Kinetics of radiation. Chemical processes in isopolymolybdates and isopolytungstates

The kinetics of radiation reduction of Mo(VI) and W(VI) in aqueous formic acid or acidified methanol solutions has been studied. The rate constants of radiation-chemical processes have been measured by pulse radiolysis technique. It has been shown that the reduction of polytungstates in aqueous formic acid solutions, contrary to polymolybdates whose reduction proceeds via lower oxidation states, leads directly to W(V) compounds. In acidified aqueous methanol solutions the isopolymetallate blues are the only optically detected products of the reduction.     

Radiation-induced nitration of organic compounds in aqueous solutions

Radiation-induced nitration of organic compounds in aqueous solutions was studied. It was found that γ-irradiation of solutions containing acetic and nitric acid and/or their salts gives nitromethane. Dependences of the product yield on the absorbed dose and the contents of components were established. The mechanism of radiation nitration involving radicals is discussed.     

Rapid analysis and characterization of multiple constituents of corn silk aqueous extract using ultra‐high‐performance liquid chromatography combined with quadrupole time‐of‐flight mass spectrometry

Corn silk is a well‐known traditional Chinese medicine that has been widely used for its antidiabetic, antioxidant, antihyperlipidemic, and other effects in China for thousands of years. Numerous studies have revealed that corn silk contains multiple bioactive constituents that are beneficial for human health. However, the constituents of corn silk in vivo remain ambiguous. In this study, high‐throughput ultra‐high‐performance liquid chromatography combined with quadrupole time‐of‐flight mass spectrometry technology using multivariate statistical analysis was established to systematically investigate the constituents migrating into blood from corn silk aqueous extract. As a result, 76 compounds were identified, including caffeic acid and ten of its derivatives, (E)‐p‐coumaric acid and two of its derivatives, ferulic acid and four of its derivatives, and five flavones. Among the identified constituents, 21 constituents, including nine prototype components and 12 metabolites derived from eight components, were characterized in sequence. Based on the significance of the results, the applied approach was powerful for the accurate determination and rapid screening of bioactive components from corn silk aqueous extract. The obtained results are valuable for the in‐depth understanding and further pharmacological study of corn silk aqueous extract.     

Cyclodextrins in Eye Drop Formulations

Ideally, eye drop formulations are aqueous solutions. Many drugs that are useful in topical application to the eye are not sufficiently water soluble to be dissolved in simple aqueous solutions. This problem is approached through hydrophilic prodrugs, suspensions, lipid based solutions and excipients such as cyclodextrins. Cyclodextrins can be used to form aqueous eye drop solutions with lipophilic drugs, such as steroids. The cyclodextrins increase the water solubility of the drug, enhance drug absorption into the eye, improve aqueous stability and reduce local irritation. Cyclodextrins are useful excipients in eye drop formulations of various ophthalmic drugs, including steroids of any kind, carbonic anhydrase inhibitors, pilocarpine and cyclosporins. Their use in ophthalmology has already begun and it is likely to expand the selection of drugs available as eye drops. In this paper we review the use of cyclodextrins in eye drop formulations. The use of cyclodextrins to formulate dexamethasone eye drops is an example of their usefulness. Cyclodextrins have been used to formulate eye drops containing corticosteroids, such as dexamethasone, with concentration and ocular absorption, which in human and animal studies is many fold that seen with presently available formulations. Such formulations offer the possibility of once a day application of corticosteroid eye drops after eye surgery, and more intensive topical steroid treatment in severe inflammation.     

