Some new triazole derivatives as inhibitors for mild steel corrosion in acidic medium

Two triazole derivatives, 3,4-dichloro-acetophenone-O-1'-(1',3',4'-triazolyl)-methaneoxime (4-DTM) and 2,5-dichloro-acetophenone-O-1'-(1',3',4'-triazolyl)-methaneoxime (5-DTM) were synthesized, and the inhibition effects for mild steel in 1 M HCl solutions were investigated by weight loss measurements, electrochemical tests and scanning electronic microscopy (SEM). The weight loss measurements showed that these compounds have excellent inhibiting effect at a concentration of 1.0 x 10(-3) M. The potentiodynamic polarization experiment revealed that the triazole derivatives are inhibitors of mixed-type and electrochemical impedance spectroscopy (EIS) confirmed that changes in the impedance parameters (R-ct and C-dl) are due to surface adsorption. The inhibition efficiencies obtained from weight loss measurements and electrochemical tests were in good agreement. Adsorption followed the Langmuir isotherm with negative values of the free energy of adsorption Delta G(ads)(o). The thermodynamic parameters of adsorption were determined and are discussed. Results show that both 4-DTM and 5-DTM are good inhibitors for mild steel in acid media.

cDNA cloning and overexpression of acidic ribosomal phosphoprotein P1 gene (RPLP1) from the Giant Panda

RPLP1 is one of acidic ribosomal phosphoproteins encoded by RPLP1 gene, which plays an important role in the elongation step of protein synthesis. The cDNA of RPLP1 was cloned successfully for the first time from the Giant Panda (Ailuropoda melanoleuca) using RT-PCR technology, which was also sequenced, analyzed preliminarily and expressed in E. coli. The cDNA fragment cloned is 449bp in size, containing an open reading frame of 344bp encoding 114 amino acids. Alignment analysis indicated that the nucleotide sequence and the deduced amino acid sequence are highly conserved to other five species studied, including Homo sapiens, Mus musculus, Rattus norvegicus, Bos Taurus and Sus scrofa. The homologies for nucleotide sequences of Giant Panda PPLP1 to that of these species are 92.4%, 89.8%, 89.0%, 91.3% and 87.5%, while the homologies for amino acid sequences are 96.5%, 94.7%, 95.6%, 96.5% and 88.6%. Topology prediction showed there are three Casein kinase II phosphorylation sites and two N-myristoylation sites in the RPLP1 protein of the Giant Panda (Ailuropoda melanoleuca). The RPLP1 gene was overexpressed in E. coli and the result indicated that RPLP1 fusion with the N-terminally His-tagged form gave rise to the accumulation of an expected 18kDa polypeptide, which was in accordance with the predicted protein and could also be used to purify the protein and study its function.

Separation of acidic compounds by strong anion-exchange capillary electrochromatography

Separation of the acidic compounds in the ion-exchange capillary electrochromatograph (IE-CEC) with strong anion-exchange packing as the stationary phase was studied. It was observed that the electroosmotic flow (EOF) in strong anion-exchange CEC moderately changed with increase of the eluent ionic strength and decrease of the eluent pH, but the acetonitrile concentration in the eluent had almost no effect on the EOF. The EOF in Strong anion-exchange CEC with eluent of low pH value was much larger than that in RP-CEC with Spherisorb-ODS as the stationary phase. The retention of acidic compounds on the strong anion-exchange packing was relatively weak due to only partial ionization of them, and both chromatographic and electrophoretic processes contributed to separation. It was observed that the retention values of acidic compounds decreased with the increase of phosphate buffer and acetonitrile concentration in the eluent as well as the decrease of the applied voltage, and even the acidic compounds could elute before the void time. These factors also made an important contribution to the separation selectivity for tested acidic compounds, which could be separated rapidly with high column efficiency of more than 220 000 plates/m under the optimized separation conditions. (C) 2000 Elsevier Science BN. All rights reserved.

Protocol of capillary isoelectric focusing to separate extremely acidic and basic proteins

A new set-up was constructed for capillary isoelectric focusing (CIEF) involving a sampling capillary as a bypass fixed to the separation capillary. Sample solutions were subjected to a previously established pH gradient from the sample capillary. Besides performing conventional CIEF, the separation of ampholytic compounds with isoelectric points (p/s) beyond the pH gradient was carried out on this system. This method was termed as pH gradient driven electrophoresis (PGDE) and the basic mathematical expressions were derived to express the dynamic fundamentals. Proteins such as lysozyme, cytochrome C, and pepsin with p/s higher than 10 or below 3 were separated in a pH gradient provided by Pharmalyte (pH 3-10). Finally, this protocol convincingly exhibited its potential in the separation of a solution of chicken egg white.

