Study of particle size distribution and formation mechanism of radioactive aerosols generated in high-energy neutron fields

The size distributions of ³⁸Cl, ³⁹Cl, ⁸²Br and ⁸⁴Br aerosols generated by irradiations of argon and krypton gases containing di-octyl phthalate (DOP) aerosols with 45 MeV and 65 MeV quasi-monoenergetic neutrons were measured in order to study the formation mechanism of radioactive particles in high energy radiation fields. The effects of the size distribution of the radioactive aerosols on the size of the added DOP aerosols, the energy of the neutrons and the kinds of nuclides were studied. The observed size distributions of the radioactive particles were explained by attachment of the radioactive atoms generated by the neutron-induced reactions to the DOP aerosols.     

Chlorofluorocarbons adsorption structures and energetic over faujasite type zeolites—a first principle study

Adsorption of ozone depleting chlorofluorocarbons (CFC) over zeolite is of major global environmental concern. The current communication describes first-principle calculation performed on faujasite models to investigate the nature of CFCs including fluoro, chlorofluoro and hydrofluoro/chloro carbons (CF₄, CF₃Cl, CF₂Cl₂, CFCl₃, CHF₃, CHCl₃) adsorption. Experimentally it is observed that separation of halocarbons are possible using Na–Y, though the cause is unknown. Reactivity index within the helm of Hard Soft Acid Base (HSAB) principle was used to monitor the activity of the interacting CFCs using Density Functional Theory (DFT) to propose a qualitative order. The importance of both H-bonding and cation–F/Cl interactions in determining the low-energy sorption sites were monitored and rationalized. The host guest interactions show a distinctive difference between the adsorption phenomenon between H–Y and Na–Y and as well for Cl and F. It is observed that Cl has more favorable interaction with hydrogen of H–Y compared to Na–Y and for F the situation is just reversed. To validate this trend periodic optimization calculations were performed. The interaction energy as obtained matches well with the reactivity index order resulted from cluster calculations. This study is a combination of DFT and periodic calculation to rationalize the electronic phenomenon of the interaction process.     

Simultaneous electroanalysis of dopamine and ascorbic acid using poly (N,N-dimethylaniline)-modified electrodes

Glassy carbon (GC) electrode is modified with an electropolymerized film of N,N-dimethylaniline (DMA). This polymer (PDMA) film-coated GC electrode is used to electrochemically detect dopamine (DA) in the presence of ascorbic acid (AA). Polymer film has the positive charge in its backbone, and in neutral solution DA exists as the positively charged species whereas AA exists as the negatively charged one. In cyclic voltammetric measurements, favorable ionic interaction (i.e., electrostatic attraction) between AA and PDMA film causes a large negative shift of the oxidation potential for AA compared to that at the bare electrode. Oxidation potential for DA is positively shifted due to the electrostatic repulsion. The PDMA film shows hydrophobicity by incorporating uncharged hydroquinone molecule within the film. DA is also incorporated into the film due to hydrophobic attraction even though DA has a positive charge. The responses of DA and AA at polymer-modified electrodes largely change with the concentration of the monomer (i.e., 0.2, 0.1 and 0.05 M DMA) used in electropolymerization and thus with the film thickness. Hydrophobicity of the polymer film shows great influence on the voltammetric responses of both DA and AA. In square wave voltammetric measurements, the PDMA film-coated electrode can separate the DA and AA oxidation potentials by about 300 mV and can detect DA at its low concentration (e.g., 0.2 microM) in the presence of 1000 times higher concentration of AA, which is close to the physiological level. AA oxidizes at more negative potential than DA. The electrode response is not affected by the oxidized product of AA. So unlike the bare electrode, the fouling effect as well as the catalytic oxidation of AA by the oxidized form of DA are eliminated at the PDMA film-coated GC electrode. The electrode exhibits the stable and sensitive response to DA.     

Analysis of the interaction between an alpha (1----6)dextran-specific mouse hybridoma antibody and dextran B512 by affinity electrophoresis.