Model Systems for Evidencing the Mediator Role of Riboflavin in the UVA Cross-Linking Treatment of Keratoconus

Riboflavin under UVA radiation generates reactive oxygen species (ROS) that can induce various changes in biological systems. Under controlled conditions, these processes can be used in some treatments for ocular or dermal diseases. For instance, corneal cross-linking (CXL) treatment of keratoconus involves UVA irradiation combined with riboflavin aiming to induce the formation of new collagen fibrils in cornea. To reduce the damaging effect of ROS formed in the presence of riboflavin and UVA, the CXL treatment is performed with the addition of polysaccharides (dextran). Hyaluronic acid is a polysaccharide that can be found in the aqueous layer of the tear film. In many cases, keratoconus patients also present dry eye syndrome that can be reduced by the application of topical solutions containing hyaluronic acid. This study presents physico-chemical evidence on the effect of riboflavin on collagen fibril formation revealed by the following methods: differential scanning microcalorimetry, rheology, and STEM images. The collagen used was extracted from calf skin that contains type I collagen similar to that found in the eye. Spin trapping experiments on collagen/hyaluronic acid/riboflavin solutions evidenced the formation of ROS species by electron paramagnetic resonance measurements.     

Partition Coefficients and Interfacial Activity for Polar Components in Oil/Water Model Systems

Partition coefficients, surface tension, and interfacial tension for some polar organic components dissolved in oil/water model systems have been investigated. The systems consist of isooctane modeling the oil phase and of water solutions of NaCl and CaCl2 modeling the water phase. The organic compounds examined were 1-naphtoic acid, 5-indanol, and quinoline, all well-defined molecules known to be representative of polar components in crude oil. The dependence on pH, salinity, and ionic strength in the water phase was investigated. The surface tension and interfacial tension were also examined as a function of component concentration. The results show a connection between the distribution of the polar components and the interfacial tension. Correspondence between the partition coefficient and the pKa value for the components is also reported. For 1-naphtoic acid none of the two ionization forms of the molecule are found to be surface active in aqueous solution. For 5-indanol both forms are surface active, and for quinoline only the nonionic form of the molecule is found to be surface active. The results indicate that the aqueous phase is the one that governs the interfacial tension. Increasing salinity increases the concentration of the component in the oil phase and decreases the interfacial tension between the oil phase and the aqueous phase. The results are explained due to the "salting-out" effect and to changes in the electrostatics for the various systems. Copyright 1999 Academic Press.     

Extraction of strontium using an irradiated extraction agent of crown structure

The partition coefficient of strontium upon its extraction from the aqueous solutions of picric acid into chloroform containing DC-18-crown-6, B-15-crown-5 after their exposition to gamma radiation has been studied. A significant decrease of the partition coefficient in the studied range of doses 10–70 kGy was observed. This effect can be attributed to the radiolytic products of chloroform. The radiation destruction as well as dehydrogenation of crown ethers were not observed.     

Studies of high linear energy transfer dosimetry by 10B(n,α)7Li reactions in aqueous and organic solvents

Advanced chemical treatment processes such as aqueous separation techniques can be used to separate the reusable materials from used nuclear fuel, reducing the radiotoxicity and storage time of the remaining waste. The degradation of chemicals in these processes has been studied utilizing gamma radiation. However, radiolytic degradation by internal alpha emitters has not been as widely investigated due to the difficulty of finding appropriate internal sources. This work presents results using a method to produce alpha particles in situ in aqueous and organic solvents representative of liquid–liquid extraction systems. The method is based on the widely studied ¹⁰B(n,α)⁷Li reaction which has previously been studied in aqueous solutions. Neutrons were supplied from the UCI TRIGA^® nuclear reactor. Comparisons were also made to gamma radiation from a ¹³⁷Cs source. We report that the method is useful for inducing high linear energy transfer (LET) doses in aqueous and organic solutions. We used the classic iron sulfate-based Fricke dosimeter for dosimetry in aqueous solutions and methyl red (2-[(4-dimethylaminophenyl)diazenyl]benzoic acid) dissolved in n-dodecane for organic solvents. High LET doses in both aqueous and organic solvents are well described and a simple linear relationship was found based on the neutron flux and total boron concentration. We have established, using spectroscopic determination, that methyl red degrades in a linear fashion with absorbed dose up to 80 kGy and G-values for the methyl red degradation in n-dodecane were found to be 4.66 × 10^?4 μmol/J for external ¹³⁷Cs gamma radiation and 3.0 × 10^?5 μmol/J for ¹⁰B(n,α)⁷Li induced high LET radiation.     