Direct synthesis of highly ordered Fe-SBA-15 mesoporous materials under weak acidic conditions

Iron-substituted SBA-15 (Fe-SBA-15) materials have been synthesized via a simple direct hydrothermal method under weak acidic conditions. The powder X-ray diffraction (XRD), NZ sorption and transmission electron microscopy (TEM) characterizations show that the resultant materials have well-ordered hexagonal meso-structures. The diffused reflectance UV-vis and UV resonance Raman spectroscopy characterizations show that most of the iron ions exist as isolated framework species for calcined materials when the Fe/Si molar ratios are below 0.01 in the gel. The presence of iron species also has significant salt effects that can greatly improve the ordering of the mesoporous structure. Different iron species including isolated framework iron species, extraframework iron clusters and iron oxides are formed selectively by adjusting the pH values of the synthesis solutions and Fe/Si molar ratios. (c) 2005 Elsevier Inc. All rights reserved.

An investigation into the tropospheric chemistry of acidic aerosols and ammonia in the laboratory

This thesis describes a broad range of experiments based on an aerosol flow-tube system to probe the interactions between atmospherically relevant aerosols with trace gases. This apparatus was used to obtain simultaneous optical and size distribution measurements using FTIR and SMPS measurements respectively as a function of relative humidity and aerosol chemical composition. Heterogeneous reactions between various ratios of ammonia gas and acidic aerosols were studied in aerosol form as opposed to bulk solutions. The apparatus is unique, in that it employed two aerosol generation methods to follow the size evolution of the aerosol while allowing detailed spectroscopic investigation of its chemical content. A novel chemiluminescence apparatus was also used to measure [NH4+]. SO2.H2O is an important species as it represents the first intermediate in the overall atmospheric oxidation process of sulfur dioxide to sulfuric acid. This complex was produced within gaseous, aqueous and aerosol SO2 systems. The addition of ammonia, gave mainly hydrogen sulfite tautomers and disulfite ions. These species were prevalent at high humidities enhancing the aqueous nature of sulfur (IV) species. Their weak acidity is evident due to the low [NH4+] produced. An increasing recognition that dicarboxylic acids may contribute significantly to the total acid burden in polluted urban environments is evident in the literature. It was observed that speciation within the oxalic, malonic and succinic systems shifted towards the most ionised form as the relative humidity was increased due to complete protonisation. The addition of ammonia produced ammonium dicarboxylate ions. Less reaction for ammonia with the malonic and succinic species were observed in comparison to the oxalic acid system. This observation coincides with the decrease in acidity of these organic species. The interaction between dicarboxylic acids and ‘sulfurous’/sulfuric acid has not been previously investigated. Therefore the results presented here are original to the field of tropospheric chemistry. SHO3-; S2O52-; HSO4-; SO42- and H1,3,5C2,3,4O4-;C2,3,4O4 2- were the main components found in the complex inorganic-organic systems investigated here. The introduction of ammonia produced ammonium dicarboxylate as well as ammonium disulfite/sulfate ions and increasing the acid concentrations increased the total amount of [NH4+].

Living in warmer, more acidic oceans retards physiological recovery from tidal emersion in the velvet swimming crab, Necora puber

The distribution patterns of many species in the intertidal zone are partly determined by their ability to survive and recover from tidal emersion. During emersion, most crustaceans experience gill collapse, impairing gas exchange. Such collapse generates a state of hypoxemia and a hypercapnia-induced respiratory acidosis, leading to hyperlactaemia and metabolic acidosis. However, how such physiological responses to emersion are modified by prior exposure to elevated CO2 and temperature combinations, indicative of future climate change scenarios, is not known. We therefore investigated key physiological responses of velvet swimming crabs, Necora puber, kept for 14 days at one of four pCO(2)/temperature treatments (400 mu atm/10 degrees C, 1000 mu atm/10 degrees C, 400 mu atm/15 degrees C or 1000 mu atm/15 degrees C) to experimental emersion and recovery. Pre-exposure to elevated pCO(2) and temperature increased pre-emersion bicarbonate ion concentrations [HCO3-], increasing resistance to short periods of emersion (90 min). However, there was still a significant acidosis following 180 min emersion in all treatments. The recovery of extracellular acid-base via the removal of extracellular pCO(2) and lactate after emersion was significantly retarded by exposure to both elevated temperature and pCO(2). If elevated environmental pCO(2) and temperature lead to slower recovery after emersion, then some predominantly subtidal species that also inhabit the low to mid shore, such as N. puber, may have a reduced physiological capacity to retain their presence in the low intertidal zone, ultimately affecting their bathymetric range of distribution, as well as the structure and diversity of intertidal assemblages.

