Carbon Fibers: Precursor Systems,Processing, Structure,and Properties

This Review gives an overview of precursor systems, their processing, and the final precursor‐dependent structure of carbon fibers (CFs) including new developments in precursor systems for low‐cost CFs. The following CF precursor systems are discussed: poly(acrylonitrile)‐based copolymers, pitch, cellulose, lignin, poly(ethylene), and new synthetic polymeric precursors for high‐end CFs. In addition, structure–property relationships and the different models for describing both the structure and morphology of CFs will be presented.     

Synergic approach to XAFS analysis for the identification of most probable binding motifs for mononuclear zinc sites in metalloproteins

In the present work a data analysis approach, based on XAFS data, is proposed for the identification of most probable binding motifs of unknown mononuclear zinc sites in metalloproteins. This approach combines multiple‐scattering EXAFS analysis performed within the rigid‐body refinement scheme, non‐muffin‐tin ab initio XANES simulations, average structural information on amino acids and metal binding clusters provided by the Protein Data Bank, and Debye–Waller factor calculations based on density functional theory. The efficiency of the method is tested by using three reference zinc proteins for which the local structure around the metal is already known from protein crystallography. To show the applicability of the present analysis to structures not deposited in the Protein Data Bank, the XAFS spectra of six mononuclear zinc binding sites present in diverse membrane proteins, for which we have previously proposed the coordinating amino acids by applying a similar approach, is also reported. By comparing the Zn K‐edge XAFS features exhibited by these proteins with those pertaining to the reference structures, key spectral characteristics, related to specific binding motifs, are observed. These case studies exemplify the combined data analysis proposed and further support its validity.     

Complementary MS Methods Assist Conformational Characterization of Antibodies with Altered S–S Bonding Networks

As therapeutic monoclonal antibodies (mAbs) become a major focus in biotechnology and a source of the next-generation drugs, new analytical methods or combination methods are needed for monitoring changes in higher order structure and effects of post-translational modifications. The complexity of these molecules and their vulnerability to structural change provide a serious challenge. We describe here the use of complementary mass spectrometry methods that not only characterize mutant mAbs but also may provide a general framework for characterizing higher order structure of other protein therapeutics and biosimilars. To frame the challenge, we selected members of the IgG2 subclass that have distinct disulfide isomeric structures as a model to evaluate an overall approach that uses ion mobility, top-down MS sequencing, and protein footprinting in the form of fast photochemical oxidation of proteins (FPOP). These three methods are rapid, sensitive, respond to subtle changes in conformation of Cys?→?Ser mutants of an IgG2, each representing a single disulfide isoform, and may be used in series to probe higher order structure. The outcome suggests that this approach of using various methods in combination can assist the development and quality control of protein therapeutics.      

S‐Alkylation of Soft Scorpionates

The alkylation reactions of soft scorpionates are reported. The hydrotris(S‐alkyl‐methimazolyl)borate dications (alkyl=methyl, allyl, benzyl), which were prepared by the reaction of Tm^Me anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C?S versus B? H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo‐μ‐aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ³‐S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S‐alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B? N bond in soft scorpionates, which has implications for their use in more advanced chemistry.     

Surfactant Hydrogels for the Dispersion of Carbon‐Nanotube‐Based Catalysts

Novel hydrogel phases based on positively charged and zwitterionic surfactants, namely, N‐[p‐(n‐dodecyloxybenzyl)]‐N,N,N‐trimethylammonium bromide (pDOTABr) and p‐dodecyloxybenzyldimethylamine oxide (pDOAO), which combine pristine carbon nanotubes (CNTs), were obtained, thus leading to stable dispersions and enhanced cross‐linked networks. The composite hydrogel featuring a well‐defined nanostructured morphology and an overall positively charged surface was shown to efficiently immobilise a polyanionic and redox‐active tetraruthenium‐substituted polyoxometalate (Ru₄POM) by complementary charge interactions. The resulting hybrid gel has been characterised by electron microscopy techniques, whereas the electrostatic‐directed assembly has been monitored by means of fluorescence spectroscopy and ζ‐potential tests. This protocol offers a straightforward supramolecular strategy for the design of novel aqueous‐based electrocatalytic soft materials, thereby improving the processability of CNTs while tuning their interfacial decoration with multiple catalytic domains. Electrochemical evidence confirms that the activity of the catalyst is preserved within the gel media.     