Über Chelate des UO22+-Ions mit Aminopolycarbonsäuren in Lösung

On Chelates of the UO₂²⁺ Ion Formed with Aminopolycarboxylic Acids in Solution Complexes of uranium(VI) with nitrilotriacetic acid, ethylenediaminetetraacetic acid as well as diethylenetriaminepentaacetic acid in aqueous solution have been controlled by spectrophotometric and electrophoretic methods. The ratio of components in the species UO₂:L is 1:1 without any exception.     

Radiation induced grafting of acrylic acid onto extruded polystyrene surface

Polystyrene materials with good solubility in liquid scintillation cocktails are used to wipe off different types of surfaces in order to determine the tritium removable contamination with the help of a liquid scintillation counter. This paper analyses hydrophilic surface modifications by radiation induced grafting of acrylic groups onto extruded polystyrene plates. Two grafting methods were used: (a) exposure of extruded polystyrene plates, immersed in aqueous acrylic acid solution, to a gamma radiation of a Co-60 source, and (b) exposure of extruded polystyrene plates to a Co-60 source, followed by the immersion of extruded polystyrene plates in aqueous acrylic acid solution. The grafting of acrylic was proved by IR spectrometry and by radiometric methods using acrylic acid labelled with tritium.     

Modeling of equilibriums of formation of polynuclear chelates of nickel(ii) with histidine

Electronic absorption spectroscopy has been applied to study of protolytic and complex formation equilibriums in binary and tertiary systems containing nickel(II) salt, ethylenediaminetetraacetic acid and 2-amino-3-(imidazol-2-yl)propionic acid (ionic strength 0.1 mol/L aqueous NaClO₄, 20±2°C). Fitting of experimental spectral properties as function of pH and the components concentration requires dissociation constants of the ligands as well as stability constants of homoligand, heteroligand, and polynuclear complexes as parameters. These parameters have been estimated from the best fit model, and possible complexes structures have been suggested.     

Reaction of water soluble polymers with oxidising agents: reaction of dextran with tetravalent cerium

Dextran, an extracellular bacterial polysaccharide, was subjected to reaction with ceric ammonium nitrate in aqueous nitric acid at varying temperatures. The polymer has been found to be degraded due to the selective oxidative cleavage of vicinal glycol units present in the monosaccharide unit of each chain. The aldehyde groups produced upon cleavage at low temperature were found to undergo further oxidation to acids and formic acid with rise in temperature of the reaction. The course of the reaction has been followed by cerimetry and by spectrophotometrical measurements. The effect of the concentration of reacting components on the reaction has been studied and various kinetic aspects have been evaluated. Depending on the kinetic results, a plausible reaction mechanism for the oxidative degradation and the subsequent reactions have been suggested by the study of the changes of solution viscosity and initiation of graft copolymerization of vinyl monomers by Ce(IV)/dextran mixture. Various thermodynamic parameters have been evaluated.     

Cholesterol-armed cyclens for helical metal complexes offering chiral self-aggregation and sensing of amino acid anions in aqueous solutions

