale stress is a function of both the strain-rate tensor and the rotation-rate tensor, is proposed to model the two-phase governing equations by applying dimension analyses. Applying the SIMPLEC algorithm and staggering grid system to the two-phase discretized governing equations and employing the slip boundary conditions on the walls, the velocity and pressure fields, and the volumetric concentration are calculated. The simulation results are in a fairly good agreement with experimental data in two operating cases in a conduit with a rectangular cross-section and these comparisons imply that these models are practical.

  6. Traveling waves for models of phase transitions of solids driven by configurational forces

    Kawashima, Shuichi


    This article is concerned with the existence of traveling wave solutions, including standing waves, to some models based on configurational forces, describing respectively the diffusionless phase transformations of solid materials, e.g., Steel, and phase transitions due to interface motion by interface diffusion, e.g., Sintering. These models are recently proposed by Alber and Zhu. We consider both the order-parameter-conserved case and the non-conserved one, under suitable assumptions. Also we compare our results with the corresponding ones for the Allen-Cahn and the Cahn-Hilliard equations coupled with linear elasticity, which are models for diffusion-dominated phase transformations in elastic solids.

  7. Density-functional theory of a lattice-gas model with vapour, liquid, and solid phases

    Prestipino, S.; Giaquinta, P. V.


    We use the classical version of the density-functional theory in the weighted-density approximation to build up the entire phase diagram and the interface structure of a two-dimensional lattice-gas model which is known, from previous studies, to possess three stable phases -- solid, liquid, and vapour. Following the common practice, the attractive part of the potential is treated in a mean-field-like fashion, although with different prescriptions for the solid and the fluid phases. It turns o...

  8. Probing the nature of phases across the phase transition at finite isospin chemical potential

    Bali, Gunnar S; Gavai, Rajiv V; Mathur, N


    We compare the low eigenvalue spectra of the Overlap Dirac operator on two sets of configurations at $\\mu_I/\\mu_I^c$ = 0.5 and 1.5 generated with dynamical staggered fermions at these isospin chemical potential on $24^3 \\times 6$ lattices. We find very small changes in the number of zero modes and low lying modes which is in stark contrast with those across the corresponding finite temperature phases where one sees a drop across the phase transition. Possible consequences are discussed.

  9. Detecting Lesch-Nyhan syndrome by solid phase primer extension

    Shumaker, J.M.; Caskey, C.T. [Baylor College of Medicine, Houston, TX (United States); Metspalu, A.


    A mutation detection method based upon the wild type human HPRT sequence is presented for identification of Lesch Nyhan syndrome. The technique consists of performing a biotinlyated PCR amplification of the region of interest, followed by isolation and purification of single stranded template using magnetic separation. Allele-specific primers are annealed adjacent to the potential mutation site on the template. A terminal fluorescent deoxynucleotide addition is performed with a DNA template-dependent polymerase to distinguish between the mutant and wild-type sequence. The products are purified from unincorporated ddNTPs, eluted and finally analyzed on an ABI 373 to identify the mutation. The length of an extension primer is used as a position signature for mutations. The fidelity of nucleotide incorporation provides an excellent signal-to-noise ratio for the detection of nine HPRT mutations within eight cell lines. This method should detect all types of mutations except for repeated sequences that are longer than the primers. Moreover, the method is being extended to a solid support assay, whereby the extension primers are attached to a two-dimensional glass surface. Following extension, the solid support is analyzed for radioactive incorporation. We have shown the sequence determination of a five base region of a wild-type sequence and two different HPRT mutations. As more dense oligonucleotide arrays are produced, this method could be extended to sequence the complete coding region of HPRT.

  10. Pentaerythrityltetramine scaffolds for solid-phase combinatorial chemistry.

    Virta, Pasi; Leppänen, Marika; Lönnberg, Harri


    Straightforward synthesis for two pentaerythrityltetramine precursors, 2,2-bis(azidomethyl)propane-1,3-diamine (1) and 2-[N-(allyloxycarbonyl)aminomethyl]-2-azidomethylpropane-1,3-diamine (2), has been described. Both propane-1,3-diamines have been attached by reductive amination to a solid-supported backbone amide linker derived from 4-(4-formyl-3,5-dimethoxyphenoxy)butyric acid. The presence of the two methoxy substituents on the linker is essential to avoid cross-linking between two linkers. The remaining free primary amino group of the propane-1,3-diamine moiety may then be selectively acylated with an appropriately protected amino acid using conventional N,N-dicyclohexylcarbodiimide/1-hydroxybenzotriazole (DCC/HOBt) activation without any interference by the secondary amino function. The latter group may be subsequently acylated by an anhydride method. Sequential reduction of the azido group and removal of the allyloxycarbonyl protection from 2 allow further coupling of two different amino acids, and hence, this handle may be utilized in construction of branched structures containing four different amino acids or peptides. Solid-supported 1 may, in turn, be used for the synthesis of similar constructs containing two identical branches. It is worth noting that no acid-labile protecting groups are required in this approach, and hence, this dimension may be saved for the cleavage of the linker. The applicability of the scaffolds to library synthesis has been demonstrated by preparation of 11 pentaerythrityl-branched tetra- and octapeptides.

  11. Stability of phases in (Ba, Gd)MnO3 solid solution system

    Migaku Kobayashi; Hidenori Tamura; Hiromi Nakano; Hirohisa Satoh; Naoki Kamegashira


    The existing phases in BaxGd1-xMnO3 solid solution system (0≦x≦1) were studied by analyzing the detailed crystal structure of each composition from the results of the Rietveld method using powder X-ray diffraction data. For a small substitution of Ba for Gd (0≦x<0.1), the orthorhombic phase with a perovskite type structure (Pnma space group) was stably formed and this fact was supported by the electron diffraction data. There existed an intermediate phase of Ba0.33Gd0.67MnO3, which was characterized as the tetragonal phase with perovskite structure. The composition range of this phase was narrow and almost line compound. Between the regions of these phases, there existed two-phase region. There was also a two-phase region between the intermediate tetragonal phase and BaMnO3. Measurement of electrical conductivities of these orthorhombic solid solutions and tetragonal phases showed semiconducting behaviors for both phases and the existence of the phase transition at high temperature for the orthorhombic phase. The transition temperature decreased as the Ba content increased.

  12. Crystalline-to-plastic phase transitions in molecularly thin n-dotriacontane films adsorbed on solid surfaces

    Cisternas, Edgardo; Corrales, T. P.; del Campo, V.;


    Crystalline-to-rotator phase transitions have been widely studied in bulk hydrocarbons, in particular in normal alkanes. But few studies of these transitions deal with molecularly thin films of pure n-alkanes on solid substrates. In this work, we were able to grow dotriacontane (n-C32H66) films...... identify with a solid-solid phase transition. At higher coverages, we observed additional steps in the ellipsometric signal that we identify with a solid-solid phase transition in multilayer islands (similar to 333 K) and with the transition to the rotator phase in bulk crystallites (similar to 337 K...

  13. Rapidly Activated Dynamic Phase Transitions in Nonlinear Solids


    I Form Approv# edAD -A263 601 AiENTA11ON PAGE- f____________18 1. AGENCY USE ONLY (Lea"e blaWk 12. REPORT DATE 13. REPORT TYPE AND OATES COVEREO Feb...phase transforming media during high energy impact. Conversion of mechanical energy to thermal ener- gy has been studied by means of an extended theory...and Phase Structures in General Media , R. Fosdick, E. Dunn & M. Slemrod eds., IMA volume series, Springer- Verlag. Song, J. and T. L. Pence (1992

  14. Influence of encapsulated functional lipids on crystal structure and chemical stability in solid lipid nanoparticles: Towards bioactive-based design of delivery systems.

    Salminen, Hanna; Gömmel, Christina; Leuenberger, Bruno H; Weiss, Jochen


    We investigated the influence of physicochemical properties of encapsulated functional lipids--vitamin A, β-carotene and ω-3 fish oil--on the structural arrangement of solid lipid nanoparticles (SLN). The relationship between the crystal structure and chemical stability of the incorporated bioactive lipids was evaluated with different emulsifier compositions of a saponin-rich, food-grade Quillaja extract alone or combined with high-melting or low-melting lecithins. The major factors influencing the structural arrangement and chemical stability of functional lipids in solid lipid dispersions were their solubility in the aqueous phase and their crystallization temperature in relation to that of the carrier lipid. The results showed that the stabilization of the α-subcell crystals in the lattice of the carrier lipid is a key parameter for forming stable solid lipid dispersions. This study contributes to a better understanding of SLN as a function of the bioactive lipid. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Two-phase anaerobic digestion of vegetable market waste fraction of municipal solid waste and development of improved technology for phase separation in two-phase reactor.

    Majhi, Bijoy Kumar; Jash, Tushar


    Biogas production from vegetable market waste (VMW) fraction of municipal solid waste (MSW) by two-phase anaerobic digestion system should be preferred over the single-stage reactors. This is because VMW undergoes rapid acidification leading to accumulation of volatile fatty acids and consequent low pH resulting in frequent failure of digesters. The weakest part in the two-phase anaerobic reactors was the techniques applied for solid-liquid phase separation of digestate in the first reactor where solubilization, hydrolysis and acidogenesis of solid organic waste occur. In this study, a two-phase reactor which consisted of a solid-phase reactor and a methane reactor was designed, built and operated with VMW fraction of Indian MSW. A robust type filter, which is unique in its implementation method, was developed and incorporated in the solid-phase reactor to separate the process liquid produced in the first reactor. Experiments were carried out to assess the long term performance of the two-phase reactor with respect to biogas production, volatile solids reduction, pH and number of occurrence of clogging in the filtering system or choking in the process liquid transfer line. The system performed well and was operated successfully without the occurrence of clogging or any other disruptions throughout. Biogas production of 0.86-0.889m(3)kg(-1)VS, at OLR of 1.11-1.585kgm(-3)d(-1), were obtained from vegetable market waste, which were higher than the results reported for similar substrates digested in two-phase reactors. The VS reduction was 82-86%. The two-phase anaerobic digestion system was demonstrated to be stable and suitable for the treatment of VMW fraction of MSW for energy generation.

  16. Modelling of Physical, Chemical, and Material Properties of Solid Oxide Fuel Cells

    Jakub Kupecki


    Full Text Available This paper provides a review of modelling techniques applicable for system-level studies to account for physical, chemical, and material properties of solid oxide fuel cells. Functionality of 0D to 3D models is discussed and selected examples are given. Author provides information on typical length scales in evaluation of power systems with solid oxide fuel cells. In each section, proper examples of previous studies done in the field of 0D–3D modelling are recalled and discussed.

  17. Positronium in solid phases of n-alkane binary mixtures

    Zgardzińska, B.; Goworek, T.


    Highlights: • Rotator phase in even alkanes C{sub n}H{sub 2n+2} with n ⩽ 20 appears in mixed samples only. • Interlamellar gap width is the same for shorter chain alkane concentration x and 1 − x. • Excess electron trapping diminishes with broadening of alkane chain distribution Δn. - Abstract: Binary mixtures of even-numbered normal alkanes C{sub n}H{sub 2n+2} and C{sub n+2}H{sub 2n+6} with n ⩽ 18 were investigated by positron annihilation spectroscopy. Formation of the rotator phase was observed in mixed structures, while no such a phase in neat alkanes in this range of n was found. Phase diagrams for n = 18 and n = 16 are very similar to the diagrams for binary mixtures of odd-numbered alkanes. The effect of positronium formation with trapped excess electrons weakens with decreasing n, at low n values the time constant of Ps rise contains the component much shorter than 1 h.

  18. All rights reserved Development of Headspace Solid-Phase ...


    Pesticide Residues in Fruit and Vegetable Samples using OFAT Design. *. 1,2. LUKMAN BOLA ... phase microextraction parameters (fiber coating type, extraction temperature and time, pH, salt addition ... production of food (Bakırcı, et al. 2014 ...

  19. SANS study of phase separation in solid {sup 3}He-{sup 4}He

    Koster, J.P.; Nagler, S.E.; Adams, E.D. [Florida Univ., Gainesville, FL (United States). Dept. of Physics; Wignall, G.D. [Oak Ridge National Lab., TN (United States). Solid State Div.


    Small angle neutron scattering has been used to study phase separation in a quantum alloy, solid {sup 3}He{sub x}-{sup 4}He{sub 1{minus}x}. The onset of phase separation is marked by a dramatic increase in the measured scattering. A simple interpretation of the results suggests that the late-stage phase separation kinetics are dominated by an increase in the concentration of {sup 3}He atoms in preexisting precipitate regions.

  20. Relation of Certain Quantum Chemical Parameters to Lubrication Behavior of Solid Oxides

    Yuansheng Jin


    Full Text Available Abstract: It is well-documented that certain oxides (such as Re2O7, B2O3, MoO3, V2O5, etc. can provide friction coefficients of 0.1-0.3 to sliding surfaces at elevated temperatures and thus they are often referred to as lubricious oxides in the tribology literature. In a recently proposed crystal chemical model, Erdemir was able to establish a close correlation between the reported friction coefficients of such oxides and their ionic potentials [1]. In the present paper, we expand on this original concept and explore the relevance of two other quantum chemical parameters, electronegativity and chemical hardness, to the lubricity of solid oxides. These parameters have already been used by scientists to explain the nature of tribochemical interactions between various oil additives and sliding surfaces. It is conceivable that electronegativity and chemical hardness may also be strongly related to the extent of adhesive interactions and shear rheology of solid oxides and hence to their lubricity. The new results have confirmed that electronegativity, like ionic potential, is indeed a valid quantum chemistry parameter that can be used in predicting the lubrication behavior of solid oxides. Generally, the higher the electronegativity of the solid oxides is, the lower the friction coefficients will be. However, chemical hardness did not yield a similar trend. In light of these new findings, we propose some guidelines for the formulation of novel oxide or alloy systems that can lead to the formation of lubricious oxides at elevated temperatures. The findings of this study may pave the way for designer-based tribosystems in general and smart tribochemical systems in particular in future tribological applications such as dry machining.

