Bioanalytical procedures for determination of drugs of abuse in blood

Determination of drugs of abuse in blood is of great importance in clinical and forensic toxicology. This review describes procedures for detection of the following drugs of abuse and their metabolites in whole blood, plasma or serum: Δ9-tetrahydrocannabinol, 11-hydroxy-Δ9-tetrahydrocannabinol, 11-nor-9-carboxy-Δ9-tetrahydrocannabinol, 11-nor-9-carboxy-Δ9-tetrahydrocannabinol glucuronide, heroin, 6-monoacetylmorphine, morphine, morphine-6-glucuronide, morphine-3-glucuronide, codeine, amphetamine, methamphetamine, 3,4-methylenedioxymethamphetamine, N-ethyl-3,4-methylenedioxyamphetamine, 3,4-methylenedioxyamphetamine, cocaine, benzoylecgonine, ecgonine methyl ester, cocaethylene, other cocaine metabolites or pyrolysis products (norcocaine, norcocaethylene, norbenzoylecgonine, m-hydroxycocaine, p-hydroxycocaine, m-hydroxybenzoylecgonine, p-hydroxybenzoylecgonine, ethyl ecgonine, ecgonine, anhydroecgonine methyl ester, anhydroecgonine ethyl ester, anhydroecgonine, noranhydroecgonine, N-hydroxynorcocaine, cocaine N-oxide, anhydroecgonine methyl ester N-oxide). Metabolites and degradation products which are recommended to be monitored for assessment in clinical or forensic toxicology are mentioned. Papers written in English between 2002 and the beginning of 2007 are reviewed. Analytical methods are assessed for their suitability in forensic toxicology, where special requirements have to be met. For many of the analytes sensitive immunological methods for screening are available. Screening and confirmation is mostly done by gas chromatography (GC)–mass spectrometry (MS) or liquid chromatography (LC)–MS(/MS) procedures. Basic information about the biosample assayed, internal standard, workup, GC or LC column and mobile phase, detection mode, and validation data for each procedure is summarized in two tables to facilitate the selection of a method suitable for a specific analytic problem.     

The effect of specific nucleation on molecular and supermolecular orientation in isotactic polypropylene

The molecular and supermolecular orientation, morphology and structural changes observed during cold drawing of injection moulded isotactic polypropylene modified by specific α, and β nucleating agents were studied by polarised photoacoustic FTIR spectroscopy, wide-angle X-ray diffraction and differential scanning calorimetry. Significantly lower molecular orientation was found in the core of the β-nucleated injection moulded specimens as compared to unmodified and α-nucleated materials. This has been ascribed to the fast growth of the β-crystallites which inevitably dislocates the flow-induced orientation within the crystalline regions and in their vicinity. Moreover, it was found that the presence of the developed β-crystallites distinctly diminishes the efficiency of the orientational solid-state drawing assessed on both levels of the hierarchical structure (molecular and crystalline). This structural observation is directly connected with macroscopic softening effect of the β-phase: lowering the yield stress and flattening the neck shoulder. Thus, the interrelation between the microstructural and macroscopic effects of the β-phase could be described as a feedback process.     

Synthesis and characterization of semifluorinated polymers and block copolymers

The goal of the investigation presented here was to evaluate the influence of semifluorinated side chains on the bulk structure and the surface properties of polysulfones with different chain structure. Thus, segmented block copolymers consisting of polysulfone and semifluorinated aromatic polyester segments as well as polysulfones having semifluorinated side chains randomly distributed over the polymer backbone were synthesized and characterized. Oxydecylperfluorodecyl side chains were used because of their strong tendency for self-organization. The influence of the chain architecture on the self-organization as well as on the surface properties, particularly the wetting behavior, was examined. It could be shown that despite of the higher self-organizing tendency of block copolymers the surface properties of both polymer types are comparable and depend only on the concentration of side chains.     

Cs2[PdCl4] — neue Ergebnisse zu einer „altbekannten”︁ Verbindung

Hochtemperatur‐Cs₂[PdCl₄] — New Results on a “wellknown” Compound Two modifications of Cs₂[PdCl₄] have been characterized by X‐ray powder and single crystal diffraction, respectively. The crystal structures are described and the group‐subgroup‐relations between these structures are discussed. In addition to the tetragonal (P4/mmm (No. 123), a = 7.4158(8) Å, c = 4.6792(6) Å) and the orthorhombic (Cmcm (No. 63), a = 10.529(1) Å, b = 10.310(1) Å, c = 9.460(1) Å) modification DSC investigations and high‐temperature X‐ray diffraction experiments with synchrotron radiation show the existence of another modification or of yet unknown decomposition products. The phase transformation from the orthorhombic to the tetragonal polymorph is completely finished at 100 °C. The second effect is detected at 319 °C.     