Cholesterol-armed cyclens worked as octadentate receptors for Na+, Ca2+, and Y3+ complexes in which four chiral cholesterol-functionalized sidearms were bundled and asymmetrically twisted above cyclen-metal complex platforms. Since the resulting helical metal complexes included chiral, hydrophobic cholesterol residues and charged, hydrophilic metal sites as well as asymmetric coordination geometries, they exhibited unique amphiphilic properties and provided chiral self-aggregates in aqueous solutions. Light scattering, fluorescence, and TEM characterizations demonstrated that Na+ complex with cholesterol-armed cyclen gave a particularly stable self-aggregate in aqueous solution and offered supramolecular environments effective for sensing and detection of amino acid anions. Various dansylamino acid derivatives (dansyl = 5-(dimethylamino)-1-naphthalenesulfonyl) were nicely accommodated in the helicate aggregates to give highly enhanced fluorescence signals, which could be detected by the naked eye at 10(-7) mol/L level. Their inclusion behaviors were analyzed by a Langmuir-type equation, indicating that enantiomer-selective inclusion occurred. MM/MD calculations and circular dichroism (CD) studies further suggested that cholesterol-armed cyclen helicates have chiral and hydrophobic cavities upon self-aggregation, in which the dansylamino acid anions were specifically accommodated. Since these helicates exhibited nonselective binding abilities in solvent extraction experiments of dansylamino acid anions, uncommon chiral recognition and sensing functions were generated by supramolecular alignments of the chiral metal helicates in the aqueous solutions.     

The photoelectrochemistry of platinum phthalocyanine films in aqueous media

Platinum phthalocyanine (PtPc) films applied to glassy carbon (GC) and platinum surfaces have been shown to exhibit complex photoelectrochemistry in aqueous media, acting as an n-type semi-conducting material. Using chopped polychromatic radiation and a lock-in amplifier to detect the modulated photocurrent, photo-responses were measured for PtPc films on GC in a variety of background electrolytes. In all instances the photo-responses were anodic over the voltage ranges used. Two peaks were seen in each sweep direction for the experiments performed in sulfuric acid and sodium hydroxide solutions. The origin of the photocurrent has been ascribed to the photo-oxidation of water in the electrolyte by positive holes produced under illumination, which accumulate at the PtPc/electrolyte interface. Photocurrent transients were also recorded and indicated some recombination of excitons within the system.     

On the Photostability of Cyanuric Acid and Its Candidature as a Prebiotic Nucleobase

Cyanuric acid is a triazine derivative that has been identified from reactions performed under prebiotic conditions and has been proposed as a prospective precursor of ancestral RNA. For cyanuric acid to have played a key role during the prebiotic era, it would have needed to survive the harsh electromagnetic radiation conditions reaching the Earth’s surface during prebiotic times (≥200 nm). Therefore, the photostability of cyanuric acid would have been crucial for its accumulation during the prebiotic era. To evaluate the putative photostability of cyanuric acid in water, in this contribution, we employed density functional theory (DFT) and its time-dependent variant (TD-DFT) including implicit and explicit solvent effects. The calculations predict that cyanuric acid has an absorption maximum at ca. 160 nm (7.73 eV), with the lowest-energy absorption band extending to ca. 200 nm in an aqueous solution and exhibiting negligible absorption at longer wavelengths. Excitation of cyanuric acid at 160 nm or longer wavelengths leads to the population of S_5,6 singlet states, which have ππ* character and large oscillator strengths (0.8). The population reaching the S_5,6 states is expected to internally convert to the S_1,2 states in an ultrafast time scale. The S_1,2 states, which have nπ* character, are predicted to access a conical intersection with the ground state in a nearly barrierless fashion (ca. ≤ 0.13 eV), thus efficiently returning the population to the ground state. Furthermore, based on calculated spin–orbit coupling elements of ca. 6 to 8 cm⁻¹, the calculations predict that intersystem crossing to the triplet manifold should play a minor role in the electronic relaxation of cyanuric acid. We have also calculated the vertical ionization energy of cyanuric acid at 8.2 eV, which predicts that direct one-photon ionization of cyanuric acid should occur at ca. 150 nm. Collectively, the quantum-chemical calculations predict that cyanuric acid would have been highly photostable under the solar radiation conditions reaching the Earth’s surface during the prebiotic era in an aqueous solution. Of relevance to the chemical origin of life and RNA-first theories, these observations lend support to the idea that cyanuric acid could have accumulated in large quantities during the prebiotic era and thus strengthens its candidature as a relevant prebiotic nucleobase.     

