Aqueous Bicarbonate Solution Research Articles

ChemInform Abstract: Efficient Acetylation of Primary Amines and Amino Acids in Environmentally Benign Brine Solution Using Acetyl Chloride.

AbstractThis new method is very simple, inexpensive, and environmentally benign.

Comparison of the kinetic rate law parameters for the dissolution of natural and synthetic autunite in the presence of aqueous bicarbonate ions

This research evaluated the effect of aqueous hydrogen carbonate solutions on the uranium rate of release from natural Ca-autunite and quantified the process kinetic rate law for a better prediction of the stability of autunite-group minerals. Testing was accomplished via a single-pass flow-through (SPFT) apparatus using buffered aqueous bicarbonate solutions (0.0005 to 0.003M) at temperatures of 23–90°C and pH values of 7–11. The release rate of uranium from Ca-autunite was directly correlated to increasing concentrations of hydrogen carbonate solutions and showed strong pH dependency. Ca-autunite kinetic rate law parameters were compared to the values obtained for synthetic Na-autunite. The power law coefficient and intrinsic rate constant were higher at pH9–11 for Ca-autunite than for Na-autunite. The lower stability of Ca-autunite was attributed to the high Ca-autunite surface cracking, fractures and basal plane cleavages as compared to Na-autunite and the combined effect of the formation of aqueous uranyl–carbonate and calcium uranyl carbonate species as a driving force for uranium(VI) detachment and the formation of secondary Ca–P hydroxyapatite and uranyl phosphate mineral phases as a driving force for phosphate and calcium detachment controlling the net release of elements.

Removal of SO2 using ammonium bicarbonate aqueous solution as absorbent in a bubble column reactor

In this work, the removal of SO2 from gas mixture with air and SO2 by ammonium bicarbonate aqueous solution as absorbent was investigated experimentally in a bubble column reactor. The effects of the concentration of ammonium bicarbonate, the SO2 inlet concentration of gas phase and the gas flow rate on the removal rate of SO2 were studied. The results showed that the higher the SO2 inlet concentration and the gas flow rate, the shorter the lasting time of SO2 completely removed in gas outlet, and then the faster the decrease in the removal rate of SO2. The lasting time of SO2 completely removed in gas outlet increased with increasing ammonium bicarbonate concentration. During the process of SO2 absorption, there was a critical pH of solution. When the solution pH was less than the critical pH, it would sharply fall, resulting in a rapid decrease of the SO2 removal rate. A theoretical model for predicting the SO2 removal rate has been developed by taking the chemical enhancement and the sulfite concentration in the liquid phase into account simultaneously.

Preparation of methotrexate-loaded, large, highly-porous PLLA microspheres by a high-voltage electrostatic antisolvent process

A high-voltage (10 kV) electrostatic antisolvent process was used to prepare methotrexate (MTX)-loaded, large, highly-porous poly-L-lactide (PLLA) microspheres. MTX solution in dimethyl sulfoxide (DMSO) and PLLA solution in dichloromethane (DCM) were homogeneously mixed, and then ammonium bicarbonate (AB) aqueous solution was added. The mixed solution was emulsified by ultrasonication with Pluronic F127 (PF127) as an emulsion stabilizer. The emulsion was electrosprayed by the specific high-voltage apparatus and dropped into a 100 mL of ethanol, which acted as an antisolvent for the solute and extracted DMSO and DCM, causing the co-precipitation of PLLA and MTX, thus forming microspheres with AB aqueous micro-droplets uniformly inlaid. The obtained MTX-PLLA microspheres were subsequently lyophilized to obtain large, highly-porous MTX-PLLA microspheres, which exhibited an identifiable spherical shape and a rough surface furnished with open pores, with a mean particle size of 25.0 μm, mass median aerodynamic diameter of 3.1 ± 0.2 μm, fine-particle fraction of 57.1 ± 1.6 %, and porosity of 81.8 %; furthermore, they offered a sustained release of MTX. X-ray diffraction and Fourier transform-infrared spectra revealed that no crystallinity or alteration of chemical structure occurred during the high-voltage electrostatic antisolvent process, which in this study was proved to have great potential for preparing highly-porous drug-loaded polymer microspheres for use in pulmonary drug delivery.