Carbohydrates are common environmental antigens. As dextran B512 is composed of a repeating structure of simple antigenic determinants, it is widely used to study the immunochemical properties of immunoglobulins. Two-dimensional affinity electrophoresis patterns of a mouse monoclonal antidextran antibody (35.8.2H; IgG1, BALB/c) were produced to obtain insights into the microheterogeneity of the monoclonal antibody. The monoclonal antibody was separated into about six spots which had an identical affinity to dextran B512, but differed in their isoelectric points (pI). In addition, the pH dependence of the binding affinity of this antidextran to dextran B512 was examined. By comparing affinities obtained by affinity electrophoresis between weakly basic (pH 9.5) and weakly acidic (pH 3.8) discontinuous buffer systems, the latter showed an affinity about 500 times lower than the former. The change in the affinity was investigated with a continuous pH gradient by an affinity titration curve and was seen to change markedly at about pH 6. This suggests that the histidine at residue 34 in the light-chain CDR1 is largely responsible for the dextran binding.     

Electrochemically Polymerized N,N-Dimethylaniline Films Containing Tris-(Bathophenanthroline Disulfonato)Iron(II/III) Complexes

The electropolymerization of N, N-dimethylaniline (DMA) was carried out in an aqueous CF₃COONa solution (pH 1.0) containing DMA in the presence of tris(bathophenanthroline disulfonato)iron(II), Fe(bphen)₃ ^4-. Poly(N, N-dimethylanilinium trifluoroacetate) (PDMA) film was formed on electrode surfaces and, at the same time, Fe(bphen)₃ ^4- ions were stably confined in the formed PDMA film by electrostatic interaction between them and the positively charged quaternary ammonium sites of the PDMA film. The PDMA-Fe(bphen)₃ ^4-/3- film thus prepared displayed well-defined reversible electroactivity and electrochromic properties ascribable to those of the Fe(bphen)₃ ^4-/3- couple confined in the film. The PDMA-Fe(bphen)₃ ^4- film is red, and the PDMA-Fe(bphen)₃ ^3- film is colorless. The response rate of the color change to a potential pulse was found to be correlated with the kinetic parameters characterizing the rate of the overall charge-transfer reaction at the PDMA-Fe(bphen)₃ ^4-/3- film-coated electrode, that is, the apparent diffusion coefficient (D _app) for the homogeneous charge-transport process within the film and the standard rate constant (k) of the heterogeneous electron-transfer reaction at the electrode/film interface. For the PDMA-Fe(bphen)₃ ^4-/3- film with larger k° and D _app values, the response rate of the color change was larger, Further, k°, D _app, and response rate depended on the concentration (C°) of the Fe(bphen)₃ ^4- (or Fe(bphen)₃ ^3-) confined in the PDMA film; and at a given film thickness, the lower C°, the higher were k°, D _app, and response rate. At a given C°, the thinner the film thickness, the greater was the response rate.     

An Organic/Inorganic Hybrid Polymer

Poly(N-acetylethylenimine) (polyoxazoline) (POZO) with a terminal triethoxysilyl group was successfully synthesized by the ring-opening polymerization of 2-methyl-2-oxazoline followed by termination with 3-aminopropyltriethoxysilane. Triethoxysilyl-terminated telechelic POZO was prepared by using a bifunctional initiator. These silane coupling POZOs were subjected to acid-catalyzed cohydrolysis polymerization with tetraethoxysilane by the so-called “sol-gel” method to produce a novel organic/inorganic hybrid polymer (block copolymer), which was a homogeneous transparent/glassy composite material. The obtained hybrid showed higher hydrophilic properties compared with silica gel without POZO segments. On the other hand, a hybrid polymer consisting of poly(2-ethyl-2-oxazoline) and silica gel, which absorbed both water and organic solvents, showed amphiphilic properties. POZO segments were eliminated by pyrolysis of the present hybrid polymer to produce a silica with micropores.     

Novel Synthesis and Structures of Amines and Triazole-Derived Glycoside and Nucleoside Derivatives of Phosphanyl Sugar Analogs