Supercritical CO2 Assisted Impregnation of Ibuprofen on Medium-Chain-Length Polyhydroxyalkanoates (mcl-PHA)

In this work, we propose the utilization of scCO₂ to impregnate ibuprofen into the mcl-PHA matrix produced by Pseudomonas chlororaphis subs. aurantiaca (DSM 19603). The biopolymer has adhesive properties, is biocompatible and has a melting temperature of 45 °C. Several conditions, namely, pressure (15 and 20 MPa) and impregnation time (30 min, 1 h and 3 h) were tested. The highest ibuprofen content (90.8 ± 6.5 mg of ibuprofen/g_PHA) was obtained at 20 MPa and 40 °C, for 1 h, with an impregnation rate of 89 mg/(g·h). The processed mcl-PHA samples suffered a plasticization, as shown by the decrease of 6.5 °C in the T_g, at 20 MPa. The polymer’s crystallinity was also affected concomitantly with the matrices’ ibuprofen content. For all the impregnation conditions tested the release of ibuprofen from the biopolymer followed a type II release profile. This study has demonstrated that the mcl-PHA produced by P. chlororaphis has a great potential for the development of novel topical drug delivery systems.     

Synthesis and characterization of fluorinated poly(imide siloxane) block copolymers

Five new block copoly(imide siloxane)s have been prepared by reacting two different diamines, 4,4″-bis(p-aminophenoxy)-3,3″-trifluoromethyl terphenyl (APTTFT) and amino-propyl terminated polydimethylsiloxane (APPS), separately with 4,4′-(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride); BPADA. The reactions were conducted by a two pot solution imidization technique. The diamine APTTFT and the dianhydride BPADA composed the hard block segment while APPS and BPADA composed the soft block segment. The soft and hard blocks of different block lengths were generated by different stoichiometric imbalance in two different flasks and the final polymers were obtained by reacting both the blocks together. Different block copoly(imide siloxane)s were prepared on increasing the hard block lengths (DP) from 7 to 12, 18, 23 and 28 and the soft block lengths (DP) from 4 to 6, 8, 10 and 12, respectively. The resulting polymers have been well characterized by NMR, DSC and DMA techniques. The properties of the block copolymers were compared with the analogous random copolymers and homopolyimide prepared without APPS.     

Design of a dinuclear nickel(II) bioinspired hydrolase to bind covalently to silica surfaces: synthesis, magnetism, and reactivity studies

Presented herein is the design of a dinuclear Ni(II) synthetic hydrolase [Ni(2)(HBPPAMFF)(μ-OAc)(2)(H(2)O)]BPh(4) (1) (H(2)BPPAMFF = 2-[(N-benzyl-N-2-pyridylmethylamine)]-4-methyl-6-[N-(2-pyridylmethyl)aminomethyl)])-4-methyl-6-formylphenol) to be covalently attached to silica surfaces, while maintaining its catalytic activity. An aldehyde-containing ligand (H(2)BPPAMFF) provides a reactive functional group that can serve as a cross-linking group to bind the complex to an organoalkoxysilane and later to the silica surfaces or directly to amino-modified surfaces. The dinuclear Ni(II) complex covalently attached to the silica surfaces was fully characterized by different techniques. The catalytic turnover number (k(cat)) of the immobilized Ni(II)Ni(II) catalyst in the hydrolysis of 2,4-bis(dinitrophenyl)phosphate is comparable to the homogeneous reaction; however, the catalyst interaction with the support enhanced the substrate to complex association constant, and consequently, the catalytic efficiency (E = k(cat)/K(M)) and the supported catalyst can be reused for subsequent diester hydrolysis reactions.     

How Accessible Is Atomic Charge Information from Infrared Intensities? A QTAIM/CCFDF Interpretation

Infrared fundamental intensities calculated by the quantum theory of atoms in molecules/charge-charge flux-dipole flux (QTAIM/CCFDF) method have been partitioned into charge, charge flux, and dipole flux contributions as well as their charge-charge flux, charge-dipole flux, and charge flux-dipole flux interaction contributions. The interaction contributions can be positive or negative and do not depend on molecular orientations in coordinate systems or normal coordinate phase definitions, as do CCFDF dipole moment derivative contributions. If interactions are positive, their corresponding dipole moment derivative contributions have the same polarity reinforcing the total intensity estimates whereas negative contributions indicate opposite polarities and lower CCFDF intensities. Intensity partitioning is carried out for the normal coordinates of acetylene, ethylene, ethane, all the chlorofluoromethanes, the X(2)CY (X = F, Cl; Y = O, S) molecules, the difluoro- and dichloroethylenes and BF(3). QTAIM/CCFDF calculated intensities with optimized quantum levels agree within 11.3 km mol(-1) of the experimental values. The CH stretching and in-plane bending vibrations are characterized by significant charge flux, dipole flux, and charge flux-dipole flux interaction contributions with the negative interaction tending to cancel the individual contributions resulting in vary small intensity values. CF stretching and bending vibrations have large charge, charge-charge flux, and charge-dipole flux contributions for which the two interaction contributions tend to cancel one another. The experimental CF stretching intensities can be estimated to within 31.7 km mol(-1) or 16.3% by a sum of these three contributions. However, the charge contribution alone is not successful at quantitatively estimating these CF intensities. Although the CCl stretching vibrations have significant charge-charge flux and charge-dipole flux contributions, like those of the CF stretches, both of these interaction contributions have opposite signs for these two types of vibrations.