Solvation Structure and Transport of Acidic Protons in Ionic Liquids: A First-principles Simulation Study

Ab initio simulations of a single molecule of HCl in liquid dimethyl imidazolium chloride [dmim][Cl] show that the acidic proton exists as a symmetric, linear ClHCl- species. Details of the solvation structure around this molecule are given. The proton-transfer process was investigated by applying a force along the antisymmetric stretch coordinate until the molecule broke. Changes in the free energy and local solvation structure during this process were investigated. In the reaction mechanism identified, a free chloride approaches the proton from the side. As the original ClHCl- distorts and the incoming chloride forms a new bond to the proton, one of the original chlorine atoms is expelled and a new linear molecule is formed.

Investigations on the adsorption of acidic gases using activated dolomite

In this work activated dolomite adsorption was investigated for removal of acidic gaseous pollutants. Charring was found to be an effective method for the activation of dolomite. This thermal processing resulted in partial decomposition, yielding a calcite and magnesium oxide structure. Adsorbents were produced over a range of char temperatures (750, 800 and 850 °C) and char times (1–8 h). The surface properties and the adsorption capability of raw and thermally treated dolomite sorbents were investigated using porosimetry, SEM and XRD. The sorbates individually investigated were CO2 and NO2. Volumetric equilibrium isotherm determinations were produced in order to quantify sorbate capacity on the various sorbents. The equilibrium data were successfully described using the Freundlich isotherm model. Despite relatively low surface area characteristics of the activated dolomite, there was a high capacity for the acidic gas sorbates investigated, showing a maximum of 12.6 mmol/g (554 mg/g) for CO2 adsorption and 9.93 mmol/g (457 mg/g) for NO2 adsorption. Potentially the most cost effective result from the work concerns the adsorptive capacity for the naturally occurring material, which gave a capacity of 9.71 mmol/g (427 mg/g) for CO2 adsorption and 4.18 mmol/g (193 mg/g) for NO2 adsorption. These results indicate that dolomitic sorbents are potentially cost effective materials for acidic gases adsorption.

Assessment of Self-Compacting Concrete Immersed in Acidic Solutions

Ettringite and thaumasite can be found among the deterioration products of cementitious materials exposed to sulfate and hydrochloric attack. The results of a test program to investigate the acid resistance of self-compacting concrete (SCC) and conventional concrete (CC), immersed up to 18 weeks at 20°C in sulfuric and hydrochloric acid solutions, are described. The SCC was prepared with 47% carboniferous limestone powder, as a replacement for cement, and an ordinary portland cement. The CC was prepared with portland cement only. The water-binder ratios of the SCC and CC were 0.36 and 0.46, respectively. The parameter investigated was the time, in weeks, taken to cause 10% mass loss of fully immersed concrete specimens in a 1% solution of sulfuric acid and the same amount of loss in a 1% solution of hydrochloric acid. The investigation indicated that the SCC performed better than the CC in sulfuric solution but was slightly more vulnerable to hydrochloric acid attack compared to CC. The mode of attack between the two solutions was different.

The contents of proteins and phospholipids in cloudy (veiled) virgin olive oils

Extra virgin olive oil is produced in the form of a

Kinetics and mechanism of a fast leuco-Methylene Blue oxidation by copper(II)-halide species in acidic aqueous media

The kinetics of a fast leuco-Methylene Blue (LMB) re-oxidation to Methylene Blue (MB) by copper(II)-halide (Cl-, Br-) complexes in acidic aqueous media has been studied spectrophotometrically using a stopped-flow technique. The reaction follows a simple first order rate expression under an excess of the copper(II) species (and H+(aq)), and the pseudo-first order rate constant (k'(obs)) is largely independent of the atmosphere used (air, oxygen, argon). The rate law, at constant Cl- (Br-) anion concentration, is given by the expression: (d[MB+])/dt = ((k(a)K[H+] + k(b))/(1 + K[H+])).[Cu-II][LMB] = k'(obs)[LMB], where K is the protonation constant, and k(a) and k(b) are the pseudo-second order rate constants for protonated and deprotonated forms of LMB, respectively The rate law was determined based on the observed k'(obs) vs. [Cu-II] and [H+] dependences. The rate dramatically increases with [Cl-] over the range: 0.1-1.5 M, reflecting the following reactivity order: Cu2+(aq)