Investigation of scale inhibition mechanisms based on the effect of scale inhibitor on calcium carbonate crystal forms

To probe the scale inhibition mechanisms,calcium carbonate scale occurring before and after the ad- dition of scale inhibitors was collected.The results from scale SEM confirm that,without scale inhibitor, calcium carbonate scale shows rhombohedron and hexagon,which are the characteristic feathers of calcite.After addition of inhibitors,morphology of scale is changed,and the more efficient the scale inhibitor is,the more greatly the morphology is modified.To elucidate the scale constitute,they were further analyzed by FT-IR,XRD.Besides calcite,vaterite and aragonite occur in calcium carbonate scale after addition of inhibitors,and the higher scale inhibition efficiency is,the more vaterite presents in scale.It can be concluded that the alteration of morphology is ascribed to the change of crystal form. There are three stages in the crystallizing process including occurrence and disappearing of unstable phase,occurrence and disappearing of metastable phase,development of stable phase.Without scale inhibitors,metastable phases usually transform into stable phase,thus the main constitute of formed scale is calcite.When scale inhibitors are added,both formation and transformation of metastable phases are inhibited,which results in the occurrence of aragonite and vaterite.From the fact that more vaterite presents in scale with a more efficient scale inhibitor added,we can see that the function of scale inhibitor is realized mainly by controlling the crystallizing process at the second stage.     

Revising the proton affinity scale of the naturally occurring α-amino acids

The proton affinities (PA) of the 20 naturally occurring alpha-amino acids (AA) have been determined computationally by means of density functional theory (DFT) and high-level G2(MP2) calculations. These theoretical PAs, together with data that have appeared since 1997 in the literature, are used to validate the most reasonable currently available PA scale for AAs (Harrison, A. G. Mass Spectrom. Rev. 1997, 16, 201-217.). Significant scatter is observed for the PAs of Ser, Asp, Phe, Asn, Met, Pro, Gln, Glu, Trp, His, Lys, and Arg, many of which have a basic side-chain functionality. Critical review of the available data leads to new consensus PAs for Asn, Gln, Met, and Arg of 222.4, 230.5, 223.7, and 250.2 kcal/mol, respectively.     

What is the best definition of a liquid cluster at the molecular scale?

We investigate the ability of different cluster definitions to serve as a good reaction coordinate in molecular simulations of nucleation. In particular, the most commonly used Stillinger criterion [J. Chem. Phys. 38, 1486 (1963)] is compared with the cluster definition introduced by ten Wolde and Frenkel [J. Chem. Phys. 109, 9901 (1998)]. The accuracy of these two different cluster definitions is tested by using molecular dynamics to study the vapor-liquid nucleation of Lennard-Jones argon as a model system. We are able to compare the size of the critical cluster identified by each cluster definition with a completely model-independent value provided by the nucleation theorem, aided by a recently introduced method that accurately extracts the location of the transition state directly from the kinetics. It is found that the Stillinger definition strongly overestimates the size of small molecular clusters by up to a factor of 2. A simple change of the Stillinger radius is unable to rectify this deficiency. On the contrary, the ten Wolde-Frenkel definition, while being only slightly more elaborate than a simple Stillinger criterion, is remarkably successful in identifying the correct molecular excess of the small clusters if the parameters are chosen adequately. The method described here can also be generalized to identify a proper reaction coordinate in other activated processes.     

Large scale synthesis of oligoribonucleotides on PEG by the phosphite triester approach

Large scale synthesis of oligoribonucleotides has been successfully performed on PEG support by the phosphoramidite approach using t-butyldimethylsilyl to protect the 2'-hydroxyl group of ribonucleoside. By means of this procedure, the dodecamer r(AGUGGUCUUUGU) was synthesized in 98.1% average coupling yield, and 55 mg pure product was obtained from one gram of functionalized PEG.     