ABSTRACT

3-Methyl-1-phenyl-2-phospholene and 1-phenyl-2-phospholene 1-oxides were converted into 2-bromo-3-hydroxy-3-methyl-1-phenylphospholane and 2-bromo-3-hydroxy-1-phenylphospholane 1-oxide (1-bromo-1,3,4-trideoxy-1,4-C-[(R, S)-phenylphosphinylidene]-glycero-tetrofuranose) by the action of bromine in aqueous medium. The bromo substituent of the phospholane was substituted by treatment with amines or an azide anion to afford novel glycoside derivatives of phosphanyl sugar analogs such as 2-amino-3-hydroxy-1-phenylphospholane (3,4-dideoxy-1,4-C-[(R, S)-phenylphosphinylidene]-glycero-tetrofuranosylamine) and 2-azido-3-hydroxy-3-methyl-1-phenylphospholane 1-oxides with retention of the configuration. The 1,3-dipolar cycloaddition of the 2-azido derivative of the phospholane with alkynes gave 3-hydroxy-3-methyl-1-phenyl-2-(triazol-1′-y1)phospholane 1-oxides as a novel triazole-derived nucleoside of phosphanyl sugar analogs. The structure of the glycoside and nucleoside derivatives of the phosphanyl sugar analogs prepared was deterimined from IR, NMR, and X-ray crystallography analysis.     

Probing DNA Mismatched and Bulged Structures by Using 19F NMR Spectroscopy and Oligodeoxynucleotides with an 19F‐Labeled Nucleobase

In this study, DNA local structures with bulged bases and mismatched base pairs as well as ordinary full‐matched base pairs by using ¹⁹F NMR spectroscopy with ¹⁹F‐labeled oligodeoxynucleotides (ODNs) were monitored. The chemical shift change in the ¹⁹F NMR spectra allowed discrimination of the DNA structures. Two types of ODNs possessing the bis(trifluoromethyl)benzene unit (F‐unit) at specified uridines were prepared and hybridized with their complementary or noncomplementary strands to form matched, mismatched, or bulged duplexes. By using ODN F1, in which an F‐unit was connected directly to a propargyl amine‐substituted uridine, three local structures, that is, full‐matched, G–U mismatch, and A‐bulge could be analyzed, whereas other structures could not be discriminated. A molecular modeling study revealed that the F‐unit in ODN F1 interacted little with the nucleobases and sugar backbone of the opposite strand because the linker length between the F‐unit and the uridine base was too short. Therefore, the capacity of ODN F1 to discriminate the DNA local structures was limited. Thus, ODN F2 was designed to improve this system; aminobenzoic acid was inserted between the F‐unit and uridine base so the F‐unit could interact more closely with the opposite strand. Eventually, the G‐bulge and T–U mismatch and the three aforementioned local structures could be discriminated by using ODN F2. In addition, the dissociation processes of these duplexes could be monitored concurrently by ¹⁹F NMR spectroscopy.     

Anthraquinone-sensitized photooxidation of 5-methylcytosine in DNA leading to piperidine-induced efficient strand cleavage

One-electron photooxidations of 5-methyl-2'-deoxycytidine (d(m)C) and 5-trideuteriomethyl-2'-deoxycytidine ([D(3)]d(m)C) by sensitization with anthraquinone (AQ) derivatives were investigated. Photoirradiation of an aerated aqueous solution containing d(m)C and anthraquinone 2-sulfonate (AQS) afforded 5-formyl-2'-deoxycytidine (d(f)C) and 5-hydroxymethyl-2'-deoxycytidine (d(hm)C) in good yield through an initial one-electron oxidation process. The deuterium isotope effect on the AQS-sensitized photooxidation of d(m)C suggests that the rate-determining step in the photosensitized oxidation of d(m)C involves internal transfer of the C5-hydrogen atom of a d(m)C-tetroxide intermediate to produce d(f)C and d(hm)C. In the case of a 5-methylcytosine ((m)C)-containing duplex DNA with an AQ chromophore that is incorporated into the backbone of the DNA strand so as to be immobilized at a specific position, (m)C underwent efficient direct one-electron oxidation by the photoexcited AQ, which resulted in an exclusive DNA strand cleavage at the target (m)C site upon hot piperidine treatment. In accordance with the suppression of the strand cleavage at 5-trideuterio-methylcytosine observed in a similar AQ photosensitization, it is suggested that deprotonation at the C5-methyl group of an intermediate (m)C radical cation may occur as a key elementary reaction in the photooxidative strand cleavage at the (m)C site. Incorporation of an AQ sensitizer into the interior of a strand of the duplex enhanced the one-electron photooxidation of (m)C, presumably because of an increased intersystem crossing efficiency that may lead to efficient piperidine-induced strand cleavage at an (m)C site in a DNA duplex.