Efficient acetylation of primary amines and amino acids in environmentally benign brine solution using acetyl chloride

Acetyl chloride is one of the most commonly available and cheap acylating agent but its high reactivity and concomitant instability in water precludes its use to carry out acetylation in aqueous medium. The present methodology illustrates the efficient acetylation of primary amines and amino acids in brine solution by means of acetyl chloride under weakly basic condition in the presence of sodium acetate and/or triethyl amine followed by trituration with aqueous saturated bicarbonate solution. This effort represents the first efficient use of this most reactive but cheap acetylating agent to acetylate amines in excellent yields in aqueous medium. This is a potentially useful green chemical transformation where reaction takes place in environment-friendly brine solution leading to easy work-up and isolation of the amide derivatives. Mechanistic rationale of this methodology is also important. Aromatic and aliphatic primary amines and amino acids have been acetylated efficiently in brine solution with acetyl chloride under weakly basic conditions in the presence of sodium acetate and/or triethyl amine. The methodology demonstrates successful use of acetyl chloride as a substitute of acetic anhydride for the purpose of acetylation in aqueous medium.

Determination of Ochratoxin A in Licorice and Licorice Extracts by High-Performance Liquid Chromatography Coupled with Fluorescence Detection: Collaborative Study

A collaborative study was conducted to validate an analytical method for the determination of ochratoxin A (OTA) in licorice (root powder) and licorice extracts (paste and powder). Contents of OTA ranged from 26 to 141 microg/kg and from 8 to 52 microg/kg for licorice extracts and root material, respectively. For the analysis, a test portion is extracted with a mixture of methanol and aqueous sodium bicarbonate solution. The extract is filtered and diluted with phosphate-buffered saline; and OTA is purified with an immunoaffinity column containing antibodies specific to OTA. The purified extract is dried, reconstituted, and quantified by HPLC with fluorescence detection. Twenty laboratories from 13 European Union member states, Uruguay, Turkey, and the United States of America participated in this study. The study was evaluated according to internationally accepted guidelines. The method performance characteristics can be summarized as follows: over a working range of 7.7 to 141 microg/kg OTA, the mean recoveries were 87% for licorice root and 84-88% for licorice extracts; and the RSDs for reproducibility ranged from 10 to 17% and from 11 to 22% in licorice extracts and licorice root, respectively. The method was found to be fit-for-purpose and to fulfill legal requirements as set in EC Regulation No. 401/2006.

Caged CO2 for the Direct Observation of CO2‐Consuming Reactions

CO(2)-consuming reactions, in particular carboxylations, play important roles in technical processes and in nature. Their kinetic behavior and the reaction mechanisms of carboxylating enzymes are difficult to study because CO(2) is inconvenient to handle as a gas, exists in equilibrium with bicarbonate in aqueous solution, and typically yields products that show no significant spectroscopic differences from the reactants in the UV/Vis range. Here we demonstrate the utility of 3-nitrophenylacetic acid and related compounds (caged CO(2)) in conjunction with infrared spectroscopy as widely applicable tools for the investigation of such reactions, permitting convenient measurement of the kinetics of CO(2) consumption. The use of isotopically labeled caged CO(2) provides a tool for the assignment of infrared absorption bands, thus aiding insight into reaction intermediates and mechanisms.

Quantification of kinetic rate law parameters of uranium release from sodium autunite as a function of aqueous bicarbonate concentrations

Environmental context Uranium is a key contaminant of concern because of its high persistence in the environment and toxicity to organisms. The bicarbonate ion is an important complexing agent for uranyl ions and one of the main variables affecting its dissolution. Results from this investigation provide rate law parameters for the dissolution kinetics of synthetic sodium autunite that can influence uranium mobility in the subsurface. Abstract Hydrogen carbonate (also known as bicarbonate) is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, bicarbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous bicarbonate solutions to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate solutions (0.0005–0.003M) over the pH range of 6–11 and temperatures of 5–60°C. Consistent with the results of previous investigations, the rate of uranium release from sodium autunite exhibited minimal dependency on temperature, but was strongly dependent on pH and increasing concentrations of bicarbonate solutions. Most notably at pH 7, the rate of uranium release exhibited a 370-fold increase relative to the rate of uranium release in the absence of bicarbonate. However, the effect of increasing concentrations of bicarbonate solutions on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release. Results indicate that the activation energies were unaffected by temperature and bicarbonate concentration variations, but were strongly dependent on pH conditions. As the pH increased from 6 to 11, the activation energy values were observed to decrease from 29.94 to 13.07kJmol–1. The calculated activation energies suggest a surface controlled dissolution mechanism.