Large‐scale Experimental Study on the Effects of Flooring Materials on Combustion Behavior of Thermoplastics

The effects of flooring materials on the combustion behavior of thermoplastics is investigated. Based on the ISO 9705 fire test setup, an experimental rig was designed. Full‐scale experiments of PP combustion were carried out using five flooring boards, namely gypsum, steel, wood, ceramic tile and PVC. The experimental results indicate that the flooring boards play an important role in the heat release rates of typical thermoplastics combustion. Specifically, the time for the sharp increase of heat release rate is generally later for the flooring boards with larger thermal conductivity, except for the case of PVC. Preliminary analyses suggest that the reason for the exception of PVC is the expansion and carbonization of PVC at high temperature. In addition, experimental results also show that the corresponding peak heat release rate of thermoplastics combustion would be generally smaller for the flooring board with a larger thermal mass, except for the case of gypsum. The primary cause for the exception of gypsum may be the heat absorption by the crystal water released from the gypsum during the burning of hot pool oil.     

Does the nanometre scale topography of titanium influence protein adsorption and cell proliferation?

To investigate the influence of titanium films with nanometre scale topography on protein adsorption and cell growth, three different model titanium films were utilized in the present study. The chemical compositions, surface topographies and wettability were investigated by using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water contact angle measurement, respectively. The films share the same surface chemistry but exhibit different topographies on a nanometre scale. Thus, they act as model systems for biological studies regarding surface topography effects. The films were obtained by varying the deposition rate and the film thickness, respectively. These films displayed nanometre scale surface roughness (root mean square roughness, R_rms) from 2 to 21 nm over areas of 50 μm × 50 μm, with different grain sizes at their surfaces. Albumin and fibrinogen adsorption on these model titanium films were performed in this study. Bicinchoninic acid assay was employed to determine the amount of adsorbed protein on titanium film surfaces. No statistically significant differences, however, were observed for either albumin or fibrinogen adsorption between the different groups of titanium films. No statistically significant influence of surface roughness on osteoblast proliferation and cell viability was detected in the present study.     

Gram scale synthesis of the C(1)–C(9) fragment of amphidinolide C

An allylic cis-epoxide prepared by Sharpless asymmetric epoxidation was transformed in nine steps and 41% overall yield to the cyclization precursor 4 via a key one carbon homologation. Cobalt-catalyzed aerobic oxidative cyclization of 4 gave the trans-THF in 94% yield at gram scale. Subsequent manipulations, including a Still–Gennari olefination, Sharpless asymmetric dihydroxylation, Corey–Fuchs alkynylation, and Kazmaier hydrostannylation provided the fully functionalized C(1)–C(9) fragment 2 suitable for cross-coupling. The sequence is readily scalable and provides gram quantities of 2.     

ESR studies on the solvation of perfluoro-n-alkyl t-butyl nitroxides — A new scale for electronegativity of perfluoro-n-alkyl groups

Pentafluoroethyl t-butyl nitroxides (3) have been generated by the use of electron-transfer reactions of O-benzoyl-N-t-butylhydroxylamine (1) and pentafluoropropanoyl peroxide (2) in F113 (CFCl₂CF₂Cl) solution. ESR measurement of a_N and a_F ^β values for 3 in 11 solvents have been carried out at 17 ± 2 °C. The a_N values for 3 in 10 aprotic solvents (but not in i-PrOH) show a linear correlation with the cybotactic solvent parameter E_T, i.e. a_N = 3.02 × 10⁻² E_T ± 10.46. Together with the similar correlation analysis for trifluoromethyl t-butyl nitroxide (4) and heptafluoropropyl t-butyl nitroxide (5) reported previously, the physical significance for the slope, slope × E_T, the extrapolated intercept on the a_N axis, is linked to the sensitivity of the nitroxide toward solvation, the magnitude of the overall solution effect on the a_N values, and the intrinsic a_N values of 3, 4, 5 in the ideal gaseous state, respectively. The intercepts on the a_N axis, 11.34 G, 11.56 G and 11.37 G may serve a new measure of electronegativity for CF₃, C₂F₅ and n-C₃F₇, respectively. The plots of a_N versus noncybotactic solvent constants, such as dipolar moment (μ) and dielectric constant (ɛ), all show random cases.     

α-Scale decoupling of the mechanical relaxation and diverging shear wave propagation length scale in triphenylphosphite

We have performed depolarized impulsive stimulated scattering experiments to observe shear acoustic phonons in supercooled triphenylphosphite (TPP) from ~10-500 MHz. These measurements, in tandem with previously performed longitudinal and shear measurements, permit further analyses of the relaxation dynamics of TPP within the framework of the mode coupling theory. Our results provide evidence of α coupling between the shear and longitudinal degrees of freedom up to a decoupling temperature T(c) = 231 K. A lower bound length scale of shear wave propagation in liquids verified the exponent predicted by theory in the vicinity of the decoupling temperature.     