Thermodynamic Studies of Amino Acid–Denaturant Interactions in Aqueous Solutions at 298.15 K

As proteins and other biomolecules consisting of amino acid residues require external additives for their dissolution and recrystallization, it is important to have information about how such additives interact with amino acids. Therefore we have studied the interactions of simple model amino acids with the additives urea and guanidine hydrochloride in aqueous solutions at 298.15 K, using vapor pressure osmometry. During the measurements, the concentration of urea was fixed as ∼2 mol⋅kg⁻¹ and that of guanidine hydrochloride was fixed as ∼1 mol⋅kg⁻¹ whereas the concentrations of amino acids were varied. The experimental water activity data were processed to get the individual activity coefficients of all the three components in the ternary mixture. Further, the activity coefficients were used to get the excess Gibbs energies of solutions and Gibbs energies for transfer of either amino acids from water to aqueous denaturant solutions or denaturant from water to aqueous amino acid solutions. An application of the McMillan-Mayer theory of solutions through virial expansion of transfer Gibbs energies was made to get pair and triplet interaction parameter whose sign and magnitude yielded information about amino acid–denaturant interactions, relative to their interactions with water. The pair interaction parameters have been further used to obtain salting constants and in turn the thermodynamic equilibrium constant values for the amino acid–denaturant mixing process in aqueous solutions at 298.15 K. The results have been explained in terms of hydrophobic hydration, hydrophobic interactions and amino acid–denaturant binding.     

Radiolysis of Aqueous Ammonia Solutions: Mathematical Modeling

High Energy Chemistry - A mathematical model has been developed for the radiolysis of an aqueous solution containing the VVER primary coolant components ammonia and boric acid. The test results...     

六种添加剂对烟丝挥发性与半挥发性成分含量的影响

分别配制1%(质量分数,下同)的柠檬酸、苹果酸、乳酸水溶液以及5%的(NH4)2HPO4、K2CO3、柠檬酸钾水溶液.分别取100.0g烟丝,均匀喷洒10.0mL上述水溶液,经平衡、实验室模拟烘丝、萃取后,进行气相色谱-质谱测定,分析烟丝中挥发性和半挥发性香味成分含量的变化.结果表明,喷洒柠檬酸和K2CO3水溶液可显著改变烟丝的化学成分含量.烟丝经K2CO3水溶液喷洒后,游离态的尼古丁含量大幅增加,醇类组分、巨豆三烯酮含量有所升高,酸类组分和酯类组分含量略有降低;而经柠檬酸水溶液喷洒后的烟丝的酸类、醇类和酯类组分含量升高,尼古丁含量下降.     

Feasibility of monitoring acetic acid process using near-infrared spectroscopy

Near-infrared (NIR) spectroscopy has been utilized to demonstrate its feasibility for the measurement of major components in the acetic acid process. In order to simulate the acetic acid process, synthetic mixtures were prepared from five different components: acetic acid, methyl acetate, methyl iodide, water, and potassium iodide. Partial least squares (PLS) regression was utilized to differentiate the spectral characteristics as well as to quantify each component for the mixtures. The spectral features of acetic acid, methyl acetate, methyl iodide, and water are noticeably different with each other over the entire NIR region. The quantity of iodide ion, which does not absorb NIR radiation, was determined using the wavelength shift and intensity change of water absorption band caused by the change of iodide ion concentration. The PLS calibration results of the five components show good correlation with reference data. They also demonstrate the technical feasibility of NIR spectroscopy for monitoring important components in the acetic acid process.     

含丙烯酸的共聚乳液的碱增稠过程与流动行为

合成了一系列苯乙烯、丙烯酸丁酯和丙烯酸共聚乳液样品，对乳液的加氢滴定过程及其流变行为进行了讨论。结果表明，氨的加入使含羧基乳液的增稠效应随共聚物中羧基含量的增加和柔性链段的增多而增大；随着氨的加入量的递增，乳液的ｐＨ值和粘度多呈两次突变；乳液因聚合物组成和ｐＨ值不同而具有不同的流动特性。