  1. Thermoelastic properties of solid phases: C++ object oriented library “SolidEOS”

    Churakov, Sergey V.


    A new object-oriented C++ library (SolidEOS) for calculating the thermoelastic properties of solids is presented. The implementation is based on the Mie-Grüneisen-Debye equation of state (EOS) augmented by lowest order correction for anharmonicity. Several commonly used static EOS like Birch-Murnaghan and Vinet models are available. Although some widely used approximation for the Debye-Grüneisen parameter and static EOS are implemented, the final behaviour of the EOS can be easily modified by overloading predefined virtual functions. The article provides a basic physical background of the modern theory of high-pressure EOS. The detailed documentation of the class hierarchy is summarized in the appendix, which accompanies the source. Several examples of practical use are given in the appendix as well. The library is appropriate for applications in geophysics, petrology, material science or any other field where thermodynamic and elastic properties of solids are relevant. The source code is available from the Computers & Geoscience software archive.

  2. Three-phase catalytic system of H2O, ionic liquid, and VOPO4-SiO2 solid acid for conversion of fructose to 5-hydroxymethylfurfural.

    Tian, Chengcheng; Zhu, Xiang; Chai, Song-Hai; Wu, Zili; Binder, Andrew; Brown, Suree; Li, Lin; Luo, Huimin; Guo, Yanglong; Dai, Sheng


    Efficient transformation of biomass-derived feedstocks to chemicals and fuels remains a daunting challenge in utilizing biomass as alternatives to fossil resources. A three-phase catalytic system, consisting of an aqueous phase, a hydrophobic ionic-liquid phase, and a solid-acid catalyst phase of nanostructured vanadium phosphate and mesostructured cellular foam (VPO-MCF), is developed for efficient conversion of biomass-derived fructose to 5-hydroxymethylfurfural (HMF). HMF is a promising, versatile building block for production of value-added chemicals and transportation fuels. The essence of this three-phase system lies in enabling the isolation of the solid-acid catalyst from the aqueous phase and regulation of its local environment by using a hydrophobic ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][Tf2N]). This system significantly inhibits the side reactions of HMF with H2O and leads to 91 mol % selectivity to HMF at 89 % of fructose conversion. The unique three-phase catalytic system opens up an alternative avenue for making solid-acid catalyst systems with controlled and locally regulated microenvironment near catalytically active sites by using a hydrophobic ionic liquid.

  3. Theoretical study on phase coexistence in ferroelectric solid solutions near the tricritical point

    Lu, Xiaoyan, E-mail:, E-mail:; Li, Hui [Key Lab of Structures Dynamic Behavior and Control of the Ministry of Education, School of Civil Engineering, Harbin Institute of Technology, Harbin 150001 (China); Zheng, Limei [Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150001 (China); Cao, Wenwu [Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150001 (China); Department of Mathematics and Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)


    Phase coexistence in ferroelectric solid solutions near the tricritical point has been theoretically analyzed by using the Landau-Devonshire theory. Results revealed that different phases having similar potential wells could coexist in a narrow composition range near the tricritical point in the classical Pb(Zr{sub 1−x}Ti{sub x})O{sub 3} system. The potential barrier between potential wells increases with the decrease of temperature. Coexisting phases or different domains of the same phase can produce adaptive strains to maintain atomic coherency at the interfaces or domain walls. Such compatibility strains have influence on the energy potential as well as the stability of relative phases, leading to the appearance of energetically unfavorable monoclinic phases. Those competing and coexisting phases also construct an easy phase transition path with small energy barrier in between, so that very small stimuli can produce large response in compositions near the morphotropic phase boundary, especially near the tricritical point.

  4. Optimizing the solid-phase immunofiltration assay. A rapid alternative to immunoassays.

    IJsselmuiden, O E; Herbrink, P; Meddens, M J; Tank, B; Stolz, E; Van Eijk, R V


    The technical variables of the solid-phase immunofiltration assay (SPIA) for the detection of antibodies bound to antigens on a solid-phase filter have been investigated. The binding to solid-phase filters of 125I-labelled axial filament proteins derived from Treponema phagedenis and the optimal conditions for blocking non-specific protein binding were analysed. Axial filament was applied to nitrocellulose, Hybond Nylon and Zeta Probe. After extensive rinsing, the highest amount (68%) of axial filament was observed bound to Zeta Probe. However, blocking non-specific protein binding by pre-wetting the filter with rinsing buffer containing 0.5% Tween 20, prevented the binding of protein to the filter only when nitrocellulose was used as solid phase. Tween 20 (0.5%) in the rinsing and incubation solutions was found to be necessary for the reduction of non-specific binding of contaminants in turbid sera. However, the use of such solutions resulted in a substantial leakage of antigen (47%) during rinsing procedures. Binding of antigen-specific antibody was analysed using 125I-labelled protein A. The maximal possible binding of the antibody occurred within 5 min when the antibody solution was filtered. For optimal binding of 125I-labelled protein A an incubation time of 1 h was needed. It is suggested that solid-phase immunofiltration may provide a rapid alternative for radioimmunoassays or enzyme immunoassays for the detection of specific antibodies.

  5. Determination of melamine in aquaculture feed samples based on molecularly imprinted solid-phase extraction.

    Lian, Ziru; Liang, Zhenlin; Wang, Jiangtao


    This research highlights the application of highly efficient molecularly imprinted solid-phase extraction for the preconcentration and analysis of melamine in aquaculture feed samples. Melamine-imprinted polymers were synthesized employing methacrylic acid and ethylene glycol dimethacrylate as functional monomer and cross-linker, respectively. The characteristics of obtained polymers were evaluated by scanning electron microscopy, Fourier transform infrared spectroscopy and binding experiments. The imprinted polymers showed an excellent adsorption ability for melamine and were applied as special solid-phase extraction sorbents for the selective cleanup of melamine. An off-line molecularly imprinted solid-phase extraction procedure was developed for the separation and enrichment of melamine from aquaculture feed samples prior to high-performance liquid chromatography analysis. Optimum molecularly imprinted solid-phase extraction conditions led to recoveries of the target in spiked feed samples in the range 84.6-96.6% and the relative standard deviation less than 3.38% (n = 3). The aquaculture feed sample was determined, and there was no melamine found. The results showed that the molecularly imprinted solid-phase extraction protocols permitted the sensitive, uncomplicated and inexpensive separation and pre-treatment of melamine in aquaculture feed samples.

  6. A High-Throughput Process for the Solid-Phase Purification of Synthetic DNA Sequences.

    Grajkowski, Andrzej; Cieślak, Jacek; Beaucage, Serge L


    An efficient process for the purification of synthetic phosphorothioate and native DNA sequences is presented. The process is based on the use of an aminopropylated silica gel support functionalized with aminooxyalkyl functions to enable capture of DNA sequences through an oximation reaction with the keto function of a linker conjugated to the 5'-terminus of DNA sequences. Deoxyribonucleoside phosphoramidites carrying this linker, as a 5'-hydroxyl protecting group, have been synthesized for incorporation into DNA sequences during the last coupling step of a standard solid-phase synthesis protocol executed on a controlled pore glass (CPG) support. Solid-phase capture of the nucleobase- and phosphate-deprotected DNA sequences released from the CPG support is demonstrated to proceed near quantitatively. Shorter than full-length DNA sequences are first washed away from the capture support; the solid-phase purified DNA sequences are then released from this support upon reaction with tetra-n-butylammonium fluoride in dry dimethylsulfoxide (DMSO) and precipitated in tetrahydrofuran (THF). The purity of solid-phase-purified DNA sequences exceeds 98%. The simulated high-throughput and scalability features of the solid-phase purification process are demonstrated without sacrificing purity of the DNA sequences. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

  7. Moisture-induced solid state instabilities in α-chymotrypsin and their reduction through chemical glycosylation

    Solá Ricardo J


    Full Text Available Abstract Background Protein instability remains the main factor limiting the development of protein therapeutics. The fragile nature (structurally and chemically of proteins makes them susceptible to detrimental events during processing, storage, and delivery. To overcome this, proteins are often formulated in the solid-state which combines superior stability properties with reduced operational costs. Nevertheless, solid protein pharmaceuticals can also suffer from instability problems due to moisture sorption. Chemical protein glycosylation has evolved into an important tool to overcome several instability issues associated with proteins. Herein, we employed chemical glycosylation to stabilize a solid-state protein formulation against moisture-induced deterioration in the lyophilized state. Results First, we investigated the consequences of moisture sorption on the stability and structural conformation of the model enzyme α-chymotrypsin (α-CT under controlled humidity conditions. Results showed that α-CT aggregates and inactivates as a function of increased relative humidity (RH. Furthermore, α-CT loses its native secondary and tertiary structure rapidly at increasing RH. In addition, H/D exchange studies revealed that α-CT structural dynamics increased at increasing RH. The magnitude of the structural changes in tendency parallels the solid-state instability data (i.e., formation of buffer-insoluble aggregates, inactivation, and loss of native conformation upon reconstitution. To determine if these moisture-induced instability issues could be ameliorated by chemical glycosylation we proceeded to modify our model protein with chemically activated glycans of differing lengths (lactose and dextran (10 kDa. The various glycoconjugates showed a marked decrease in aggregation and an increase in residual activity after incubation. These stabilization effects were found to be independent of the glycan size. Conclusion Water sorption leads to

  8. Quantitative Infrared Spectra of Vapor Phase Chemical Agents

    Sharpe, Steven W.; Johnson, Timothy J.; Chu, P. M.; Kleimeyer, J.; Rowland, Brad


    Quantitative, moderately high resolution (0.1 cm-1) infrared spectra have been acquired for a number of nitrogen broadened (1 atm N2) vapor phase chemicals including: Sarin (GB), Soman (GD), Tabun (GA), Cyclosarin (GF), VX, Nitrogen Mustard (HN3), Sulfur Mustard (HD), and Lewisite (L). The spectra are acquired using a heated, flow-through White Cell1 of 5.6 meter optical path length. Each reported spectrum represents a statistical fit to Beer’s law, which allows for a rigorous calculation of uncertainty in the absorption coefficients. As part of an ongoing collaboration with the National Institute of Standards and Technology (NIST), cross-laboratory validation is a critical aspect of this work. In order to identify possible errors in the Dugway flow-through system, quantitative spectra of isopropyl alcohol from both NIST and Pacific Northwest National Laboratory (PNNL) are compared to similar data taken at Dugway proving Grounds (DPG).

  9. Influence of temperature and chemical composition on phase transformations of selected oxide melts

    J. Dobrovská


    Full Text Available The paper deals with structural changes of solid phase of selected oxide systems during their transition into liquid state. Analyses concerned poly-component systems forming basis of casting powders for CCM mould. Industrially used oxide system with prevailing contents of CaO–Al2O3–SiO2 components and with numerous accompanying admixtures was tested. Investigation was focused on temperatures, during which individual phases disappear and precipitate, as well as on influence of CaO content on phase composition at selected temperatures. The experiments were realised with use of original methodology consisting of shock cooling of the tested melt in liquid nitrogen. Thus obtained samples were further investigated by X-ray diffraction phase analyses at ambient temperatures. The obtained results provide additional data on physical-chemical properties of oxide systems, such as surface tension, viscosity, sintering intervals, etc., which can be used in technological practice for appropriate lubrication effect of casting powders in the mould.

  10. Solid phase DNA extraction on PDMS and direct amplification.

    Pasquardini, Laura; Potrich, Cristina; Quaglio, Marzia; Lamberti, Andrea; Guastella, Salvatore; Lunelli, Lorenzo; Cocuzza, Matteo; Vanzetti, Lia; Pirri, Candido Fabrizio; Pederzolli, Cecilia


    In this paper we report an innovative use of Poly(DiMethyl)Siloxane (PDMS) to design a microfluidic device that combines, for the first time, in one single reaction chamber, DNA purification from a complex biological sample (blood) without elution and PCR without surface passivation agents. This result is achieved by exploiting the spontaneous chemical structure and nanomorphology of the material after casting. The observed surface organization leads to spontaneous DNA adsorption. This property allows on-chip complete protocols of purification of complex biological samples to be performed directly, starting from cells lysis. Amplification by PCR is performed directly on the adsorbed DNA, avoiding the elution process that is normally required by DNA purification protocols. The use of one single microfluidic volume for both DNA purification and amplification dramatically simplifies the structure of microfluidic devices for DNA preparation. X-Ray Photoelectron Spectroscopy (XPS) was used to analyze the surface chemical composition. Atomic Force Microscopy (AFM) and Field Emission Scanning Electron Microscopy (FESEM) were employed to assess the morphological nanostructure of the PDMS-chips. A confocal fluorescence analysis was utilized to check DNA distribution inside the chip.

  11. Solid solution, phase separation, and cathodoluminescence of GaP-ZnS nanostructures.

    Liu, Baodan; Bando, Yoshio; Dierre, Benjamin; Sekiguchi, Takashi; Golberg, Dmitri; Jiang, Xin


    Quaternary solid-solution nanowires made of GaP and ZnS have been synthesized through well-designed synthetic routines. The as-synthesized GaP-ZnS solid-solution nanowires exhibit decent crystallinity with the GaP phase as the host, while a large amount of twin structural defects are observed in ZnS-rich nanowires. Cathodoluminescence studies showed that GaP-rich solid-solution nanowires have a strong visible emission centered at 600 nm and the ZnS-rich solid-solution nanowires exhibited a weak emission peak in the UV range and a broad band in the range 400-600 nm. The formation mechanism, processes, and optical emissions of GaP-ZnS solid-solution nanowires were discussed in detail.