Investigation of Microstructure, Electrical and Decorative Properties of WO<sub>3</sub> Film by PVD Magnetron Sputtering with Ar/O<sub>2</sub>

In this experiment, we use the opaque mirror stainless steel as the substrate to investigate decorative color variations after insertion of the Na+ ion in the film and prescribe the combination coating film with reversible and excellent coating characteristics. In manufacturing of the coating film, reactive gas pass through the metal tungsten target and form the amorphous tungsten oxide thin film on stainless steel and the various colors, such as green and pink color, on the mirror stainless by adjusting the process parameters. The coating film device then immerse in sodium bicarbonate aqueous solution and induce cyclic potential of -2V～+2V. Base color of stainless steel produce the color change reaction by inserting Na+ in the film. Experimental observations show that the green base color will transform to pink then blue and the pink base color transform to green then blue.

Extraction and Characterization of Seed Oil from Naturally Grown Chinese Tallow Trees

AbstractSeeds were collected from locally and naturally grown Chinese tallow trees (CTT) and characterized for general physical and chemical properties and fatty acid composition of the lipids. The effects of four different solvents (petroleum ether, hexane, diethyl ether, and 95 % ethanol) and two extraction methods (supercritical carbon dioxide (SC‐CO2) and conventional Soxhlet) on the properties of the CTT seed oil, including Chinese vegetable tallow (CVT) and stillingia oil (SO), were also investigated. In general, the yields of CVT and SO did not vary based on solvent for Soxhlet extraction and solvent‐free SC‐CO2 extraction, except that the yield of CVT from SC‐CO2 extraction was substantially lower. Nevertheless, the CTT seed oil, extracted by SC‐CO2 displayed better quality than those extracted by Soxhlet extraction in terms of color, residual precipitation, and acid value of the oils. The pretreatment of CTT seed by 3 % aqueous sodium bicarbonate solution likely promoted the hydrolysis of triglyceride and caused the high acid value in the CVT samples. The iodine value at around 180 indicated that the SO is a highly unsaturated drying oil. Palmitic (76 %) and oleic (23 %) are two dominant fatty acids in CVT while linolenic (43 %), linoleic (31 %), and oleic (13 %) are the dominant fatty acids in SO.

Electrothermal Supercharging of Proteins in Native Electrospray Ionization

The formation of high charge-state protein ions with nanoelectrospray ionization (nESI) from purely aqueous ammonium bicarbonate solutions at neutral pH, where the proteins have native or native-like conformations prior to ESI droplet formation, is demonstrated. This "electrothermal" supercharging method depends on the temperature of the instrument entrance capillary, the nESI spray potential, and the solution ionic strength and buffer, although other factors almost certainly contribute. Mass spectra obtained with electrothermal supercharging appear similar to those obtained from denaturing solutions where charging beyond the total number of basic sites can be achieved. For example, a 17+ ion of bovine ubiquitin was formed by nESI of a 100 mM ammonium bicarbonate, pH 7.0, solution, which is three more charges than the total number of basic amino acids plus the N-terminus. Heating of the ESI droplets in the vacuum/atmosphere interface and the concomitant denaturation of the protein in the ESI droplets prior to ion formation appears to be the primary origin of the very high charge-state ions formed from these purely aqueous, buffered solutions. nESI mass spectra resembling those obtained under traditional native or denaturing conditions can be reversibly obtained simply by toggling the spray voltage between low and high values.

Effect of the Composition of Nickel Alloys on the Anodic Behavior in Aqueous Solutions of Chloride and Bicarbonate

ABSTRACTThe stress corrosion cracking (SCC) of Alloy 22 in concentrated ground waters was associated to the presence of bicarbonate and chloride ions in the water. SCC occurred when an anodic peak appeared in the polarization curve of Alloy 22. The aim of this work was to investigate further which element in Alloy 22 was responsible for the anodic peak and therefore SCC. Four alloys (22, 800H, 600 and 201) were mainly used for this study. It has been found that Alloy 22, 600 and 800H show anodic peaks; which are affected by chloride and temperature. It is likely that the anodic peak is associated to the presence of either chromium, molybdenum or both.