What is the time scale for α-helix nucleation?

Helix formation is an elementary process in protein folding, influencing both the rate and mechanism of the global folding reaction. Yet, because helix formation is less cooperative than protein folding, the kinetics are often multiexponential, and the observed relaxation times are not straightforwardly related to the microscopic rates for helix nucleation and elongation. Recent ultrafast spectroscopic measurements on the peptide Ac-WAAAH(+)-NH(2) were best fit by two relaxation modes on the ～0.1-1 ns time scale, (1) apparently much faster than had previously been experimentally inferred for helix nucleation. Here, we use replica-exchange molecular dynamics simulations with an optimized all-atom protein force field (Amber ff03w) and an accurate water model (TIP4P/2005) to study the kinetics of helix formation in this peptide. We calculate temperature-dependent microscopic rate coefficients from the simulations by treating the dynamics between helical states as a Markov process using a recently developed formalism. The fluorescence relaxation curves obtained from simulated temperature jumps are in excellent agreement with the experimentally determined results. We find that the kinetics are multiphasic but can be approximated well by a double-exponential function. The major processes contributing to the relaxation are the shrinking of helical states at the C-terminal end and a faster re-equilibration among coil states. Despite the fast observed relaxation, the helix nucleation time is estimated from our model to be 20-70 ns at 300 K, with a dependence on temperature well described by Arrhenius kinetics.     

Anchor points for the unified Brønsted acidity scale: the rCCC model for the calculation of standard Gibbs energies of proton solvation in eleven representative liquid media

The COSMO cluster-continuum (CCC) solvation model is introduced for the calculation of standard Gibbs solvation energies of protons. The solvation sphere of the proton is divided into an inner proton-solvent cluster with covalent interactions and an outer solvation sphere that interacts electrostatically with the cluster. Thus, the solvation of the proton is divided into two steps that are calculated separately: 1) The interaction of the proton with one or more solvent molecules is calculated in the gas phase with high-level quantum-chemical methods (modified G3 method). 2) The Gibbs solvation energy of the proton-solvent cluster is calculated by using the conductor-like screening model (COSMO). For every solvent, the solvation of the proton in at least two (and up to 11) proton-solvent clusters was calculated. The resulting Gibbs solvation energies of the proton were weighted by using Boltzmann statistics. The model was evaluated for the calculation of Gibbs solvation energies by using experimental data of water, MeCN, and DMSO as a reference. Allowing structural relaxation of the proton-solvent clusters and the use of structurally relaxed Gibbs solvation energies improved the accordance with experimental data especially for larger clusters. This variation is denoted as the relaxed COSMO cluster-continuum (rCCC) model, for which we estimate a 1σ error bar of 10 kJ mol(-1) . Gibbs solvation energies of protons in the following representative solvents were calculated: Water, acetonitrile, sulfur dioxide, dimethyl sulfoxide, benzene, diethyl ether, methylene chloride, 1,2-dichloroethane, sulfuric acid, fluorosulfonic acid, and hydrogen fluoride. The obtained values are absolute chemical standard potentials of the proton (pH=0 in this solvent). They are used to anchor the individual solvent specific acidity (pH) scales to our recently introduced absolute acidity scale.     

Simulation of aerobic landfill in laboratory scale lysimeters — effect of aeration rate

Aeration of municipal landfills contributes to the acceleration of organic matter degradation and to the decrease of pollutant emission into air, water, and soil. Biodegradation of organic matter present in municipal waste, deposited in a landfill, by microorganisms under anaerobic conditions is a slow process. The aim of the study was to carry out simulations of an aerobic landfill in lysimeters, to determine the influence of aeration rate on the degradation of organic matter present in landfills, and to formulate a mathematical model defining the changes of carbon content in leachate and in gas produced. In this work, simulation of aerobic landfill leachate degradation was carried out in laboratory scale lysimeters with the working volume of 15 L. The changes of BOD5, COD, and ammonium nitrogen concentration during aeration were similar for all aeration rates. During aeration, the BOD5 index decreased by 99.9 %, COD decreased by 95.1 %, and ammonium nitrogen concentration by 93 %. The proposed kinetic model defines the processes of organic carbon content changes in simulated leachate and the quantity of carbon dioxide for aerobic landfill simulation quite well.     