  12. A modified method for estimation of chemical oxygen demand for samples having high suspended solids.

    Yadvika; Yadav, Asheesh Kumar; Sreekrishnan, T R; Satya, Santosh; Kohli, Sangeeta


    Determination of chemical oxygen demand (COD) of samples having high suspended solids concentration such as cattle dung slurry with open reflux method of APHA-AWWA-WPCF did not give consistent results. This study presents a modification of the open reflux method (APHA-AWWA-WPCF) to make it suitable for samples with high percentage of suspended solids. The new method is based on a different technique of sample preparation, modified quantities of reagents and higher reflux time as compared to the existing open reflux method. For samples having solids contents of 14.0 g/l or higher, the modified method was found to give higher value of COD with much higher consistency and accuracy as compared to the existing open reflux method.

  13. Sol-gel molecularly imprinted polymer for selective solid phase microextraction of organophosphorous pesticides.

    Wang, Yu-Long; Gao, Yuan-Li; Wang, Pei-Pei; Shang, Huan; Pan, Si-Yi; Li, Xiu-Juan


    A sol-gel technique was applied for the preparation of water-compatible molecularly imprinted polymer (MIP) for solid phase microextraction (SPME) using diazinon as template and polyethylene glycol as functional monomer. The MIP-coated fiber demonstrated much better selectivity to diazinon and its structural analogs in aqueous cucumber sample than in distilled water, indicating its potential in real samples. Thanks to its specific adsorption as well as rough and porous surface, the coating revealed rather larger extraction capability than the non-imprinted polymer and commercial fibers. In addition, the fiber exhibited excellent thermal (about 350°C) and chemical stability (organic and inorganic). After optimization of several parameters affecting extraction efficiency, a method based on MIP-SPME combined with gas chromatography was developed for the determination of organophosphorus pesticides (OPPs) in vegetable samples. The limits of detection for the tested OPPs were in the range of 0.017-0.77 μg kg(-1). The proposed method was applied to evaluate OPPs in spiked cucumber, green pepper, Chinese cabbage, eggplant and lettuce samples, and recoveries of 81.2-113.5% were obtained by the standard addition method with three spiking levels in each kind of vegetable.

  14. Thermal Diffusivity and Thermal Conductivity of Five Different Steel Alloys in the Solid and Liquid Phases

    Wilthan, B.; Schützenhöfer, W.; Pottlacher, G.


    The need for characterization of thermophysical properties of steel and nickel-based alloys was addressed in the FFG-Bridge Project 810999 in cooperation with a partner from industry, Böhler Edelstahl GmbH & Co KG. To optimize numerical simulations of production processes, such as remelting or plastic deformation, additional, and more accurate data were necessary for the alloys under investigation. With a fast ohmic pulse heating circuit system, the temperature-dependent specific electrical resistivity, density, and specific heat capacity for a set of five high alloyed steels were measured. Hence, using the Wiedemann-Franz law with a Lorenz number of , the thermal diffusivity and thermal conductivity could be calculated for the solid and liquid phases up to temperatures of 2500 K. This experimental approach is limited by the following requirements for the specimens: they have to be electrically conducting, the melting point has to be high enough for the implemented pyrometric temperature measurement, and one has to be able to draw wires of the material. The latter restriction is technologically challenging with some of the materials being very brittle. For all samples, electrical and temperature signals are recorded and a fast shadowgraph method is used to measure the volume expansion. For each material under investigation, a set of data including the chemical composition, the density at room temperature, solidus and liquidus temperatures, and the change of enthalpy, resistivity, density, thermal conductivity, and thermal diffusivity as a function of temperature is reported.

  15. Laboratory investigation of aluminum solubility and solid-phase properties following alum treatment of lake waters.

    Berkowitz, Jacob; Anderson, Michael A; Graham, Robert C


    Water samples from two southern California lakes adversely affected by internal nutrient loading were treated with a 20 mg/L dose of Al3+ in laboratory studies to examine Al solubility and solid-phase speciation over time. Alum [Al2(SO4)3 . 18 H2O] applications to water samples from Big Bear Lake and Lake Elsinore resulted in a rapid initial decrease in pH and alkalinity followed by a gradual recovery in pH over several weeks. Dissolved Al concentrations increased following treatment, reaching a maximum of 2.54 mg/L after 17 days in Lake Elsinore water and 0.91 mg/L after 48 days in Big Bear Lake water; concentrations in both waters then decreased to Lake Elsinore water. Surface areas also decreased over time as crystals reordered to form gibbsite/microcrystalline gibbsite species. DSC-TGA results suggested that the initially formed amorphous Al(OH)3 underwent transformation to >45% gibbsite. These results were supported by geochemical modeling using Visual MINTEQ, with Al solubility putatively controlled by amorphous Al(OH)3 shortly after treatment and approaching that of microcrystalline gibbsite after about 150 days. These findings indicate that Al(OH)3 formed after alum treatment undergoes significant chemical and mineralogical changes that may alter its effectiveness as a reactive barrier to phosphorus release from lake sediments.

  16. Epitaxially grown polycrystalline silicon thin-film solar cells on solid-phase crystallised seed layers

    Li, Wei; Varlamov, Sergey; Xue, Chaowei


    This paper presents the fabrication of poly-Si thin film solar cells on glass substrates using seed layer approach. The solid-phase crystallised P-doped seed layer is not only used as the crystalline template for the epitaxial growth but also as the emitter for the solar cell structure. This paper investigates two important factors, surface cleaning and intragrain defects elimination for the seed layer, which can greatly influence the epitaxial grown solar cell performance. Shorter incubation and crystallisation time is observed using a simplified RCA cleaning than the other two wet chemical cleaning methods, indicating a cleaner seed layer surface is achieved. Cross sectional transmission microscope images confirm a crystallographic transferal of information from the simplified RCA cleaned seed layer into the epi-layer. RTA for the SPC seed layer can effectively eliminate the intragrain defects in the seed layer and improve structural quality of both of the seed layer and the epi-layer. Consequently, epitaxial grown poly-Si solar cell on the RTA treated seed layer shows better solar cell efficiency, Voc and Jsc than the one on the seed layer without RTA treatment.

  17. Molecularly imprinted calixarene fiber for solid-phase microextraction of four organophosphorous pesticides in fruits.

    Li, Jing-Wen; Wang, Yu-Long; Yan, Shan; Li, Xiu-Juan; Pan, Si-Yi


    Calixarene was used as a functional monomer to fabricate a molecularly imprinted polymer (MIP) by sol-gel technique for solid-phase microextraction (SPME) of parathion-methyl and its structural analogs. The MIP-coated fiber possessed excellent thermal and chemical stability as well as high extraction capacity. Its selectivity and possible recognition mechanism were investigated. The similarities in molecular shape and functional group play a key role in the selective recognition of the imprinted material. Any changes to the structure of the template would decrease the imprinting factor. A comparison of MIP-SPME was made with liquid-liquid extraction coupled with gas chromatography for the determination of organophosphorus pesticides (OPPs) in fruits. Much lower limits of detection and better recoveries were achieved by SPME in spiked apple and pineapple samples. The experiment demonstrates that the proposed method using the calixarene MIP fiber was more suitable for selective determination of trace OPPs in those fruit samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Graphene-coated fiber for solid-phase microextraction of triazine herbicides in water samples.

    Wu, Qiuhua; Feng, Cheng; Zhao, Guangying; Wang, Chun; Wang, Zhi


    Graphene is a novel and interesting carbon material that could be used for the separation and purification of some chemical compounds. In this investigation, graphene was used as a novel fiber-coating material for the solid-phase microextraction (SPME) of four triazine herbicides (atrazine, prometon, ametryn and prometryn) in water samples. The main parameters that affect the extraction and desorption efficiencies, such as the extraction time, stirring rate, salt addition, desorption solvent and desorption time, were investigated and optimized. The optimized SPME by graphene-coated fiber coupled with high-performance liquid chromatography-diode array detection (HPLC-DAD) was successfully applied for the determination of the four triazine herbicides in water samples. The linearity of the method was in the range from 0.5 to 200 ng/mL, with the correlation coefficients (r) ranging from 0.9989 to 0.9998. The limits of detection of the method were 0.05-0.2 ng/mL. The relative standard deviations varied from 3.5 to 4.9% (n=5). The recoveries of the triazine herbicides from water samples at spiking levels of 20.0 and 50.0  ng/mL were in the range between 86.0 and 94.6%. Compared with two commercial fibers (CW/TPR, 50 μm; PDMS/DVB, 60 μm), the graphene-coated fiber showed higher extraction efficiency.

  19. Volatile composition of peppermint (Mentha piperita L.) commercial teas through solid phase extraction.

    Riachi, L G; Abi-Zaid, I E; Moreira, R F A; De Maria, C A B


    Volatiles from aqueous extract of peppermint commercial sachets were investigated through gas chromatography/flame ionization detection (GC/FID) and GC/mass spectrometry (MS). Samples were prepared under similar conditions as in homemade tea. Volatiles were isolated using solid phase extraction method (SPE) with Porapak Q trap followed by desorption with acetone. Estimated mean values for short and medium chain carboxylic acids (C2-C12) and ketones lay in the range of 50-64 microg kg(-1) whilst aliphatic alcohols and acyclic hydrocarbons had values lower than 6 microg kg(-1). The major volatiles were terpenes (275-382 microg kg(-1)) that reached 89 % of the total composition. A total of 16 compounds, among them dodecane, acetoin, acetol, citral, geraniol and octanoic acid have been described by the first time in peppermint tea. These findings could be attributed to the different analytical approach employed, mainly to the use of different extraction/pre-concentration techniques. Given the apparently lower proportion of terpenes in the aqueous extract it may be that the chemical properties of the peppermint essential oil are not entirely reproduced with homemade tea.

  20. Conductive polymeric ionic liquids for electroanalysis and solid-phase microextraction.

    Young, Joshua A; Zhang, Cheng; Devasurendra, Amila M; Tillekeratne, L M Viranga; Anderson, Jared L; Kirchhoff, Jon R


    Three novel electropolymerizable thiophene-based ionic liquids (ILs) were synthesized and characterized as potential candidates for developing selective extraction media for chemical analysis. Electropolymerization of the bis[(trifluoromethyl)sulfonyl]imide ([NTf2](-)) analogs successfully produced uniform polymeric thin-films on macro- and microelectrode substrates from both vinyl and methylimidazolium IL monomer derivatives. The resultant conducting polymer IL (CPIL) films were characterized by electrochemical methods and found to exhibit attractive behavior towards anionic species while simultaneously providing an exclusion barrier toward cationic species. Thermogravimetric analysis of the thiophene-based IL monomers established a high thermal stability, particularly for the methylimidazolium IL, which was stable until temperatures above 350 °C. Subsequently, the methylimidazolium IL was polymerized on 125 μm platinum wires and utilized for the first time as a sorbent coating for headspace solid-phase microextraction (HS-SPME). The sorbent coating was easily prepared in a reproducible manner, provided high thermal stability, and allowed for the gas chromatographic analysis of polar analytes. The normalized response of the poly[thioph-C6MIm][NTf2]-based sorbent coating exhibited higher extraction efficiency compared to an 85 μm polyacrylate fiber and excellent fiber-to-fiber reproducibility. Therefore, the electropolymerizable thiophene-based ILs were found to be viable new materials for the preparation of sorbent coatings for HS-SPME.

  1. The solid-liquid phase diagrams of binary mixtures of consecutive, even saturated fatty acids.

    Costa, Mariana C; Sardo, Mariana; Rolemberg, Marlus P; Coutinho, João A P; Meirelles, Antonio J A; Ribeiro-Claro, Paulo; Krähenbühl, M A


    For the first time, the solid-liquid phase diagrams of five binary mixtures of saturated fatty acids are here presented. These mixtures are formed of caprylic acid (C(8:0))+capric acid (C(10:0)), capric acid (C(10:0))+lauric acid (C(12:0)), lauric acid (C(12:0))+myristic acid (C(14:0)), myristic acid (C(14:0))+palmitic acid (C(16:0)) and palmitic acid (C(16:0))+stearic acid (C(18:0)). The information used in these phase diagrams was obtained by differential scanning calorimetry (DSC), X-ray diffraction (XRD), FT-Raman spectrometry and polarized light microscopy, aiming at a complete understanding of the phase diagrams of the fatty acid mixtures. All of the phase diagrams reported here presented the same global behavior and it was shown that this was far more complex than previously imagined. They presented not only peritectic and eutectic reactions, but also metatectic reactions, due to solid-solid phase transitions common in fatty acids and regions of solid solution not previously reported. This work contributes to the elucidation of the phase behavior of these important biochemical molecules, with implications in various industrial applications.

  2. Characterization of rhamnolipids by liquid chromatography/mass spectrometry after solid-phase extraction.

    Behrens, Beate; Engelen, Jeannine; Tiso, Till; Blank, Lars Mathias; Hayen, Heiko


    Rhamnolipids are surface-active agents with a broad application potential that are produced in complex mixtures by bacteria of the genus Pseudomonas. Analysis from fermentation broth is often characterized by laborious sample preparation and requires hyphenated analytical techniques like liquid chromatography coupled to mass spectrometry (LC-MS) to obtain detailed information about sample composition. In this study, an analytical procedure based on chromatographic method development and characterization of rhamnolipid sample material by LC-MS as well as a comparison of two sample preparation methods, i.e., liquid-liquid extraction and solid-phase extraction, is presented. Efficient separation was achieved under reversed-phase conditions using a mixed propylphenyl and octadecylsilyl-modified silica gel stationary phase. LC-MS/MS analysis of a supernatant from Pseudomonas putida strain KT2440 pVLT33_rhlABC grown on glucose as sole carbon source and purified by solid-phase extraction revealed a total of 20 congeners of di-rhamnolipids, mono-rhamnolipids, and their biosynthetic precursors 3-(3-hydroxyalkanoyloxy)alkanoic acids (HAAs) with different carbon chain lengths from C8 to C14, including three rhamnolipids with uncommon C9 and C11 fatty acid residues. LC-MS and the orcinol assay were used to evaluate the developed solid-phase extraction method in comparison with the established liquid-liquid extraction. Solid-phase extraction exhibited higher yields and reproducibility as well as lower experimental effort.

