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.     

Salt effects in the aqueous alkaline hydrolysis of N-hydroxyphthalimide. Kinetic evidence for the ion-pair formation

The effects of the concentrations of LiCl, NaCl, KCl, CsCl, Na₂CO₃, BaCl₂, and Me₄NCl on the rates of reactions of hydroxide ion with ionized N-hydroxyphthalimide (NHP) at 30°C and in a H₂O–MeCN solvent containing 98%, v/v, H₂O reveal a nonlinear increase in observed rate constants with increase in salt concentrations. The observed rate constants are highly sensitive to the valence state of cations and almost insensitive to the valence state of anions of the salts. These observations are explained in terms of ion-pair formation between cations and NHP^?.     

The influence of synthetic conditions on the stability of methotrexate-monoclonal antibody conjugates determined by reversed phase high performance liquid chromatography.

Methotrexate (MTX) has been convalently attached to an IgG-type monoclonal antibody (791T/36) directed to tumour-associated antigen gp72. Conjugates were synthesized by the active ester method using MTX N-succinimidyl ester at various pH values (7.5-10.5). Following purification by gel filtration, high performance liquid chromatography was used to assess the free drug or its derivatives in samples of MTX-791T/36 conjugates previously treated (or not) with hydroxylamine. Quantitative analysis, performed on a reversed phase column (pore size 300 A) with isocratic acetonitrile-sodium acetate buffer (pH 4.8) as mobile phase, indicated no detectable amount of free methotrexate in hydroxylamine-treated conjugates even six months after their preparation. Similar observations were made with conjugates, whose synthesis were performed at pH greater than or equal to 10. In contrast, the presence of increasing amounts of drug/metabolite could be demonstrated in samples produced at lower pH values. Based on these findings, the pH-dependent kinetics of MTX release has been determined and used to design conditions under which stable MTX-791T/36 conjugates could be prepared without hydroxylamine reaction.     

Studies on recoil proton tracks in NTA films with the T(d,n)He reaction

Recoil proton tracks in nuclear emulsion are counted by scanning them using strip, square or circular field of view of optical microscope. In this paper, the overestimate due to the edge effects in counting recoil proton tracks at different neutron energies produced from the T(d,n)⁴He reaction has been determined by measuring the true track density in NTA film. The overestimate has also been calculated using the measured value of the mean projected track length (L) in the film. The percentage of measured overestimates has been compared with those obtained by calculation and the results agree reasonably well. Fading effect in NTA film has been studied and found to be 22% more in the summer than in the winter season. A great reduction in fading rate could be achieved if the films are desiccated and sealed in highly pure dry nitrogen maintained at an over-pressure of 1000 Pa to reduce water vapour ingress. After the edge effect correction, the sensitivity of NTA film has been calculated from (1.72±0.08)×10⁻³ tracksn⁻¹ to (1.97±0.16)×10⁻³ tracksn⁻¹ in the neutron energy ranges from 15.91 to 18.88 MeV. The response was found to be from 0.24±0.02 trackscm⁻² permSv to 0.26±0.01 trackscm⁻² permSv in the same energy range.     

Novel route to synthesis of allyl starch and biodegradable hydrogel by copolymerizing allyl‐modified starch with methacrylic acid and acrylamide

Maize starch was modified by allyl chloride adopting an interfacial reaction technique with cetyltrimethyl ammonium bromide as a phase‐transfer catalyst and pyridine as an acid acceptor. The degree of substitution was determined from an increasing carbon content of the modified starch. The percentage of carbon and hydrogen of the allyl‐modified starch was estimated by elemental analysis (C, H, and N), and the product characterization was done through ¹H NMR and ¹³C NMR analyses. The allyl‐modified starch was then copolymerized with methacrylic acid and a combination of methacrylic acid and acrylamide at 50 and 70 °C with potassium persulfate as an initiator. The copolymer thus formed swelled in distilled water after neutralization with sodium carbonate. The percentage of absorption capacity of the hydrogels was determined with distilled water and 0.9% NaCl solution. The highest percentage of absorption, 6500%, was achieved for the developed hydrogel containing allyl starch and acrylic monomer in a 1.7:1 w/w ratio and acrylic monomer, namely, methacrylic acid and acrylamide in a 3.2:1 w/w ratio. The study on biodegradability of the developed hydrogel showed that the hydrogel is degradable in the presence of diastase (amylase). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1650–1658, 2003     

MITATT mode in DDR heterostructure Impatt

Large signal characterisation of double heterostructure DDR Impatt diode has been carried out in the millimeter-wave range considering the MITATT mode of operation. The structure of the device is p⁺-p₂-p₁-n₁-n₂-n⁺ where impact ionisation and tunneling takes place in the p₁-n₁ region. In this study we have considered two well-known heterostructures, e.g., InP/GaInAs/InP and InP/InGaAsP/InP and one nonconventional structure GaAs/InP/GaAs. The theoretical results of the performances of these devices as regards of output power, efficiency, and negative conductance revealed that the structures are quite promising as the source of power in the millimeter-wave range. The analysis may be used for other mm wave DDR heterostructure Impatts.     

An optimal repeat inspection plan with several classifications

Multicharacteristic critical components exist in many systems. Such components could be a part of an aircraft, space shuttle or a gas ignition system. A component is critical if it causes disaster or a very high cost upon failure. In this paper, a new inspection plan for critical multicharacteristic components is presented. A mathematical model that depicts the plan is developed. An algorithm is proposed for finding the optimal number of repeat inspections and the sequence of characteristics for inspection that minimizes expected total cost per accepted component. The expected cost consists of the cost of inspection and the cost of misclassifications. The inspection plan and the model developed generalize existing models in the literature and provide a more realistic formulation. An example is given to demonstrate the plan and the model.     

Poly(ortho‐phenylene ethynylene)s: Synthetic accessibility and optical properties

Poly(ortho‐phenylene ethynylene)s (PoPEs) have been synthesized via an in situ activation/coupling AB′ polycondensation protocol. The resulting polymers have been characterized by several analytical methods and are shown to have no structural defects. Although the Sonogashira–Hagihara polycondensation reaction is less efficient than for the preparation of the corresponding meta‐ and para‐linked polymers, presumably because of steric hindrance caused by the ortho substituents, the process can be accelerated by the use of microwave irradiation. Optical spectroscopy indicates solvent‐dependent conformational changes between extended transoid and helical cisoid conformations, providing the first experimental evidence for solvophobically driven folding of the PoPE backbone. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1619–1627, 2006