Synthesis and characterization of isotopically enriched methylmercury (CH3201Hg+)

A simple procedure for the synthesis of an important standard, isotopically enriched methylmercury, which is not commercially available, has been established successfully. The isotopically enriched standard synthesized is utilized in conventional isotope dilution mass spectrometry (IDMS), as well as in speciated IDMS (SIDMS), for determination of the true concentration of methylmercury in environmental samples. The CH₃²⁰¹Hg⁺ standard has been synthesized from commercially available ²⁰¹HgO and tetramethyltin. The synthesis time required is 1 h at 60°C. The product is highly pure, yielding more than 90% as ²⁰¹Hg in CH₃²⁰¹Hg⁺. Hazardous dimethylmercury does not occur during this synthesis procedure. The product synthesized was analyzed using high‐performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (ICP‐MS) and ICP‐MS alone in order to determine its concentration, isotopic composition and purity. The stability of the product was also evaluated for over 6 months and found to be stable at 4°C in the dark. The isotopically enriched methylmercury synthesized can be used in SIDMS and IDMS analyses as a standard. Copyright © 2003 John Wiley & Sons, Ltd.     

Retention mechanism of L-glutamide-derived noncrystalline stationary phases in reversed-phase high-performance liquid chromatography and application for separation of nucleic acid constituents

Double alkylated L-glutamide-derived noncrystalline stationary phases Sil-DSG and Sil-DBG have been prepared by coupling N',N'-dioctadecyl-N-[4-carboxybutanoyl]-L-glutamide (DSG) and N',N',-dibutyl-N-[4-carboxybutanoyl]-L-glutamide (DBG) with aminopropylated silica (Sil-APS). TEM observations of DSG and DBG showed that lipid DSG can aggregate in organic solvents (methanol, chloroform, toluene, etc.) and self-assembled nano fibers are observed while such fibrous aggregations are not observed for DBG. The resulting chromatographic data have been provided information about its selective interaction with guest molecules (PAHs) in RP-HPLC. We have observed that the carbonyl groups in Sil-DSG exist in ordered state by forming a condensing thin layer over silica surface while DBG cannot form such an ordered state due to its lower order of short alkyl chain. The ordered carbonyl groups present in Sil-DSG promotes multiple carbonyl pi-benzene pi interactions with guest PAHs isomers which enhance the selectivity for these compounds. The contribution of pi-pi interactions was also supported by the substantial effects on the selectivity of benzene and nitrobenzenes. The effect of pi-electron containing solvent on the retention behavior of the PAHs was also studied. The selectivity for nucleic acid constituents, i.e. nucleosides and its bases were also evaluated by Sil-DSG and the selectivity for these compounds on Sil-DSG was compared with the selectivity of conventional polymeric ODS phase. It has been found that Sil-DSG provided higher selectivity for nucleic acid constituents than polymeric ODS and that HPLC packing materials can be efficiently employed for routine analysis of these compounds. The effect of methanol content on the separation behavior of nucleosides was also studied.     

One-step synthesis of labeled sugar nucleotides for protein O-GlcNAc modification studies by chemical function analysis of an archaeal protein

Herein we present the chemical function analysis of a recombinant sugar nucleotidyltransferase from the hyperthermophile Pyrococcus furiosus and its use in the one-pot synthesis of chloroacetyl- and alkyne-tagged analogues of uridinediphospho-N-acetylglucosamine (UDP-GlcNAc). The gene was originally annotated as a glucose-1-phosphate deoxythymidylyltransferase; however, kinetic analysis of a panel of sugar-1-phosphates with the protein shows that it is better described as a bifunctional protein that synthesizes UDP-GlcNAc from glucosamine-1-phosphate and acetyl coenzyme A (CoA). A new mass-spectrometry-based assay for the rapid analysis of the acyltransferase activity demonstrates that the enzyme can also accept cheaper truncated N-acetylcysteamine thioester substrates in place of the natural acetyl CoA. The enzyme can tolerate alkyne or chloride substitutions in the acyl moiety, thereby allowing the facile synthesis of tagged sugar nucleotides for future use in protein O-GlcNAc modification studies.     

Ultrasound-induced membrane lipid peroxidation and cell damage of Escherichia coli in the presence of non-woven TiO2 fabrics

A non-woven titanium dioxide (TiO₂) fabric was applied to disinfection by ultrasound (US) irradiation, and the disinfection efficiency and lipid peroxidation of Escherichia coli (E. coli) cell membrane were evaluated to investigate the killing process. The addition of non-woven TiO₂ fabric enhanced hydroxyl (OH) radical generation and disinfection efficiency. Judging from the disinfection experiments using glutathione or t-butanol as a radical scavenger, the OH radical played a major role in cell killing in sonodynamic disinfection with non-woven TiO₂ fabric. Moreover, to understand the detailed killing process, damage to cell membrane was also evaluated using a diphenyl-1-pyrenylphosphine (DPPP) fluorescent probe, which detects the membrane’s lipid peroxidation. The addition of non-woven TiO₂ fabric aggravated this peroxidation. This aggravation was caused by the OH radical according to an assay using a radical scavenger. From these results, it was concluded that non-woven TiO₂ fabric as a sonocatalyst promoted peroxidation of the polyunsaturated phospholipid component of the lipid membrane initially and induced a major disorder in the E. coli cell membrane under US irradiation.     