  3. Mixed Model for Silt-Laden Solid-Liquid Two-Phase Flows

    唐学林; 徐宇; 吴玉林


    The kinetic theory of molecular gases was used to derive the governing equations for dense solid-liquid two-phase flows from a microscopic flow characteristics viewpoint by multiplying the Boltzmann equation for each phase by property parameters and integrating over the velocity space. The particle collision term was derived from microscopic terms by comparison with dilute two-phase flow but with consideration of the collisions between particles for dense two-phase flow conditions and by assuming that the particle-phase velocity distribution obeys the Maxwell equations. Appropriate terms from the dilute two-phase governing equations were combined with the dense particle collision term to develop the governing equations for dense solid-liquid turbulent flows. The SIMPLEC algorithm and a staggered grid system were used to solve the discretized two-phase governing equations with a Reynolds averaged turbulence model. Dense solid-liquid turbulent two-phase flows were simulated for flow in a duct. The simulation results agree well with experimental data.

  4. Solid-Phase Synthesis of Amine/Carboxyl Substituted Prolines and Proline Homologues: Scope and Limitations.

    Zhou, Ziniu; Scott, William L; O'Donnell, Martin J


    A solid-phase procedure is used to synthesize racemic peptidomimetics based on the fundamental peptide unit. The peptidomimetics are constructed around proline or proline homologues variably substituted at the amine and carbonyl sites. The procedure expands the diversity of substituted peptidomimetic molecules available to the Distributed Drug Discovery (D3) project. Using a BAL-based solid-phase synthetic sequence the proline or proline homologue subunit is both constructed and incorporated into the peptidomimetic by an α-alkylation, hydrolysis and intramolecular cyclization sequence. Further transformations on solid-phase provide access to a variety of piperazine derivatives representing a class of molecules known to exhibit central nervous system activity. The procedure works well with proline cores, but with larger six- and seven-membered ring homologues the nature of the carboxylic acid acylating the cyclic amine can lead to side reactions and result in poor overall yields.

  5. Rotating belt sieves for primary treatment, chemically enhanced primary treatment and secondary solids separation.

    Rusten, B; Rathnaweera, S S; Rismyhr, E; Sahu, A K; Ntiako, J


    Fine mesh rotating belt sieves (RBS) offer a very compact solution for removal of particles from wastewater. This paper shows examples from pilot-scale testing of primary treatment, chemically enhanced primary treatment (CEPT) and secondary solids separation of biofilm solids from moving bed biofilm reactors (MBBRs). Primary treatment using a 350 microns belt showed more than 40% removal of total suspended solids (TSS) and 30% removal of chemical oxygen demand (COD) at sieve rates as high as 160 m³/m²-h. Maximum sieve rate tested was 288 m³/m²-h and maximum particle load was 80 kg TSS/m²-h. When the filter mat on the belt increased from 10 to 55 g TSS/m², the removal efficiency for TSS increased from about 35 to 60%. CEPT is a simple and effective way of increasing the removal efficiency of RBS. Adding about 1 mg/L of cationic polymer and about 2 min of flocculation time, the removal of TSS typically increased from 40-50% without polymer to 60-70% with polymer. Using coagulation and flocculation ahead of the RBS, separation of biofilm solids was successful. Removal efficiencies of 90% TSS, 83% total P and 84% total COD were achieved with a 90 microns belt at a sieve rate of 41 m³/m²-h.

  6. Dissolved organic matter: Fractional composition and sorbability by the soil solid phase (Review of literature)

    Karavanova, E. I.


    The behavior of dissolved organic matter (DOM) in soils under varying environmental conditions represents a poorly studied aspect of the problem of organic matter loss from soils. The equilibrium and sustainable development of ecosystems in the northern latitudes are largely determined by the balance between the formation of DOM, its accumulation in the lower soil horizons, and its input with runoff into surface waters. The residence time, retention strength in the soil, and thermodynamic and biochemical stabilities depend on the localization of DOM in the pore space and its chemical structure. Amphiphilic properties represent a valuable diagnostic parameter, which can be used to predict the behavior of DOM in the soil. Acidic components of hydrophobic and hydrophilic nature constitute the major portion of DOM in forest soils of the temperate zone. The hydrophilic fraction includes short-chain aliphatic carboxylic acids, hydrocarbons, and amino acids and is poorly sorbed by the solid phase. However, the existence of this fraction in soil solution is also limited both in space (in the finest pores) and time because of higher accessibility to microbial degradation. The hydrophilic fraction composes the major portion of labile DOM in soils. The hydrophobic fraction consists of soluble degradation products of lignin; it is enriched in structural ortho-hydroxybenzene fragments, which ensure its selective sorption and strong retention in soils. Sorption is favored by low pH values (3.5-5), the high ionic strength of solution, the heavy texture and fine porous structure of soil, the high contents of oxalate- and dithionite-soluble iron (and aluminum) compounds, and hydrological conditions characterized by slow water movement. The adsorbed DOM is chemically and biochemically recalcitrant and significantly contributes to the humus reserves in the low mineral horizons of soils.

  7. [Determination of short chain chlorinated paraffins in leather products by solid phase extraction coupled with gas chromatography-mass spectrometry].

    Zhang, Weiya; Wan, Xin; Li, Lixia; Wang, Chengyun; Jin, Shupei; Xing, Jun


    The short chain chlorinated paraffins (SCCPs) are the additives frequently used in the leather production in China, but they have been put into the list of forbidden chemicals issued by European Union recently. In fact, there is not a commonly recognized method for the determination of the SCCPs in the leather products due to the serious matrix interferences from the leather products and the complex chemical structures of the SCCPs. A method of solid phase extraction coupled with gas chromatography-mass spectrometry (SPE-GC-MS) was established for the determination of the SCCPs in the leather products after the optimization of the SPE conditions. It was found that the interferences from the leather products were thor- oughly separated from the analyte of the SCCPs on a home-made solid phase extraction (SPE) column filled with silica packing while eluted with a mixed solvent of n-hexane-methylene chloride (2:1, v/v). With this method, the recoveries for the SCCPs spiked in the real leather samples varied from 90.47% to 99.00% with the relative standard deviations (RSDs) less than 6.7%, and the limits of detection (LODs) were between 0.069 and 0.110 mg/kg. This method is suitable for qualitative and quantitative analysis of SCCPs in the leather products.

  8. Binary Solid-Liquid Phase Diagram of Phenol and t-Butanol: An Undergraduate Physical Chemistry Experiment

    Xu, Xinhua; Wang, Xiaogang; Wu, Meifen


    The determination of the solid-liquid phase diagram of a binary system is always used as an experiment in the undergraduate physical chemistry laboratory courses. However, most phase diagrams investigated in the lab are simple eutectic ones, despite the fact that complex binary solid-liquid phase diagrams are more common. In this article, the…

  9. Binary Solid-Liquid Phase Diagram of Phenol and t-Butanol: An Undergraduate Physical Chemistry Experiment

    Xu, Xinhua; Wang, Xiaogang; Wu, Meifen


    The determination of the solid-liquid phase diagram of a binary system is always used as an experiment in the undergraduate physical chemistry laboratory courses. However, most phase diagrams investigated in the lab are simple eutectic ones, despite the fact that complex binary solid-liquid phase diagrams are more common. In this article, the…

  10. DNA extraction on bio-chip: history and preeminence over conventional and solid-phase extraction methods.

    Ayoib, Adilah; Hashim, Uda; Gopinath, Subash C B; Md Arshad, M K


    This review covers a developmental progression on early to modern taxonomy at cellular level following the advent of electron microscopy and the advancement in deoxyribonucleic acid (DNA) extraction for expatiation of biological classification at DNA level. Here, we discuss the fundamental values of conventional chemical methods of DNA extraction using liquid/liquid extraction (LLE) followed by development of solid-phase extraction (SPE) methods, as well as recent advances in microfluidics device-based system for DNA extraction on-chip. We also discuss the importance of DNA extraction as well as the advantages over conventional chemical methods, and how Lab-on-a-Chip (LOC) system plays a crucial role for the future achievements.

  11. Extraction of Pb2+ using Silica from Rice Husks Ash (RHA – Chitosan as Solid Phase

    Hanandayu Widwiastuti


    Full Text Available The existence of lead (Pb compounds in waters can be caused of waste pollution from industrial activities such as dye and battery industries. Lead has toxic characteristic and is able to causing deseases. The levels of Cr(VI can be decreased by methods such as electroplating, oxidation, reduction, and membrane separation. But this methods require high cost and produce a lot of waste. Furthermore, those methods cannot determine the small concentration of Pb2+. Therefore, solid phase extraction is used because it’s a simple method and can be used to preconcentrate Pb2+ ion. The aim of this study is to create solid phase from nature material as an alternative method to determine Pb2+ in water samples. The solid phase is silica from rice husks ash (RHA that was modified using chitosan. To achieve that aim, the optimization of silica : chitosan composition was done. The influence of Pb2+ concentration and citric acid concentration was studied to obtain optimum recovery of Pb2+. Interaction between Pb2+ ion and solid phase silica – chitosan could be estimated based on the result. The result showed the optimum composition of silica : chitosan is 65% silica : 35% chitosan with Cation Exchange Capacity (CEC 0.00455 mek/g. Mass Adsorbed Pb2+for 1 g silica : chitosan 65% is 9.715 mg/g. Optimum recovery of Pb2+ on solid phase extraction is reached at concentration of Pb2+ 10 ppm and citric acid concentration 0.05 M (88.25 % and 81.18 %. This result showed that solid phase extraction using silica – chitosan can be used as an alternative method to determine Pb2+ in water.

  12. A photolabile linker for the solid-phase synthesis of peptide hydrazides and heterocycles.

    Qvortrup, Katrine; Komnatnyy, Vitaly V; Nielsen, Thomas E


    A photolabile hydrazine linker for the solid-phase synthesis of peptide hydrazides and hydrazine-derived heterocycles is presented. The developed protocols enable the efficient synthesis of structurally diverse peptide hydrazides derived from the standard amino acids, including those with side-chain protected residues at the C-terminal of the resulting peptide hydrazide, and are useful for the synthesis of dihydropyrano[2,3-c]pyrazoles. The linker is compatible with most commonly used coupling reagents and protecting groups for solid-phase peptide synthesis.

  13. Development of orthogonally protected hypusine for solid-phase peptide synthesis.

    Song, Aimin; Tom, Jeffrey; Yu, Zhiyong; Pham, Victoria; Tan, Dajin; Zhang, Dengxiong; Fang, Guoyong; Yu, Tao; Deshayes, Kurt


    An orthogonally protected hypusine reagent was developed for solid-phase synthesis of hypusinated peptides using the Fmoc/t-Bu protection strategy. The reagent was synthesized in an overall yield of 27% after seven steps from Cbz-Lys-OBzl and (R)-3-hydroxypyrrolidin-2-one. The side-chain protecting groups (Boc and t-Bu) are fully compatible with standard Fmoc chemistry and can be readily removed during the peptide cleavage step. The utility of the reagent was demonstrated by solid-phase synthesis of hypusinated peptides.

  14. Synthesis of indium tin oxide powder by solid-phase reaction with microwave heating

    Fukui, Kunihiro; Kanayama, Keiji; Katoh, Manabu; Yamamoto, Tetsuya; Yoshida, Hideto


    Indium tin oxide (ITO) powder was synthesized from indium oxide and tin oxide powders by a solid-phase method using microwave heating and conventional heating methods. Microwave heating could reduce the treatment time necessary for the completion of the solid-phase reaction by 1/30. This decrease was attributed to an increase in the diffusion rate of Sn at the local heat spot in the indium oxide formed by microwave irradiation. However, microwave heating also decreased the amount of ITO produ...

  15. Detection of ibuprofen and ciprofloxacin by solid-phase extraction and UV/Vis spectroscopy

    Zhou, Zhengwei; Jiang, Jia Qian


    A simple and economic solid-phase extraction coupled with UV/Vis spectrophotometric method is described for the analysis of ibuprofen and ciprofloxacin. Following solid-phase extraction from model wastewater samples containing standard ibuprofen or ciprofloxacin, elutes were analyzed by a UV/Vis spectrophotometer at 225 nm for ibuprofen and 280 nm for ciprofloxacin. The assay was linear for both compounds with good coefficients of correlation. This method shows good recoveries for both compounds with 101.0 ± 9.8% for ibuprofen and 99.4 ± 11.8% ciprofloxacin.

  16. A Photolabile Linker for the Solid-Phase Synthesis of Peptide Hydrazides and Heterocycles

    Qvortrup, Katrine; Komnatnyy, Vitaly V.; Nielsen, Thomas Eiland


    A photolabile hydrazine linker for the solid-phase synthesis of peptide hydrazides and hydrazine-derived heterocycles is presented. The developed protocols enable the efficient synthesis of structurally diverse peptide hydrazides derived from the standard amino adds, including those with side-cha......-chain protected residues at the C-terminal of the resulting peptide hydrazide, and are useful for the synthesis of dihydropyrano[2,3-c]pyrazoles. The linker is compatible with most commonly used coupling reagents and protecting groups for solid-phase peptide synthesis....

