Validated method using liquid chromatography-electrospray ionization tandem mass spectrometry for the determination of contamination of the exterior surface of vials containing platinum anticancer drugs

Contamination of the exterior surface of vials of cytostatic drugs by the drugs themselves is a potential hazard to human health. This study developed a validated method using liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) for the determination of contamination of the exteriors of vials of cisplatin and carboplatin. Large Alpha^® sampling swabs were employed to wipe the vial exterior. Cisplatin or carboplatin and gold(III) as an internal standard were derivatized by N,N-diethyldithiocarbamate (DDTC). Pt(DDTC)₃⁺ and Au(DDTC)₂⁺ were monitored by the respective transitions of m/z 639.3-490.9 and 493.0-345.0, respectively. Each separation was completed within 9 min using a 3 μm particle ODS-column. Calibration curves for cisplatin and carboplatin were linear over concentration ranges of 30-10,000 and 30-30,000 pg vial⁻¹, respectively. The accuracies and precisions were 96.1-102.5% and within 8.2% for intra-assay and 99.6-103.3% and within 7.6% for inter-assay, respectively. Their lower limit of quantification was 30 pg vial⁻¹. Amounts of 0.17-17.0 ng vial⁻¹ as cisplatin and 0.48-794 ng vial⁻¹ as carboplatin were detected from the exterior surface of the vials. This validated method using LC-ESI-MS/MS for the determination of platinum anticancer drugs is helpful for monitoring contamination of the exterior surface of drug vials.     

ChemInform Abstract: The Crystal Structures of m,o‐Ce3Pt4Sn6 and Ce1‐xPt6Al13+2x.

Single crystals of Ce₃Pt₄Sn₆ (I) and Ce_1‐xPt₆Al_13+2x (x = 0.207, (II)) are isolated by mechanical fragmentation of specimens grown from self‐fluxes (Sn or Al, resp.) by slow cooling from the melt.     

Modification of poly(vinyl chloride). XIII. Crosslinking of poly(vinyl chloride) with dithiols and properties of the crosslinked products

PVC was crosslinked by immersing PVC–dithiol blends in ethylenediamine at 30°C. Properties of the products depended on the chain length and chemical structure of the crosslinkage and on the molecular weight of the polymer chain between crosslinks M_c. Crosslinking by the agent of soft structure and long molecular chain resulted in high tensile strength at break and impact strength and low brittle temperature. The use of the crosslinking agent of short molecular chain gave high yield strength, Young's modulus, and heat distortion temperature. The relation of M_c and the chemical structure of the crosslinks to the properties of the crosslinked rigid polymer was discussed in regard to the crosslinking effect and plasticizing effect.     

Adsorption and micellization behavior of novel gluconamide-type gemini surfactants

The adsorption and micellization behavior of novel sugar-based gemini surfactants (N,N(')-dialkyl-N,N(')-digluconamide ethylenediamine, Glu(n)-2-Glu(n), where n is the hydrocarbon chain length of 8, 10 and 12) has been studied on the basis of static/dynamic surface tension, fluorescence, dynamic light scattering (DLS) and cryogenic transmission electron microscope (cryo-TEM) data. The static surface tension of the aqueous Glu(n)-2-Glu(n) solutions measured at the critical micelle concentration (cmc) is observed to be significantly lower than that of the corresponding monomeric surfactants. This suggests that the gemini surfactants, newly synthesized in the current study, are able to form a closely packed monolayer film at the air/aqueous solution interface. The greater ability in the molecular association is supported by the remarkably (approximately 100-200 times) lower cmc of the gemini surfactants compared with the corresponding monomeric ones. With a combination of the fluorescence and DLS data, a structural transformation of the Glu(n)-2-Glu(n) micelles is suggested to occur with an increase in the concentration. The cryo-TEM measurements clearly confirm the formation of worm-like micelles of Glu(12)-2-Glu(12) at the concentration well above the cmc.     

Molecular structure of 1,1-difluoroethylene as determined by gas phase electron diffraction and microwave data

The structure of 1,1-difluoroethylene was determined, from gas phase electron diffraction data obtained independently in Leiden and Tokyo and the rotational constants of F₂CCH₂, F₂CCHD and F₂CCD₂ derived from the microwave study by Chauffoureaux. The two electron diffraction data agreed without significant discrepancy. From a joint least squares analysis of the diffraction and microwave data, the following r_g bond distances and r_z bond angles were derived: CC = 1.340 ± 0.006 Å, C-F = 1.315 ± 0.003 Å, C-H = 1.091 ± 0.010 Å, ∠C-C-F = 124.7 ± 0.3°, ∠C-C-H = 119.0 ± 0.4°, where the uncertainties represent estimated limits of error.     

Determination of glutamate-pyruvate transaminase activity in blood serum with a pyruvate oxidase/poly(vinyl chloride) membrane sensor

Pyruvate oxidase (E.C. 1.2.3.3.) is immobilized by adsorption on a wet PVC membrane. Glutamate-pyruvate transaminase activity (5–1600 IU l^?1) in serum is determined by a pyruvate oxidase sensor consisting of the immobilized pyruvate oxidase coupled to a platinum electrode for measuring hydrogen peroxide, after an l-alanine—α-ketoglutarate reaction. The assay requires ?60 s, and has a precision of 2–3%. Endogenous pyruvate should not interfere if measurements are made > 30 s after starting the reaction.     

Phomactins K–M,three novel phomactin-type diterpenes from a marine-derived fungus

Three novel diterpenes, phomactins K–M (1–3), were isolated from the cultures of an unidentified marine-derived fungus. The structures of 1–3 were elucidated from spectroscopic data (NMR, MS, IR), and the absolute configurations of 1, 2, and the relative configuration of 3 were determined by X-ray diffraction analysis.     

Heterogeneous polycondensation for composition control of poly(p‐mercaptobenzoyl‐co‐p‐benzamide) by shearing

Composition control of aromatic poly(thioester‐amide) was examined by the reaction‐induced phase separation during polymerization of S‐acetyl‐4‐mercaptobenzoic acid (AMBA) and p‐acetylaminobenzoic acid (AABA) in aromatic solvent. The poly(thioester‐amide)s were obtained as precipitates and their yields became lower at the middle range of the content of AMBA in feed (χ_f). The contents of p‐mercaptobenzoyl (MB) moiety (χ_p) in the precipitates prepared without shearing were in good agreement with the χ_f values. In contrast to this, the χ_p values of the precipitates prepared at χ_f of 50–70 mol % under shearing were much lower than the χ_f values. The reaction rate of AMBA increased with shearing, whereas that of AABA was unchanged by shearing. This shearing effect on the reaction rates accelerated to form the homo‐oligomers. The solubility of MB oligomers enhanced by shearing, whereas that of p‐benzamide oligomers did not enhance owing to the strong interaction through hydrogen bonding. The MB oligomers were inhibited to be precipitated, resulting in the lower χ_p values than the χ_f values. The composition could be controlled by the application of the shearing to the heterogeneous polymerization. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4301–4308