Anion-exchange membranes for alkaline polymer electrolyte fuel cells: comparison of pendent benzyltrimethylammonium- and benzylmethylimidazolium-head-groups

Radiation-grafted alkaline anion-exchange membranes (AAEM) containing pendent groups with either benzyltrimethylammonium (BTM) or benzylmethylimidazolium (BMI) functionality were successfully synthesised from the same base membrane and with identical ion-exchange capacities. The conductivity of the new BMI-AAEM is comparable to the BTM-benchmark AAEM. The fuel cell performance obtained with the BMI-AAEM was, however, significantly poorer due to in situ AAEM degradation. FT-Raman spectroscopic studies on the stability of the two head-groups at 60 °C in aqueous potassium hydroxide (1 mol dm−3) indicates that the BMI-group is intrinsically less chemically stable in strongly alkaline conditions compared to the BTM-benchmark head-group. However, the stabilities of both head-groups are improved when treated at 60 °C in lower pH aqueous carbonate and bicarbonate solutions (1 mol dm−3). Contrary to a portion of the prior literature, there appears to be no real advantage in using anion-exchange polymer electrolytes containing pendent imidazolium groups in highly alkaline systems.

Bicarbonate produced from carbon capture for algae culture

Using captured CO(2) to grow microalgae is limited by the high cost of CO(2) capture and transportation, as well as significant CO(2) loss during algae culture. Moreover, algae grow poorly at night, but CO(2) cannot be temporarily stored until sunrise. To address these challenges, we discuss a process where CO(2) is captured as bicarbonate and used as feedstock for algae culture, and the carbonate regenerated by the culture process is used as an absorbent to capture more CO(2). This process would significantly reduce carbon capture costs because it does not require additional energy for carbonate regeneration. Furthermore, not only would transport of the aqueous bicarbonate solution cost less than for that of compressed CO(2), but using bicarbonate would also provide a superior alternative for CO(2) delivery to an algae culture system.

CO2 desorption using high-pressure bipolar membrane electrodialysis

The electrodialysis of gas evolving solutions may prove to be an important technology for many gas-separation applications, including CO2 and SO2 separation from mixed-gas streams. Progress on the use of electrodialysis for gas separation has been hampered by the increased resistance caused by gas bubbles on the surface of the electrodialysis membranes. This effect reduces the effective membrane surface area, causing increased voltages and reduced membrane lifetimes due to localized “hot spots” of high current density. To overcome this problem, we designed, constructed, and tested a bipolar membrane electrodialysis (BPMED) system designed to operate up to pressures as high as 20 atm. For given process conditions, operation at a sufficiently high pressure keeps all gas dissolved in solution, eliminating the problems caused by gas bubbles on the membrane surfaces. We performed CO2 desorption from aqueous bicarbonate solutions, demonstrating that high pressures decrease the resistance, voltage, and energy of the desorption process. Our results demonstrate that at high current densities (139 mA cm−2), the CO2 desorption energy from aqueous bicarbonate solutions under high-pressure operation can be 29% lower than under ambient-pressure operation.

CO2separation using bipolar membrane electrodialysis

Caustic solvents such as sodium or potassium hydroxides, converted viaCO2 capture to aqueous carbonates or bicarbonates, are a likely candidate for atmospheric CO2 separation. We have performed a comprehensive experimental investigation of CO2 gas regeneration from aqueous potassium carbonate and bicarbonate solutions using bipolar membrane electrodialysis (BPMED). This system allows the regeneration of pure CO2 gas, suitable for subsequent sequestration or reaction to synthetic hydrocarbons and their products, from aqueous carbonate/bicarbonate solutions. Our results indicate that the energy consumption required to regenerate CO2 gas from aqueous bicarbonate (carbonate) solutions using this method can be as low as 100 kJ (200 kJ) per mol of CO2 in the small-current-density limit.