  17. CuAAC: An Efficient Click Chemistry Reaction on Solid Phase.

    Castro, Vida; Rodríguez, Hortensia; Albericio, Fernando


    Click chemistry is an approach that uses efficient and reliable reactions, such as Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC), to bind two molecular building blocks. CuAAC has broad applications in medicinal chemistry and other fields of chemistry. This review describes the general features and applications of CuAAC in solid-phase synthesis (CuAAC-SP), highlighting the suitability of this kind of reaction for peptides, nucleotides, small molecules, supramolecular structures, and polymers, among others. This versatile reaction is expected to become pivotal for meeting future challenges in solid-phase chemistry.

  18. Headspace solid phase microextraction (HSSPME) for the determination of volatile and semivolatile pollutants in soils

    Llompart, Maria [Departamento de Quimica Analitica Nutricion y Bromatologia, Facultad de Quimica, Universidad de Santiago de Compostela, E-15706 Santiago de Compostela (Spain); Li, Ken; Fingas, Merv [Emergencies Science Division, Environment Canada, Environmental Technology Centre, 3439 River Road, Ottawa, ON (Canada)


    We have investigated the use of headspace solid phase microextraction (HSSPME) as a sample concentration and preparation technique for the analysis of volatile and semivolatile pollutants in soil samples. Soil samples were suspended in solvent and the SPME fibre suspended in the headspace above the slurry. Finally, the fibre was desorbed in the Gas Chromatograph (GC) injection port and the analysis of the samples was carried out. Since the transfer of contaminants from the soil to the SPME fibre involves four separate phases (soil-solvent-headspace and fibre coating), parameters affecting the distribution of the analytes were investigated. Using a well-aged artificially spiked garden soil, different solvents (both organic and aqueous) were used to enhance the release of the contaminants from the solid matrix to the headspace. It was found that simple addition of water is adequate for the purpose of analysing the target volatile organic chemicals (VOCs) in soil. The addition of 1 ml of water to 1 g of soil yielded maximum response. Without water addition, the target VOCs were almost not released from the matrix and a poor response was observed. The effect of headspace volume on response as well as the addition of salt were also investigated. Comparison studies between conventional static headspace (HS) at high temperature (95C) and the new technology HSSPME at room temperature (=20C) were performed. The results obtained with both techniques were in good agreement. HSSPME precision and linearity were found to be better than automated headspace method and HSSPME also produced a significant enhancement in response. The detection and quantification limits for the target VOCs in soils were in the sub-ng g{sup -1} level. Finally, we tried to extend the applicability of the method to the analysis of semivolatiles. For these studies, two natural soils contaminated with diesel fuel and wood preservative, as well as a standard urban dust contaminated with polyaromatic

  19. Fast Atomic-Scale Chemical Imaging of Crystalline Materials and Dynamic Phase Transformations.

    Lu, Ping; Yuan, Ren Liang; Ihlefeld, Jon F; Spoerke, Erik David; Pan, Wei; Zuo, Jian Min


    Atomic-scale phenomena fundamentally influence materials form and function that makes the ability to locally probe and study these processes critical to advancing our understanding and development of materials. Atomic-scale chemical imaging by scanning transmission electron microscopy (STEM) using energy-dispersive X-ray spectroscopy (EDS) is a powerful approach to investigate solid crystal structures. Inefficient X-ray emission and collection, however, require long acquisition times (typically hundreds of seconds), making the technique incompatible with electron-beam sensitive materials and study of dynamic material phenomena. Here we describe an atomic-scale STEM-EDS chemical imaging technique that decreases the acquisition time to as little as one second, a reduction of more than 100 times. We demonstrate this new approach using LaAlO3 single crystal and study dynamic phase transformation in beam-sensitive Li[Li0.2Ni0.2Mn0.6]O2 (LNMO) lithium ion battery cathode material. By capturing a series of time-lapsed chemical maps, we show for the first time clear atomic-scale evidence of preferred Ni-mobility in LNMO transformation, revealing new kinetic mechanisms. These examples highlight the potential of this approach toward temporal, atomic-scale mapping of crystal structure and chemistry for investigating dynamic material phenomena.

  20. Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction of herbicides in peanuts.

    Li, Na; Wang, Zhibing; Zhang, Liyuan; Nian, Li; Lei, Lei; Yang, Xiao; Zhang, Hanqi; Yu, Aimin


    Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction was developed and applied to the extraction of pesticides in high fatty matrices. The herbicides were ultrasonically extracted from peanut using ethyl acetate as extraction solvent. The separation of the analytes from a large amount of co-extractive fat was achieved by dispersive solid-phase extraction using MIL-101(Cr) as sorbent. In this step, the analytes were adsorbed on MIL-101(Cr) and the fat remained in bulk. The herbicides were separated and determined by high-performance liquid chromatography. The experimental parameters, including type and volume of extraction solvent, ultrasonication time, volume of hexane and eluting solvent, amount of MIL-101(Cr) and dispersive solid phase extraction time, were optimized. The limits of detection for herbicides range from 0.98 to 1.9 μg/kg. The recoveries of the herbicides are in the range of 89.5-102.7% and relative standard deviations are equal or lower than 7.0%. The proposed method is simple, effective and suitable for treatment of the samples containing high content of fat.

  1. Recent developments and future trends in solid phase microextraction techniques towards green analytical chemistry.

    Spietelun, Agata; Marcinkowski, Łukasz; de la Guardia, Miguel; Namieśnik, Jacek


    Solid phase microextraction find increasing applications in the sample preparation step before chromatographic determination of analytes in samples with a complex composition. These techniques allow for integrating several operations, such as sample collection, extraction, analyte enrichment above the detection limit of a given measuring instrument and the isolation of analytes from sample matrix. In this work the information about novel methodological and instrumental solutions in relation to different variants of solid phase extraction techniques, solid-phase microextraction (SPME), stir bar sorptive extraction (SBSE) and magnetic solid phase extraction (MSPE) is presented, including practical applications of these techniques and a critical discussion about their advantages and disadvantages. The proposed solutions fulfill the requirements resulting from the concept of sustainable development, and specifically from the implementation of green chemistry principles in analytical laboratories. Therefore, particular attention was paid to the description of possible uses of novel, selective stationary phases in extraction techniques, inter alia, polymeric ionic liquids, carbon nanotubes, and silica- and carbon-based sorbents. The methodological solutions, together with properly matched sampling devices for collecting analytes from samples with varying matrix composition, enable us to reduce the number of errors during the sample preparation prior to chromatographic analysis as well as to limit the negative impact of this analytical step on the natural environment and the health of laboratory employees.

  2. Solubility and hydrolysis of Np(V) in dilute to concentrated alkaline NaCl solutions. Formation of Na-Np(V)-OH solid phases at 22 C

    Petrov, Vladimir G. [Lomonosov Moscow State Univ. (Russian Federation). Dept. of Chemistry; Fellhauer, David; Gaona, Xavier; Dardenne, Kathy; Rothe, Joerg; Altmaier, Marcus [Karlsruhe Institute of Technology (Germany). Inst. for Nuclear Waste Disposal; Kalmykov, Stepan N. [Lomonosov Moscow State Univ. (Russian Federation). Dept. of Chemistry; NRC Kurchatov Institute, Moscow (Russian Federation)


    The solubility of Np(V) was investigated at T=22±2 C in alkaline NaCl solutions of different ionic strength (0.1-5.0 M). The solid phases controlling the solubility at different -log{sub 10} m{sub H{sup +}}(pH{sub m}) and NaCl concentration were characterized by XRD, quantitative chemical analysis, SEM-EDS and XAFS (both XANES and EXAFS). Aqueous phases in equilibrium with Np(V) solids were investigated for selected samples within 8.9≤pH{sub m}≤10.3 by UV-vis/NIR absorption spectroscopy. In 0.1 M NaCl, the experimental solubility of the initial greenish NpO{sub 2}OH(am) solid phase is in good agreement with previous results obtained in NaClO{sub 4} solutions, and is consistent with model calculations for fresh NpO{sub 2}OH(am) using the thermodynamic data selection in NEA-TDB. Below pH{sub m}∝11.5 and for all NaCl concentrations studied, Np concentration in equilibrium with the solid phase remained constant during the timeframe of this study (∝2 years). This observation is in contrast to the aging of the initial NpO{sub 2}OH(am) into a more crystalline modification with the same stoichiometry, NpO{sub 2}OH(am, aged), as reported in previous studies for concentrated NaClO{sub 4} and NaCl. Instead, the greenish NpO{sub 2}OH(am) transforms into a white solid phase in those systems with [NaCl]≥1.0 M and pH{sub m}≥11.5, and into two different pinkish phases above pH{sub m}∝13.2. The solid phase transformation is accompanied by a drop in Np solubility of 0.5-2 log{sub 10}-units (depending upon NaCl concentration). XANES analyses of green, white and pink phases confirm the predominance of Np(V) in all cases. Quantitative chemical analysis shows the incorporation of Na{sup +} in the original NpO{sub 2}OH(am) material, with Na:Np ≤ 0.3 for the greenish solids and 0.8 ≤ Na:Np ≤ 1.6 for the white and pinkish phases. XRD data confirms the amorphous character of the greenish phase, whereas white and pink solids show well-defined but discrepant XRD patterns

  3. Solid solution and amorphous phase in Ti–Nb–Ta–Mn systems synthesized by mechanical alloying

    Aguilar, C., E-mail: [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Guzman, P. [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Lascano, S. [Departamento de Ingeniería Mecánica, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Parra, C. [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Bejar, L. [Instituto de Investigaciones Metalúrgicas, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, Morelia C.P. 58000, Michoacán (Mexico); Medina, A. [Facultad de Ingeniería Mecánica, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, C.P. 58000, Michoacán (Mexico); Guzman, D. [Departamento de Metalurgia, Universidad de Atacama, Av. España 485, Copiapó (Chile)


    This work discusses the formation of Ti–30Nb–13Ta–xMn (x: 2, 4 and 6 wt%) solid solution by mechanical alloying using a shaker mill. A solid solution was formed after 15 h of milling and an amorphous phase was formed after 30 h of milling, according to X-ray diffraction results. Disappearance of strongest X-ray diffraction peaks of Nb, Ta and Mn indicated the formation of solid solution, while, X-ray diffraction patterns of powders milled for 30 h showed an amorphous hump with crystalline peaks in the angular range of 35–45° in 2θ. TEM image analysis showed the presence of nanocrystalline intermetallic compounds embedded in an amorphous matrix. Mn{sub 2}Ti, MnTi and NbTi{sub 4} intermetallic compounds were detected and revealed crystallites with size ranging from 3 to 20 nm. The Gibbs free energy for the formation of solid solution and amorphous phase of three ternary systems (Ti–Nb–Ta, Ti–Nb–Mn and Ti–Ta–Mn) was calculated using extended Miedema's model. Experimental and thermodynamic data confirmed that solid solution was first formed in the alloy with 6wt% Mn followed by the formation of an amorphous phase as milling time increases. The presence of Mn promoted the formation of amorphous phase because the atomic radius difference between Mn with Ti, Nb and Ta. - Highlights: • Thermodynamics analysis of extension of solid solution of the Ti–Nb–Ta–Mn system. • Formation of amorphous phase and intermetallic compounds were observed. • Nanocrystalline intermetallic compounds were formed with the sizes between 3 and 20 nm.

  4. Optical manipulation of Berry phase in a solid-state spin qubit

    Yale, Christopher G; Zhou, Brian B; Auer, Adrian; Burkard, Guido; Awschalom, David D


    The phase relation between quantum states represents an essential resource for the storage and processing of quantum information. While quantum phases are commonly controlled dynamically by tuning energetic interactions, utilizing geometric phases that accumulate during cyclic evolution may offer superior robustness to noise. To date, demonstrations of geometric phase control in solid-state systems rely on microwave fields that have limited spatial resolution. Here, we demonstrate an all-optical method based on stimulated Raman adiabatic passage to accumulate a geometric phase, the Berry phase, in an individual nitrogen-vacancy (NV) center in diamond. Using diffraction-limited laser light, we guide the NV center's spin along loops on the Bloch sphere to enclose arbitrary Berry phase and characterize these trajectories through time-resolved state tomography. We investigate the limits of this control due to loss of adiabiaticity and decoherence, as well as its robustness to noise intentionally introduced into t...

  5. In-Situ Chemical Dynamics and Phase Mapping Under Steep Thermal Gradients Using Time-Resolved and Spatially Resolved X-Ray Diffraction

    Wong, J.; Larson, E.M.; Holt, J.B.; Ressler, T.; Elmer, J.W.


    Time-resolved and spatially-resolved diffraction techniques have been developed recently to perform materials dynamics study in-situ extending into the time and spatial domain in high temperature processes. The applications of these methods to investigate the chemical dynamics of solid combustion reactions and to map phases and their transformation in fusion welds are exemplified in this paper.

  6. Rotating disk sorbent extraction for pre-concentration of chromogenic organic compounds and direct determination by solid phase spectrophotometry.

    Richter, Pablo; Cañas, Alejandro; Muñoz, Carlos; Leiva, Claudio; Ahumada, Inés


    A novel and very simple microextraction approach for pre-concentration and direct solid phase spectrophotometric measurement has been developed for the determination of chromogenic analytes. The model analyte to assess this approach was the chromophore malachite green (MG). The analyte was extracted from water samples onto a small rotating disk made of Teflon containing a sorbent phase of polydimethylsiloxane (PDMS) on one of its surfaces. We refer to the extraction procedure as rotating disk sorptive extraction (RDSE). After extraction, the sorbent phase with the concentrated analyte was separated from the Teflon disk and used directly for MG determination by solid phase spectrophotometry at 624 nm, without the necessity of a desorption step. Chemical and extraction variables such as concentration of sodium sulfate, pH, disk rotational velocity, extraction time, and temperature were studied in order to establish the best conditions for extraction. Under optimum conditions, the extraction of MG was carried out in 18 min and 90 min, for sample volumes of 100mL or 1000 mL, respectively. The detection limit, based on three times the standard deviation of the blank phase (3σ(b)), was 1.4 μg L⁻¹ and the repeatability, expressed as relative standard deviation (RSD), for 20 μg L⁻¹ MG was 8.1%. This study also applied the method to real samples, obtaining quantitative recovery (mean recovery of 99.3%). The PDMS phases could be reused after desorbing the MG into methanol for 3h. Replacement of the PDMS film onto the disk is very easy and low cost.