Evaluation of selectivity for l-glutamide-derived highly ordered assemblies in reversed-phase high-performance liquid chromatography

Two dioctadecyl l-glutamic acid derivatives with amide and ester type bondings have been synthesized and immobilized from 3-aminopropyltrimethoxysilane (APS) grafted silica (Sil-APS) to be used in reversed-phase high-performance liquid chromatography (RP-HPLC). Subsequent studies showed that dioctadecyl-l-glutamide derivative (GLN) can self-assemble into highly ordered structures by forming three-dimensional fibrillar aggregates as observed in scanning and transmission electron microscopes (SEM and TEM). Variable temperature ¹H NMR and FT-IR spectra of organogel revealed that the special aggregation morphology shown by GLN was stabilized by inter and or intra molecular hydrogen bonding among amide moieties. However, such ordered aggregated or self-assembled structures were not observed for the dioctadecyl-l-glutamate (GLU) derivative. The stationary phases Sil-GLN and Sil-GLU were characterized by DRIFT, elemental analysis, TGA, and ¹³C and ²⁹Si CP-MAS NMR spectroscopic measurements. The chromatographic selectivity for both stationary phases was evaluated from the retention studies of different size and shape polycyclic aromatic hydrocarbons (PAHs). The chromatographic experiment for PAHs and geometrical isomers in RP-HPLC showed that Sil-GLN demonstrated extremely enhanced selectivity than Sil-GLU. The higher selectivity attributed by Sil-GLN has been brought by multiple π-π interactions among the π-electrons of the grafted organic phase and π-electrons of the guest PAHs molecules. Thermodynamic studies for linear and nonlinear PAHs revealed that the retention behavior does not change over a temperature range from 10 to 60 °C for both stationary phases.     

Exploring k and ? with R–Equation Model Using Elliptic Relaxation Function

An extended version of the isotropic R?Cequation model accompanied by an elliptic relaxation approach to account for the distinct effects of low-Reynolds number (LRN) and wall proximity is proposed. The turbulent kinetic energy k and the dissipation rate ? are evaluated using the R ( $=k^2/\tilde{\epsilon}$ ) transport equation together with some empirical relations. The eddy viscosity formulation maintains the positivity of normal Reynolds stresses and the Schwarz?? inequality for turbulent shear stresses. The model coefficients/functions preserve the anisotropic characteristics of turbulence in the sense that they are sensitized to rotational and nonequilibrium flows. The model is validated against a few well-documented flow cases, yielding predictions in good agreement with the direct numerical simulation (DNS) and experimental data. Comparisons indicate that the present model offers some improvement over the Spalart?CAllmaras one?Cequation model and competitiveness with the SST k?C?? model.     

Combination of LFP‐TRIR spectroscopy and DFT computation as a tool to determine the intermediate during the photooxidation of triarylphosphine

Laser flash photolysis‐time‐resolved infrared spectroscopy (LFP‐TRIR) was performed on an acetonitrile or dichloromethane solution of triarylphosphines, Ar₃P, in air. A transient spectrum consisting of several absorption bands appeared in the region of 1050–1300 cm^?1 on the TRIR on a microsecond timescale, which disappeared on a millisecond timescale. To identify the observed transient intermediate, the IR spectra of possible intermediates of the photoreaction were simulated by theoretical calculations based on density functional theory (DFT). The IR spectrum simulated for the phosphine peroxidic radical cation, Ar₃P⁺OO^?, well predicted the observed IR spectrum, showing that Ar₃P⁺OO^? is formed as a transient intermediate upon the LFP of Ar₃P in air. Copyright © 2014 John Wiley & Sons, Ltd.     

Nickel(II), copper(II), palladium(II) and platinum(II) complexes of bidentate SN ligands derived from S-alkyldithiocarbazates and the X-ray crystal structures of the [Ni(tasbz)2] and [Cu(tasbz)2] · CHCl3 complexes

New complexes of general empirical formula, [M(NS)₂] · nCHCl₃ (M = Ni^II, Cu^II, Pd^II or Pt^II; NS = anionic form of the thiophene-2-aldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazate; n = 0, 1) have been synthesized and characterized by physico-chemical techniques. Magnetic and spectroscopic evidence support a square-planar structure for these complexes. The crystal structures of the [Ni(tasbz)₂] and [Cu(tasbz)₂] · CHCl₃ complexes (tasbz = anionic form of the thiophene-2-aldehyde Schiff base of S-benzyldithiocarbazate) have been determined by X-ray diffraction. Both complexes have a trans-planar structure in which the two Schiff base ligands are coordinated to the metal(II) ion as uninegatively charged bidentate ligands via the thiolate sulfur and the azomethine nitrogen atoms. This revised version was published online in June 2006 with corrections to the Cover Date.     

Assessment of terrestrial radionuclides in the sandy soil from Guliakhali beach area of Chattogram,Bangladesh

Journal of Radioanalytical and Nuclear Chemistry - A study was conducted to assess the concentrations of primordial radionuclides in fifteen sandy soil samples collected from a newly discovered...