Synthesis of enantiomerically pure phosphonic analog of natural aspartic acid

Methyl ester of L-serine I was Boc-protected at the NH-group [1], then the obtained (S)-hydroxyaminocarboxylate II was transformed into bromide (R)-III through reaction with triphenylphosphine and trichlorobromomethane in methylene chloride at 70°С. Bromide III was purified by vacuum distillation and brought into the Arbuzov reaction with five-fold excess of triethyl phosphite, the reaction proceeded at 135–140°С over 12 h. After distilling off the volatile reaction product at 0.1 mm Hg at 120°С, the phosphonate IV was obtained, which was purified by column chromatography. Its structure was proved by the Н, С and Р NMR spectroscopy and mass spectrometry. The heating of compound IV with hydrochloric acid affords (R)-(+)-С-phosphonoaspartic acid V. This compound have been earlier obtained by a more complicated method [2]. The physical properties and optical rotation angle coincided with the published data. Methyl (S)-tert-buthoxycarbonylamino-3-hydroxypropionate (II). To a solution of 10.5 g (0.05 mol) of (S)-methyl serinate hydrochloride in 10 ml of THF was added 15 g of triethylamine at 0°С and this mixture was stirred for 30 min. Then 12 g of Boc2O was added, and the reaction mixture was warmed to room temperature, stirred for 6 h, and then refluxed for 3 h. Then it was cooled, poured into the saturated aqueous sodium hydrogen bicarbonate solution, extracted with diethyl ether, and concentrated. Yield 90%, [α]D 18.0 (MeOH, c 5), colorless oil. Н NMR spectrum (CDCl3), δ, ppm: 1.44 s [9H, (CH3)3C], 3.77 s (3H, CH3O), 3.9 m (2H, CH2), 4.38 m (1H, CHN), 5.57 br.s (1H, NH).

Polymeric Functionalized Stationary Phase for Separation of Ionic Compounds by IC

Synthesis and properties are described of multilayered stationary phases containing quaternary amine functional groups used for the analysis of inorganic anions by ion chromatography. The bonded phases were characterized by elemental analysis, solid state 13C NMR spectroscopy and chromatographic methods. The surface of polyhydroxyethyl methacrylate (solid support) was coated with polymeric layers formed by condensation polymerization of primary amine with diepoxide. Each layer of the anion exchange stationary phase consisted of methylamine and 1,4-butanedioldiglycidyl ether copolymer. A series of stationary phases with different number of polymerized layers were tested. Separation of inorganic anions, such as F−, Cl−, NO2 −, Br−, NO3 −, were performed. Aqueous hydroxide, carbonate and bicarbonate solutions were used as mobile phases.

Experimental approaches to feed solution permeability in pressure-driven membrane separation processes

This study demonstrates the application of the solution-diffusion pore-flow fluid-resistance (SDPFFR) model, which is used to describe solvent transfer in pressure-driven membrane separation processes. The experimental work is carried out in a reverse osmosis (RO) setup by using two different membranes, TFC-HR and TFC-ULP, manufactured by Koch Membranes Systems, Inc. (USA). Characterization for these membranes by using the transmission electron microscopy (TEM) is also presented. Aqueous solutions of sodium chloride and ammonium bicarbonate were used as feed at 15, 25, and 35 °C. The results show that water transfer in the feed side of the membrane is controlled by the molecular properties of the solute in addition to the operational conditions. Water permeability in the feed solution has been observed to increase as the solute hydration strength or concentration decrease, and as the temperature and the hydraulic pressure increase. The validated model explains the interaction between water permeability in the feed solution and water permeability inside the membrane material. The model shows good agreement with the experimental results. It provides good description for solvent transfer in membrane separation processes and may be useful for future development and design applications, when based on experimental data.

ChemInform Abstract: Decarboxylative Elimination of Enol Triflates as a General Synthesis of Acetylenes.

The enol trifluoromethanesulfonates 4, 8, 12, 17 and 20 of tert-butyl β-ketodiesters and β-ketoesters can be hydrolysed to the corresponding carboxylic acids by dissolution in trifluoroacetic acid. The dicarboxylic acids undergo mild decarboxylative elimination to give the acetylenic acids 4 and 9 in aqueous sodium bicarbonate solution at room temperature. Similarly, the monocarboxylic acids give the terminal and mid-chain acetylenes 13, 18, 21 and 24 by refluxing in acetone with potassium carbonate. One of the substituents on the acetylenes can be methyl, primary alkyl, secondary alkyl or ethynyl, and the other can be a carboxylic acid, hydrogen or primary alkyl, but the enol trifluoromethanesulfonates could not be prepared when one of the substituents was tert-butyl, nor when both substituents on the precursor to the acetylene were secondary alkyl.