  7. Bioproduction of benzaldehyde in a solid-liquid two-phase partitioning bioreactor using Pichia pastoris.

    Jain, Ashu N; Khan, Tanya R; Daugulis, Andrew J


    The bioproduction of benzaldehyde from benzyl alcohol using Pichia pastoris was examined in a solid-liquid two-phase partitioning bioreactor (TPPB) to reduce substrate and product inhibition. Rational polymer selection identified Elvax 40W as an effective sequestering phase, possessing partition coefficients for benzyl alcohol and benzaldehyde of 3.5 and 35.4, respectively. The use of Elvax 40W increased the overall mass of benzaldehyde produced by approx. 300% in a 5 l bioreactor, relative to a single phase biotransformation. The two-phase system had a molar yield of 0.99, indicating that only minor losses occurred. These results provide a promising starting point for solid-liquid TPPBs to enhance benzaldehyde production, and suggest that multiple, targeted polymers may provide relief for transformations characterized by multiple inhibitory substrates/product/by-products.

  8. Chemical characterization of agroforestry solid residues aiming its utilization as adsorbents for metals in water

    Francisco H. M. Luzardo


    Full Text Available In this work, a study of the correlation between the functional groups present in the chemical structure of the fibers of coconut shells, cocoa and eucalyptus, and their adsorption capacity of Cd+2 and Cu+2 ions from water was performed. The content of soluble solids and reactive phenols in aqueous extracts were determined. The chemical functional groups present in the fibers were examined using the IR spectra. The adsorption capacity of the peels was determined using atomic absorption spectrophotometer. For Cd+2, a significant correlation between the adsorption capacity and some specific chemical functional groups present in the fiber was verified. The potential use of these peels, as adsorbent of Cd+2 ions, is based on the presence of OH functional groups such as aryl-OH, aryl-O-CH2 of phenol carboxylic acids, as well as carbonyl groups derived from carboxylic acid salts, in these fibers.

  9. Indirect Determination of Chemical Composition and Fuel Characteristics of Solid Waste

    Riber, Christian; Christensen, Thomas Højlund

    Determination of chemical composition of solid waste can be performed directly or indirectly by analysis of combustion products. The indirect methodology instrumented by a full scale incinerator is the only method that can conclude on elements in trace concentrations. These elements are of great...... interest in evaluating waste management options by for example LCA modeling. A methodology description of indirect determination of chemical composition and fuel properties of waste is provided and validated by examples. Indirect analysis of different waste types shows that the chemical composition...... of toxic elements is shown exemplified by Hg. The average concentration is evaluated to be affected by three occurrences; background, rare items and very rare items (1/800 tonnes), that are all important to the Hg average concentration....

  10. Homogenization of. beta. -solid solution during fast heating of two-phase titanium alloys

    Gridnev, V.N.; Zhuravlev, A.F.; Zhuravlev, B.F.; Ivasishin, O.M.; Markovskij, P.E. (AN Ukrainskoj SSR, Kiev. Inst. Metallofiziki)


    Using model alloy Ti-10%Mo as an example the homogenization of high-temperature ..beta..-phase during fast heating has been studied by calculational and experimental methods. The effect of heating rate and the initial structure disoersion on the homogenization is shown. A method is suggested for evaluation of the concentration state of ..beta..-solid solution depleted parts of commercial two-phase titanium alloys. The method has been used to study the homogenization process.

  11. Numerical investigation of confined swirling gas-solid two phase jet


    This paper presents a k-ε-kp multi-fluid model for simulating confined swirling gas-solid two phase jet comprised of particle-laden flow from a center tube and a swirling air stream entering the test section from the coaxial annular. A series of numerical simulations of the two-phase flow of 30 μm, 45 μm, 60 μm diameter particles respectively yielded results fitting well with published experimental data.

  12. Numerical Simulation of Swirling Gas-solid Two Phase Flow through a Pipe Expansion

    Jin Hanhui; Xia Jun; Fan Jianren; Cen Kefa


    A k- ε -kp multi-fluid model is stated and adopted to simulate swirling gas-solid two phase flow. A particle-laden flow from a center tube and a swirling air stream from the coaxial annular enter the test section. A series of numerical simulations of the two-phase flow are performed based on 30 μ m, 45 μ m, 60 μ m diameter particles respectively. The results fit well with published experimental data.

  13. Numerical investigation of confined swirling gas-solid two phase jet

    金晗辉; 夏钧; 樊建人; 岑可法


    This paper presents a k-e-kp multi-fluid model for simulating confined swirling gas-solid two phase jet comprised of particle-laden flow from a center tube and a swirling air stream entering the test section from the coaxial annular. A series of numerical simulations of the two-phase flow of 30μm, 45μm, 60μm diameter particles respectively yielded results fitting well with published experimental data.


    S. Manna


    Full Text Available High performance liquid chromatographic determination of organophosphorous compound has been done by reverse phase chromatography in goats. The goats were dying showing the symptoms of organophosphorous poisoning. The viscera and stomach contents sample were received from Project Co-Ordinator, Animal Disease Research Institute, Phulnakhara, Cuttack, Orissa. The analysis of samples by HPLC with UV detector after cleaning up in Solid Phase Extraction (SPE revealed presence of malathion that was later quantified.

  15. The 2D Alternative Binary L-J System: Solid-Liquid Phase Diagram

    ZHANG Zhi; CHEN Li-Rong


    The Lennard-Jones potential is introduced into the Collins model and is generalized to the two-dimensionalalternative binary system. The Gibbs free energy of the binary system is calculated. According to the thermodynamicconditions of solid-liquid equilibrium, the "cigar-type" phase diagram and the phase diagram with a minimum areobtained. The results are quite analogous to the behavior of three-dimensional substances.


    Silas R. Ferreira


    Full Text Available Asphaltenes are blamed for various problems in the petroleum industry, especially formation of solid deposits and stabilization of water-in-oil emulsions. Many studies have been conducted to characterize chemical structures of asphaltenes and assess their phase behavior in crude oil or in model-systems of asphaltenes extracted from oil or asphaltic residues from refineries. However, due to the diversity and complexity of these structures, there is still much to be investigated. In this study, asphaltene (subfractions were extracted from an asphaltic residue (AR02, characterized by NMR, elemental analysis, X-ray fluorescence and MS-TOF, and compared to asphaltene subfractions obtained from another asphaltic residue (AR01 described in a previous article. The (subfractions obtained from the two residues were used to prepare model-systems containing 1 wt% of asphaltenes in toluene and their phase behavior was evaluated by measuring asphaltene precipitation onset using optical microscopy. The results obtained indicated minor differences between the asphaltene fractions obtained from the asphaltic residues of distinct origins, with respect to aromaticity, elemental composition (CHN, presence and content of heteroelements and average molar mass. Regarding stability, minor differences in molecule polarity appear to promote major differences in the phase behavior of each of the asphaltene fractions isolated.

  17. The Solid Phase Curing Time Effect of Asbuton with Texapon Emulsifier at the Optimum Bitumen Content

    Sarwono, D.; Surya D, R.; Setyawan, A.; Djumari


    Buton asphalt (asbuton) could not be utilized optimally in Indonesia. Asbuton utilization rate was still low because the processed product of asbuton still have impracticable form in the term of use and also requiring high processing costs. This research aimed to obtain asphalt products from asbuton practical for be used through the extraction process and not requiring expensive processing cost. This research was done with experimental method in laboratory. The composition of emulsify asbuton were 5/20 grain, premium, texapon, HCl, and aquades. Solid phase was the mixture asbuton 5/20 grain and premium with 3 minutes mixing time. Liquid phase consisted texapon, HCl and aquades. The aging process was done after solid phase mixing process in order to reaction and tie of solid phase mixed become more optimal for high solubility level of asphalt production. Aging variable time were 30, 60, 90, 120, and 150 minutes. Solid and liquid phase was mixed for emulsify asbuton production, then extracted for 25 minutes. Solubility level of asphalt, water level, and asphalt characteristic was tested at extraction result of emulsify asbuton with most optimum ashphal level. The result of analysis tested data asphalt solubility level at extract asbuton resulted 94.77% on 120 minutes aging variable time. Water level test resulted water content reduction on emulsify asbuton more long time on occurring of aging solid phase. Examination of asphalt characteristic at extraction result of emulsify asbuton with optimum asphalt solubility level, obtain specimen that have rigid and strong texture in order that examination result have not sufficient ductility and penetration value.

  18. Rapid and simple solid-phase esterification of sialic acid residues for quantitative glycomics by mass spectrometry.

    Miura, Yoshiaki; Shinohara, Yasuro; Furukawa, Jun-ichi; Nagahori, Noriko; Nishimura, Shin-Ichiro


    A rapid and quantitative method for solid-phase methyl esterification of carboxy groups of various sialylated oligosaccharides has been established. The method employed a triazene derivative, 3-methyl-1-p-tolyltriazene, for facile derivatization of oligosaccharides immobilized onto general solid supports such as Affi-Gel Hz and gold colloidal nanoparticles in a multiwell plate. The workflow protocol was optimized for the solid-phase processing of captured sialylated/unsialylated oligosaccharides separated from crude sample mixtures by chemical ligation. From tryptic and/or PNGase F-digest mixtures of glycoproteins, purification by chemoselective immobilization, esterification and recovery were achieved in the same well of the filter plate within three hours when used in conjunction with "glycoblotting technology" (S.-I. Nishimura, K. Niikura, M. Kurogochi, T. Matsushita, M. Fumoto, H. Hinou, R. Kamitani, H. Nakagawa, K. Deguchi, N. Miura, K. Monde, H. Kondo, High-throughput protein glycomics: Combined use of chemoselective glycoblotting and MALDI-TOF/TOF mass spectrometry: Angew. Chem. 2005, 117, 93-98; Angew. Chem. Int. Ed. 2005, 44, 91-96). The recovered materials were directly applicable to subsequent characterization by mass spectrometric techniques such as MALDI-TOF for large-scale glycomics of both neutral and sialylated oligosaccharides. On-bead/on-gold nanoparticle derivatization of glycans containing sialic acids allowed rapid and quantitative glycoform profiling by MALDI-TOF MS with reflector and positive ion mode. In addition to its simplicity and speed, the method eliminates the use of unfavorable halogenated solvents such as chloroform and dichloromethane or volatile solvents such as diethyl ether and hexane, resulting in a practical and green chemical method for automated robotic adaptation.

  19. Direct molecular dynamics simulation of liquid-solid phase equilibria for two-component plasmas.

    Schneider, A S; Hughto, J; Horowitz, C J; Berry, D K


    We determine the liquid-solid phase diagram for carbon-oxygen and oxygen-selenium plasma mixtures using two-phase molecular dynamics simulations. We identify liquid, solid, and interface regions using a bond angle metric. To study finite-size effects, we perform 27,648- and 55,296-ion simulations. To help monitor nonequilibrium effects, we calculate diffusion constants D(i). For the carbon-oxygen system we find that D(O) for oxygen ions in the solid is much smaller than D(C) for carbon ions and that both diffusion constants are 80 or more times smaller than diffusion constants in the liquid phase. There is excellent agreement between our carbon-oxygen phase diagram and that predicted by Medin and Cumming. This suggests that errors from finite-size and nonequilibrium effects are small and that the carbon-oxygen phase diagram is now accurately known. The oxygen-selenium system is a simple two-component model for more complex rapid proton capture nucleosynthesis ash compositions for an accreting neutron star. Diffusion of oxygen, in a predominantly selenium crystal, is remarkably fast, comparable to diffusion in the liquid phase. We find a somewhat lower melting temperature for the oxygen-selenium system than that predicted by Medin and Cumming. This is probably because of electron screening effects.

  20. Solid-Phase Organic Synthesis and Catalysis: Some Recent Strategies Using Alumina, Silica, and Polyionic Resins

    Basudeb Basu


    Full Text Available Solid-phase organic synthesis (SPOS and catalysis have gained impetus after the seminal discovery of Merrifield’s solid-phase peptide synthesis and also because of wide applicability in combinatorial and high throughput chemistry. A large number of organic, inorganic, or organic-inorganic hybrid materials have been employed as polymeric solid supports to promote or catalyze various organic reactions. This review article provides a concise account on our approaches involving the use of (i alumina or silica, either having doped with metal salts or directly, and (ii polyionic resins to either promote various organic reactions or to immobilize reagents/metal catalysts for subsequent use in hydrogenation and cross-coupling reactions. The reaction parameters, scopes, and limitations, particularly in the context of green chemistry, have been highlighted with pertinent approaches by other groups.

  1. Advances in automatic, manual and microwave-assisted solid-phase peptide synthesis.

    Sabatino, Giuseppina; Papini, Anna M


    Solid-phase strategies speed up the production of both short- and long-sequence peptides compared with solution methodologies. Therefore, solid-phase peptide synthesis (SPPS), proposed by Merrifield in the early 1960s, contributed to the 'Peptide Revolution' in the fields of diagnostics, and drug and vaccine development. Since then, peptide chemistry research has aimed to optimize these synthetic procedures, focusing on areas such as amide bond formation (the coupling step), solid supports and automation. Particular attention was devoted to the environmental impact of SPPS: the requirement for large amounts of organic solvents meant high costs for industrial peptide manufacturing that needed to be reduced. SPPS, alone or in hybrid technologies, has become strategic for the production of peptides as active pharmaceutical ingredients on a commercial scale.