Flow in porous media — scale up of multiphase flow

This review will highlight recent developments in methods for scale-up of multi-phase flow in porous media. Scale-up is a necessary step when going from multi-million cell geostatistical models to reservoir simulation models. Multi-phase scale-up methods available include steady state methods as well as dynamic methods, along with recent developments which may remove the need for scale-up as an activity separate from simulation.     

Synthesis and bioassay of all four stereoisomers of (2E,4E)-4,6,10,12-tetramethyl-2,4-tridecadien-7-one, the assignment of the absolute configuration of the sex pheromone of Matsucoccus matsumurae Japanese pine bast scale

A facile enantioselective synthesis of all four stereoisomers of (2E,4E)-4,6,10,12-tetramethyl-2,4-tridecadien-7-one (1) is described. The stereochemistry at 6-C and 10-C of 1 was constructed by using optically active citronellal as starting material and by the asymmetric crotylic metal reaction. In the bioassay and field tests, only la, i.e. (6R,10R)-1 was active. The other three isomers 1b (6S,10R), 1c (6R,10S) and 1d (6S,10S) were inactive. Therefore, the naturally occurring pheromone was assigned as (6K,10R)-1.     

Anionic polymerization of ϵ-caprolactam-lix effect of the ratio of reacting components,of the medium and of the ring size on the initial stage of the anionic polymerization of lactams

Effects of the concentrations and ratio of reacting components and of temperature on the kinetics of reaction of N-propionyllactam (I) with potassium salt of lactam (KL) were studied for derivatives of ϵ-caprolactam, 8-octanelactam and 12-dodecanelactam. For ϵ-caprolactam, the initial rates of propagation, acylation of open-chain amide groups and condensation of growth centres were estimated. At the ratio of the starting components [I]₀/[KL]₀ = 0.5-3, the participation of the polymerization reaction is constant, amounting to ca 45% of the overall consumption of 1. The condensation reaction is 14–36% of the total consumption of I; its initial rate passes through a maximum at [I]₀/[KL]₀ = 2. With increasing permittivity of the medium, the total rate of consumption of I increases; in two media with the same bulk permittivity, however, the rates may differ by as much as one order of magnitude.     

Construction of the Skeleton of Phthalascidin, Mechanism of the Formation of the Key Tricyclic Lactam Intermediate

Phthalascidin is a structurally simplified version of Et-743, which is a potent anti-tumor marine natural product isolated from Ecteinascidia turbinata. Its antiproliferative activity is greater than that of the agents taxol, camptothecin, adriamycin, mitomycin C, cisplatin, bleomycin, and etoposide by 1-3 orders of magnitude. An elegant synthesis of Et-743 and phthalascidin has been reported by E. J. Corey and co-workers1,2. As part of our continuing program, we have also engaged in dev…     

Synthesis of two peptides of α-bungarotoxin and the participation of the amino acid residue Trp-28 of the neurotoxin in the antigenicity of the molecule

Using the method of solid-phase peptide synthesis, two peptides have been synthesized, one of which corresponds to the central ring structure of -bungarotoxin (-BTX), while the second has in position 28 a Gly residue in place of the Trp in the first peptide, and their interrelationship with antitoxin antibodies has been investigated. It has been shown that the amino acid residue Trp-28 of -BTX, which is the contact residue in binding with the acetylcholine receptor, also participates directly in binding with the active centers of antibodies to -BTX.Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 628–631, July–August, 1997.     

Studies of the dissociation and the protonation of TB-chlorosulphophenol

The dissociation constant of each step for TB-chlorosulphophenol has been determined by potentiometric method, and the thermodynamic constants, △G°, △H° and △S°, of the dissociation process have been calculated. The protonation constants were measured by the spectrophotometric method. The pH values of various forms of anions of the chromogenic reagent at their concentrations were also calculated.     

Large scale preparation of (+)- and (−)-endo-norbornenol by enzymatic hydrolysis

A multigram preparation of (+)-(1R,2R,4R)-endo-bicyclo[2.2.1]hept-5-en-2-ol ((+)-2) and its enantlomer (−)−2 with an optical purity of 90% and > 96%, respectively, was accomplished via enantioselective hydrolysis of (±)-5-endo-norbornen-2-ylacetate using lipase from Candida cylindracea.