  2. Soxhlet-assisted matrix solid phase dispersion to extract flavonoids from rape (Brassica campestris) bee pollen.

    Ma, Shuangqin; Tu, Xijuan; Dong, Jiangtao; Long, Peng; Yang, Wenchao; Miao, Xiaoqing; Chen, Wenbin; Wu, Zhenhong


    Soxhlet-assisted matrix solid phase dispersion (SA-MSPD) method was developed to extract flavonoids from rape (Brassica campestris) bee pollen. Extraction parameters including the extraction solvent, the extraction time, and the solid support conditions were investigated and optimized. The best extraction yields were obtained using ethanol as the extraction solvent, silica gel as the solid support with 1:2 samples to solid support ratio, and the extraction time of one hour. Comparing with the conventional solvent extraction and Soxhlet method, our results show that SA-MSPD method is a more effective technique with clean-up ability. In the test of six different samples of rape bee pollen, the extracted content of flavonoids was close to 10mg/g. The present work provided a simple and effective method for extracting flavonoids from rape bee pollen, and it could be applied in the studies of other kinds of bee pollen.

  3. Understanding processing-induced phase transformations in erythromycin-PEG 6000 solid dispersions

    Mirza, Sabiruddin; Heinämäki, Jyrki; Miroshnyk, Inna


    Since the quality and performance of a pharmaceutical solid formulation depend on solid state of the drug and excipients, a thorough investigation of potential processing-induced transformations (PITs) of the ingredients is required. In this study, the physical phenomena taking place during...... formulation of erythromycin (EM) dihydrate solid dispersions with polyethylene glycol (PEG) 6000 by melting were investigated. PITs were monitored in situ using variable temperature X-ray powder diffraction (VT-XRPD), differential scanning calorimetry (DSC), and hot-stage microscopy (HSM). Possible...... intermolecular interactions between the drug and polymer in the solid state were further studied by Fourier transform infrared (FTIR) spectroscopy. While in the absence of PEG the dehydration was the only transformation observed, hot-melt processing with the polymer caused the drug to undergo multiple phase...

  4. Ni coarsening in the three-phase solid oxide fuel cell anode - a phase-field simulation study

    Chen, Hsun-Yi; Cronin, J Scott; Wilson, James R; Barnett, Scott A; Thornton, Katsuyo


    Ni coarsening in Ni-yttria stabilized zirconia (YSZ) solid oxide fuel cell anodes is considered a major reason for anode degradation. We present a predictive, quantative modeling framework based on the phase-field approach to systematically examine coarsening kinetics in such anodes. The initial structures for simulations are experimentally acquired functional layers of anodes. Sample size effects and error analysis of contact angles are examined. Three phase boundary (TPB) lengths and Ni surface areas are quantatively identified on the basis of the active, dead-end, and isolated phase clusters throughout coarsening. Tortuosity evolution of the pores is also investigated. We find that phase clusters with larger characteristic length evolve slower than those with smaller length scales. As a result, coarsening has small positive effects on transport, and impacts less on the active Ni surface area than the total counter part. TPBs, however, are found to be sensitive to local morphological features and are only i...

  5. Indirect solid-phase immunosorbent assay for detection of arenavirus antigens and antibodies

    Ivanov, A.P.; Rezapkin, G.V.; Dzagurova, T.K.; Tkachenko, E.A. (Institute of Poliomyelitis anU Viral Encephalities of the U.S.S.R. Academy of Medical Sciences, Moscow)


    Indirect enzyme-linked immunosorbent assay (ELISA) and solid phase radioimmunoassay (SPRIA) using either enti-human or anti-mouse IgG labelled with horseradish peroxidase and /sup 125/I, respectively, were developed for the detection of Junin, Machupo, Tacaribe, Amapari, Tamiami, Lassa and LCM arenaviruses. Both methods allow high sensitivity detection of arenavirus antigens and antibodies.

  6. Solid-phase synthesis of an apoptosis-inducing tetrapeptide mimicking the Smac protein

    Le Quement, Sebastian Thordal; Ishøy, Mette; Petersen, Mette Terp;


    An approach for the solid-phase synthesis of apoptosis-inducing Smac peptidomimetics is presented. Using a Rink linker strategy, tetrapeptides mimicking the N-4-terminal residue of the Smac protein [(N-Me)AVPF sequence] were synthesized on PEGA resin in excellent purities and yields. Following tw...

  7. Detection and specifity of class specific antibodies to whole bacteria cells using a solid phase radioimmunoassay

    Czerkinsky, C.; Rees, A.S.; Bergimeier, L.A.; Challacombe, S.J. (Guy' s Hospital Medical and Dental Schools, London (UK))


    A solid phase radioimmunoassay has been developed which can be used for the detection of isotype specific antibodies to whole bacteria and other particulate antigens, and is applicable to a variety of species. Bacteria are bound to the solid phase by the use either of antibodies, or of methyl glyoxal. Both methods result in a sensitive and reproducible assay, and bacteria do not appear to desorb from the solid phase. The specificity of antibodies to whole bacteria was examined by absorption of antisera with various species of bacteria and retesting, or by determining the binding of antisera to various bacteria bound to the solid phase. Both methods revealed specificity for the bacteria examined. Inhibition studies showed that antibodies to Streptococcus mutans whole cells could be inhibited by purified cell surface antigens glucosyltransferase and antigen I/II, but only minimally by lipoteichoic acid, c polysaccharide or dextran. In murine antisera antibodies of the IgG, IgM, and IgA classes could be detected at amounts of less than 1 ng/ml.

  8. New method for the preparation of solid-phase bound isocyanocarboxylic acids and Ugi reactions therewith

    Henkel, Bernd; Sax, Michael; Dömling, Alexander


    A novel method of synthesizing solid-phase bound isocyanocarboxylic acids is reported. The potassium salts of four different isocyanocarboxylic acids are coupled onto a brominated resin in DMF in good yields. 32 Ugi reactions were performed using these resins and 24 products were obtained in good to

  9. A Discovery-Oriented Approach to Solid-Phase Peptide Synthesis

    Bockman, Matthew R.; Miedema, Christopher J.; Brennan, Brian B.


    In this discovery-oriented laboratory experiment, students use solid-phase synthesis techniques to construct a dipeptide containing an unknown amino acid. Following synthesis and cleavage from the polymeric support, electrospray ionization-mass spectrometry is employed to identify the unknown amino acid that was used in the peptide coupling. This…

  10. Solid Phase Extraction: Applications to the Chromatographic Analysis of Vegetable Oils and Fats

    Panagiotopoulout, P. M.; Tsimidou, M.


    Applications of solid-phase extraction for the isolation of certain lipid classes prior to chromatographic analysis are given. More information was found for sterols and related compounds, polar phenols and contaminants such as polycyclic aromatic hydrocarbons. Detailed analytical protocols are presented and discussed in many cases. (Author) 120 refs.

  11. Comparison of solid and liquid-phase bioassays using ecoscores to assess contaminated soils

    Lors, Christine [Universite Lille Nord de France, 1bis rue Georges Lefevre, 59044 Lille Cedex (France); Ecole des Mines de Douai, LGCgE-MPE-GCE, 941 rue Charles-Bourseul, 59500 Douai (France); Centre National de Recherche sur les Sites et Sols Pollues, 930 Boulevard Lahure, BP 537, 59505 Douai Cedex (France); Ponge, Jean-Francois, E-mail: [Museum National d' Histoire Naturelle, Departement Ecologie et Gestion de la Biodiversite, CNRS UMR 7179, 4 Avenue du Petit-Chateau, 91800 Brunoy (France); Martinez Aldaya, Maite [Museum National d' Histoire Naturelle, Departement Ecologie et Gestion de la Biodiversite, CNRS UMR 7179, 4 Avenue du Petit-Chateau, 91800 Brunoy (France); Damidot, Denis [Universite Lille Nord de France, 1bis rue Georges Lefevre, 59044 Lille Cedex (France); Ecole des Mines de Douai, LGCgE-MPE-GCE, 941 rue Charles-Bourseul, 59500 Douai (France)


    Bioassays on aqueous and solid phases of contaminated soils were compared, belonging to a wide array of trophic and response levels and using ecoscores for evaluating ecotoxicological and genotoxicological endpoints. The method was applied to four coke factory soils contaminated mainly with PAHs, but also to a lesser extent by heavy metals and cyanides. Aquatic bioassays do not differ from terrestrial bioassays when scaling soils according to toxicity but they are complementary from the viewpoint of ecological relevance. Both aquatic and terrestrial endpoints are strongly correlated with concentrations of 3-ring PAHs. This evaluation procedure allows us to propose a cost-effective battery which embraces a wide array of test organisms and response levels: it includes two rapid bioassays (Microtox) and springtail avoidance), a micronucleus test and three bioassays of a longer duration (algal growth, lettuce germination and springtail reproduction). This battery can be recommended for a cost-effective assessment of polluted/remediated soils. - Highlights: > Comparison of liquid- and solid-phase bioassays on contaminated soils, using ecoscores. > Complementarity of liquid- and solid-phase bioassays for the evaluation of environmental hazards. > Proposal for a restricted battery of 5 most sensitive tests. > Use of this restricted battery for a cost-effective assessment of polluted/remediated soils. - Aqueous and solid phases of contaminated soils give similar results in terms of toxicity but are complementary for the evaluation of environmental hazards by ecoscores.

  12. Solid-phase synthesis of polyfunctional polylysine dendrons using aldehyde linkers

    Svenssen, Daniel K.; Mirsharghi, Sahar; Boas, Ulrik


    A straightforward method for the solid-phase synthesis of C-terminally modified polylysine dendrons has been developed by applying bisalkoxybenzaldehyde and trisalkoxybenzaldehyde linkers. The method has been used for the synthesis of polylysine dendrons with a variety of C-terminal ‘tail groups’...

  13. Micro versus macro solid phase extraction for monitoring water contaminants: a preliminary study using trihalomethanes.

    Alexandrou, Lydon D; Spencer, Michelle J S; Morrison, Paul D; Meehan, Barry J; Jones, Oliver A H


    Solid phase extraction is one of the most commonly used pre-concentration and cleanup steps in environmental science. However, traditional methods need electrically powered pumps, can use large volumes of solvent (if multiple samples are run), and require several hours to filter a sample. Additionally, if the cartridge is open to the air volatile compounds may be lost and sample integrity compromised. In contrast, micro cartridge based solid phase extraction can be completed in less than 2 min by hand, uses only microlitres of solvent and provides comparable concentration factors to established methods. It is also an enclosed system so volatile components are not lost. The sample can also be eluted directly into a detector (e.g. a mass spectrometer) if required. However, the technology is new and has not been much used for environmental analysis. In this study we compare traditional (macro) and the new micro solid phase extraction for the analysis of four common volatile trihalomethanes (trichloromethane, bromodichloromethane, dibromochloromethane and tribromomethane). The results demonstrate that micro solid phase extraction is faster and cheaper than traditional methods with similar recovery rates for the target compounds. This method shows potential for further development in a range of applications.

  14. Solid-phase oligosaccharide synthesis with tris(alkoxy)benzyl amine (BAL) safety-catch anchoring

    Tolborg, Jakob Fjord; Jensen, Knud Jørgen


    A tris(alkoxy)benzylamine (BAL) handle strategy was developed for safety-catch anchoring of D-glucosamine derivatives in solid-phase synthesis of oligosaccharides; the linkage between the BAL handle and the amine proved stable to conc. TFA and Lewis acids, but after N-acylation the amide could...

  15. A Long Chain Alcohol as Support in Solid Phase Organic Synthesis

    Nurlela, Yeni; Minnaard, Adrian J.; Achmad, Sadijah; Wahyuningrum, Deana


    The solid phase synthesis is a method by which organic compound synthesis are performed on a support. With this method, the purification can be carried out easily by simple filtration and washing procedures. Long-chain alcohol (C-100 alcohol) can be used as a support because of its insolubility in o

  16. A Solid Phase Synthesis of Chalcones by Claisen-Schmidt Condensations


    In order to accelerate the development of relatively inexpensive antimalarials that are effective against chloroquine-resistant strains of Plasmodium falclparum, a methodology for the solid phase synthesis of chalcone (l, 3-diphenyl-2-propen-l-one) analogues in reasonably high yields has been developed.

  17. Development of a Solid Phase Extraction Method for Agricultural Pesticides in Large-Volume Water Samples

    An analytical method using solid phase extraction (SPE) and analysis by gas chromatography/mass spectrometry (GC/MS) was developed for the trace determination of a variety of agricultural pesticides and selected transformation products in large-volume high-elevation lake water sa...

  18. Microwave-assisted solid-phase Ugi four-component condensations

    Nielsen, John


    An 18-member library was constructed from 2 isocyanides, 3 aldehydes and 3 carboxylic acids via microwave-assisted solid-phase Ugi reactions on TentaGel S RAM. Products of high purity were obtained in moderate to excellent yields after reaction times of 5 minutes or less (irradiation at 60W). (C...

  19. Determination of lidocaine in plasma by direct solid-phase microextraction combined with gas chromatography

    Koster, EHM; Wemes, C; Morsink, JB; de Jong, GJ


    Direct-immersion solid-phase microextraction (SPME) has been used to extract the local anesthetic lidocaine from human plasma. A simplified model shows the relationship between the total amount of drug in plasma and the amount of drug extracted. The model takes into account that the drug participate

  20. Side-chain-anchored N(alpha)-Fmoc-Tyr-OPfp for bidirectional solid-phase synthesis

    Olsen, Christian A; Jørgensen, Malene; Hansen, Steen H;


    [reaction: see text] A mild resin-immobilization strategy employing a readily prepared trityl bromide resin for anchoring building blocks via a phenol group has been developed. With N(alpha)-Fmoc-Tyr-OPfp as a starter building block, it was possible to prepare asymmetrically substituted hybrids o...... of spider- and wasp-type polyamine toxins using solid-phase peptide synthesis conditions....

  1. Speciation analysis of aqueous nanoparticulate diclofenac complexes by solid-phase microextraction

    Zielinska, K.; Leeuwen, van H.P.; Thibault, S.; Town, R.M.


    The dynamic sorption of an organic compound by nanoparticles (NPs) is analyzed by solid-phase microextraction (SPME) for the example case of the pharmaceutical diclofenac in dispersions of impermeable (silica, SiO(2)) and permeable (bovine serum albumin, BSA) NPs. It is shown that only the protonate

  2. Solid-phase synthesis of succinylhydroxamate peptides : Functionalized matrix metalloproteinase inhibitors

    Leeuwenburgh, MA; Geurink, PP; Klein, T; Kauffman, HF; van der Marel, GA; Bischoff, R; Overkleeft, HS


    A novel solid-phase synthesis strategy toward succinylhydroxamate peptides, using an appropriately protected hydroxamate building block, is described. Rapid and efficient access is gained to amine-functionalized peptides, which can be decorated with, for instance, a fluorescent label. In addition, w

  3. A convenient procedure for the solid-phase synthesis of hydroxamic acids on PEGA resins

    Nandurkar, Nitin Subhash; Petersen, Rico; Qvortrup, Katrine


    An efficient method for the solid-phase synthesis of hydroxamic acids is described. The method comprises the nucleophilic displacement of esters immobilized on PEGA resins with hydroxylamine/sodium hydroxide in isopropanol. The hydroxyaminolysis protocol is compatible with a broad range of PEGA-s...

  4. A Rapid Solid-phase Synthesis to Soluble Oligothiophene Molecular Wires


    A novel method for the preparation of oligothiophene molecular wires is described via a bi-directional solid-phase synthesis. Using an alternating sequence of bromination and Stille coupling reactions, oligomers were obtained up to the heptamer in excellent yield and purity.

  5. Linkers, resins, and general procedures for solid-phase peptide synthesis

    Shelton, Anne Pernille Tofteng; Jensen, Knud Jørgen


    and linkers for solid-phase synthesis is a key parameter for successful peptide synthesis. This chapter provides an overview of the most common and useful resins and linkers for the synthesis of peptides with C-terminal amides, carboxylic acids, and more. The chapter finishes with robust protocols for general...

  6. Total synthesis of human urotension-Ⅱ by microwave-assisted solid phase method


    Human urotension-Ⅱ was synthesized efficiently on Wang resin under microwave irradiation using Fmoc/tBu orthogonal protection strategy. Disulphide bridge was formed on solid phase with the irradiation of microwave, then the whole peptide was cleaved from the resin. The purity of crude peptide cyclized under microwave irradiation was higher than that under room temperature.

  7. Electrocatalytic phenomena in gas phase reactions in solid electrolyte electrochemical cells

    Gellings, P.J.; Koopmans, H.J.A.; Burggraaf, A.J.


    The recent literature on electrocatalysis and electrocatalytic phenomena occurring in gas phase reactions on solid, oxygen conducting electrolytes is reviewed. In this field there are a number of different subjects which are treated separately. These are: the use of electrochemical methods to study

  8. Solid-phase Synthesis of a Novel Kind of Hydroxylated Heterocyclic Ketene Aminals

    Tao PENG; Chu Yi YU; Zhi Tang HUANG


    An efficient solid-phase synthesis method for novel heterocyclic ketene aminals containing a hydroxyl group has been developed. The loading of the substrate on the resin through the hydroxyl group and the protection of the amine by the Schiff base were the key steps in the synthesis.

  9. Fibers coated with molecularly imprinted polymers for solid-phase microextraction

    Koster, E.H M; Crescenzi, C; den Hoedt, W; Ensing, K; de Jong, G.J.


    The simplicity and flexibility of solid-phase microextraction have been combined with the selectivity of molecularly imprinted polymers (MIPs), Silica fibers were coated reproducible with a 75-mum layer of methacrylate polymer either nonimprinted or imprinted with clenbuterol to compare their extrac

  10. Dynamic speciation analysis of atrazine in aqueous latex nanoparticle dispersions using solid phase microextraction (SPME)

    Benhabib, K.; Town, R.M.; Leeuwen, van H.P.


    Solid phase microextraction (SPME) is applied in the dynamic speciation analysis of the pesticide atrazine in an aqueous medium containing sorbing latex nanoparticles. It is found that the overall rate of extraction of the analyte is faster than in the absence of nanoparticles and governed by the

  11. Investigating the Retention Mechanisms of Liquid Chromatography Using Solid-Phase Extraction Cartridges

    O'Donnell, Mary E.; Musial, Beata A.; Bretz, Stacey Lowery; Danielson, Neil D.; Ca, Diep


    Liquid chromatography (LC) experiments for the undergraduate analytical laboratory course often illustrate the application of reversed-phase LC to solve a separation problem, but rarely compare LC retention mechanisms. In addition, a high-performance liquid chromatography instrument may be beyond what some small colleges can purchase. Solid-phase…

  12. Solid-Phase Synthesis of Smac Peptidomimetics Incorporating Triazoloprolines and Biarylalanines

    Le Quement, Sebastian T.; Ishoey, Mette; Petersen, Mette T.;


    -Me)AVPF sequence, peptides incorporating triazoloprolines and biarylalanines were synthesized by means of Cu(I)-catalyzed azide–alkyne cycloaddition and Pd-catalyzed Suzuki cross-coupling reactions. Solid-phase procedures were optimized to high efficiency, thus accessing all products in excellent crude purities...

  13. Highly Selective Liquid-Phase Benzylation of Anisole with Solid-Acid Zeolite Catalysts

    Poreddy, Raju; Shunmugavel, Saravanamurugan; Riisager, Anders


    Zeolites were evaluated as solid acid catalysts for the liquid-phase benzylation of anisole with benzyl alcohol, benzyl bromide, and benzyl chloride at 80 °C. Among the examined zeolites, H-mordenite-10 (H-MOR-10) demonstrated particular high activity (>99 %) and excellent selectivity (>96...

  14. Rapid and convenient semi-automated microwave-assisted solid-phase synthesis of arylopeptoids

    Rasmussen, Jakob Ewald; Boccia, Marcello Massimo; Nielsen, John


    A facile and expedient route to the synthesis of arylopeptoid oligomers (N-alkylated aminomethyl benz-amides) using semi-automated microwave-assisted solid-phase synthesis is presented. The synthesis was optimized for the incorporation of side chains derived from sterically hindered or unreactive...

  15. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: chemical characterization of the products

    Grgić, Irena; Kitanovski, Zoran; Kroflič, Ana; Čusak, Alen


    One of the largest primary sources of organic aerosol in the atmosphere is biomass burning (BB) (Laskin et al. 2009); in Europe its contribution to annual mean of PM10 is between 3 and 14 % (Maenhaut et al. 2012). During the process of wood burning many different products are formed via thermal degradation of wood lignin. Hardwood burning produces mainly syringol (2,6-dimetoxyphenol) derivatives, while softwood burning exclusively guaiacol (2-methoxyphenol) and its derivatives. Taking into account physical properties of methoxyphenols only, their concentrations in atmospheric waters might be underestimated. So, their aqueous phase reactions can be an additional source of SOA, especially in regions under significant influence of wood combustion. An important class of compounds formed during physical and chemical aging of the primary BBA in the atmosphere is nitrocatechols, known as strong absorbers of UV and Vis light (Claeys et al. 2012). Very recently, methyl-nitrocatechols were proposed as suitable markers for highly oxidized secondary BBA (Iinuma et al. 2010, Kitanovski et al. 2012). In the present work, the formation of SOA through aqueous phase photooxidation and nitration of guaiacol was examined. The key objective was to chemically characterize the main low-volatility products and further to check their possible presence in the urban atmospheric aerosols. The aqueous phase reactions were performed in a thermostated reactor under simulated sunlight in the presence of H2O2 and nitrite. Guaiacol reaction products were first concentrated by solid-phase extraction (SPE) and then subjected to semi-preparative liquid chromatography.The main product compounds were fractionated and isolated as pure solids and their structure was further elucidated by using nuclear magnetic resonance spectroscopy (1H, 13C and 2D NMR) and direct infusion negative ion electro-spray ionization tandem mass spectrometry (( )ESI-MS/MS). The main photonitration products of guaiacol (4

  16. Coupling among three chemical oscillators: Synchronization, phase death, and frustration

    Yoshimoto, Minoru; Yoshikawa, Kenichi; Mori, Yoshihito


    Various modes in three coupled chemical oscillators in a triangular arrangement were observed. As a well-defined nonlinear oscillator, the Belousov-Zhabotinsky reaction was studied in a continuous-flow stirred tank reactor (CSTR). Coupling among CSTR's was performed by mass exchange. The coupling strength was quantitatively controlled by changing the flow rate of reacting solutions among the three CSTR's using peristaltic pumps between each pair of the reactors. As a key parameter to control the model of coupling, we changed the symmetry of the interaction between the oscillators. In the case of the symmetric coupling, a quasiperiodic state or a biperiodic mode, an all-death mode and two kinds of synchronized modes appeared, depending on the coupling strength. On the other hand, under the asymmetric coupling, a quasiperiodic state or a biperiodic mode, an all death mode and four kinds of synchronized modes appeared. Those modes have been discussed in relation to the idea of ``frustration'' in the Ising spin system, where the three-phase mode appears as a transition from the Ising spin system to the XY spin system.

  17. Black Hole Phase Transitions and the Chemical Potential

    Maity, Reevu; Sarkar, Tapobrata


    In the context of extended phase space thermodynamics and the AdS-CFT correspondence, we consider the chemical potential ($\\mu$) dual to the number of colours ($N$) of the boundary gauge theory, in the grand canonical ensemble. By appropriately defining $\\mu$ via densities of thermodynamic quantities, we show that it changes sign precisely at the Hawking-Page transition for AdS-Schwarzschild and RN-AdS black holes in five dimensions, signalling the onset of quantum effects at the transition point. Such behaviour is absent for non-rotating black holes in four dimensions. For Kerr-AdS black holes in four and five dimensions, our analysis points to the fact that $\\mu$ can change sign in the stable black hole region, i.e above the Hawking-Page transition temperature, for a range of angular frequencies. We also analyse AdS black holes in five dimensional Gauss-Bonnet gravity, and find similar features for $\\mu$ as in the Kerr-AdS case.

  18. Chemically modified cellulose paper as a thin film microextraction phase.

    Saraji, Mohammad; Farajmand, Bahman


    In this paper, chemically modified cellulose paper was introduced as a novel extracting phase for thin film microextraction (TFME). Different reagents (Octadecyltrichlorosilane, diphenyldichlorosilane, cyclohexyl isocyanate and phenyl isocyanate) were used to modify the cellulose papers. The modified papers were evaluated as a sorbent for the extraction of some synthetic and natural estrogenic hormones (17α-ethynylestradiol, estriol and estradiol) from aqueous samples. Liquid chromatography-fluorescence detection was used for the quantification of the extracted compounds. The cellulose paper modified with phenyl isocyanate showed the best affinity to the target compounds. TEME parameters such as desorption condition, shaking rate, sample ionic strength and extraction time were investigated and optimized. Limit of detections were between 0.05 and 0.23μgL(-1) and relative standard deviations were less than 11.1% under the optimized condition. The calibration curves were obtained in the range of 0.2-100μgL(-1) with a good linearity (r(2)>0.9935). Wastewater, human urine, pool and river water samples were studied as real samples for the evaluation of the method. Relative recoveries were found to be between 75% and 101%.

  19. Determination of aflatoxins in rice samples by ultrasound-assisted matrix solid-phase dispersion.

    Manoochehri, Mahboobeh; Asgharinezhad, Ali Akbar; Safaei, Mahdi


    This work describes the application of ultrasound-assisted matrix solid-phase dispersion as an extraction and sample preparation approach for aflatoxins (B1, B2, G1 and G2) and subsequent determination of them by high-performance liquid chromatography-fluorescence detection. A Box-Behnken design in combination with response surface methodology was used to determine the affecting parameters on the extraction procedure. The influence of different variables including type of dispersing phase, sample-to-dispersing phase ratio, type and quantity of clean-up phase, ultrasonication time, ultrasonication temperature, nature and volume of the elution solvent was investigated in the optimization study. C18, primary-secondary amine (PSA) and acetonitrile were selected as dispersing phase, clean-up phase and elution solvent, respectively. The obtained optimized values were sample-to-dispersing phase ratio of 1 : 1, 60 mg of PSA, 11 min ultrasonication time, 30°C ultrasonication temperature and 4 mL acetonitrile. Under the optimal conditions, the limits of detection were ranged from 0.09 to 0.14 ng g(-1) and the precisions [relative standard deviation (RSD%)] were <8.6%. The recoveries of the matrix solid-phase dispersion process ranged from 78 to 83% with RSD <10% in all cases. Finally, this method was successfully applied to the extraction of trace amounts of aflatoxins in rice samples. © The Author [2014]. Published by Oxford University Press. All rights reserved. For Permissions, please email:

  20. Fluid dynamics of the unsteady two phase processes leading to DDT in granular solid propellants

    Krier, H.; Butler, P. B.; Lembeck, M. F.


    Deflagration to Detonation (DDT) was predicted to occur in porous beds of high-energy solid propellants by solving the unsteady fluid mechanical convective heat transfer from hot gas products, obtained from the rapid burning at high pressures, provides the impetus to develop a narrow combustion zone and a resulting strong shock. A parametric study clearly indicates that DDT occurs only when a combination of the solids loading fraction, the burning rate constants, the propellant chemical energy, and the particle size provide for critical energy and gas release to support a detonation wave. Predictions for the run-up length to detonation as a function of these parameters are presented.