Determination of bis-carboxyethyl germanium sesquioxide by gas chromatography with microwave-induced plasma-atomic emission detection after derivatization with alkyl chloroformates

Organic germanium compounds, especially Ge-132, more corrctly denoted as bis-beta-carboxyethyl germanium sesquioxide ([Ge(=O)CH₂CH₂CO₂H]₂O), are of continued interest as they are said to promote health and display anticancer activity. Although these beneficial effects have never been substantiated by comprehensive clinical studies, this drug can still be obtained through various sources and is usually marketed as a nutritional supplementation rather than an anticancer medication. As the quality standards under which this drug is produced are unknown, the need for an effective quality control of these products arises. To date, Ge-132 is considered generally as a safe compound for application in contrast to inorganic germanium which demonstrates severe renal toxicity. In this paper, a new approach to the determination of Ge-132, based on derivatization by ethyl chloroformate reagent (ECF), in the presence of ethanol and pyridine in the mixture, and subsequent analysis by gas chromatography coupled with microwave-induced plasma-atomic emission detection (GC-MIP-AED), is reported. Reaction conditions of the derivatization procedure were optimized with particular respect to the reagent (ECF) and catalyst (pyridine) concentrations. The proposed method is capable of distinguishing Ge-132 from inorganic germanium. The derivatization procedure was also tested with the use of methyl chloroformate (MCF) as alternative reagent, providing interesting additional information about the nature of the final product and the proposed reaction scheme. Among the two types of chloroformates, i.e., MCF and ECF, the latter proved to be more suitable for the proposed method, providing a calibration curve of superior sensitivity and linearity compared with the one obtained with MCF. The method was applied successfully in three real samples, two food supplements, and one commercially available fertilizer. The analysis of the Ge-132 derivative showed good linearity in the concentration of 1–250 mg L^?1 (r ²?=?0.9986) and a satisfactory precision (RSD?=?6.8 %), which qualifies the proposed method for the speciation analysis of Ge in various matrices.     

Design,Synthesis, and Validation of a Novel [11C]Promethazine PET Probe for Imaging Abeta Using Autoradiography

Promethazine, an antihistamine drug used in the clinical treatment of nausea, has been demonstrated the ability to bind Abeta in a transgenic mouse model of Alzheimer’s disease. However, so far, all of the studies were performed in vitro using extracted tissues. In this work, we report the design and synthesis of a novel [¹¹C]promethazine PET radioligand for future in vivo studies. The [¹¹C]promethazine was isolated by RP-HPLC with radiochemical purity >95% and molar activity of 48 TBq/mmol. The specificity of the probe was demonstrated using human hippocampal tissues via autoradiography.     

Diffusion changes in patients with systemic lupus erythematosus

BACKGROUND AND PURPOSE: Systemic lupus erythematosus (SLE) is an autoimmune disease in which almost all the organs are involved. Neuropsychiatric SLE is of one of the major concerns in the clinical evaluation of this disease. Routine magnetic resonance imaging (MRI) findings are often nonspecific or negative. In this study, we explored the use of diffusion tensor imaging in assisting with the diagnosis of SLE. METHODS: Data from 34 SLE patients (age range, 18-73 years) and 29 age-matched volunteers (age range, 29-64 years) were analyzed. MRI was performed on a 1.5-T clinical MR scanner with a quadrature head coil. The average diffusion constant (D(av)) and diffusion anisotropy maps [fractional anisotropy (FA)] were determined on a pixel-by-pixel basis. Regional diffusion measurements were made by region of interest in the genu and splenium of the corpus callosum (CC), anterior and posterior limb of the internal capsule (IC) and frontal lobe and thalamus. The diffusion distribution was fitted to a triple-Gaussian model. The mean of the brain tissue distribution was determined as a mean diffusion constant for the whole brain (BD(av)). Student's t test was used to determine the diffusion difference between SLE patients and control subjects. The SLE patients were separated into two groups according to their MRI results. A P value lower than .05 was considered to be statistically significant. RESULTS: Twenty of the 34 SLE patients with abnormal MRI results showed findings dominated by nonspecific white matter disease. The BD(av) and D(av) values of the frontal lobe, splenium CC and anterior IC were significantly higher in all SLE patients as compared with the control subjects. The SLE patients with normal MRI results also showed higher BD(av) and D(av) values in the frontal lobe, splenium and anterior and posterior limbs of the IC as compared with the control subjects. There was no significant difference in the D(av) values of the thalamus between the SLE patients and the control subjects. The BD(av) value in the SLE patient group was robustly correlated with the D(av) values of the frontal lobe, splenium and thalamus. These correlations were found to be similarly significant for the SLE patients with normal MRI findings. The diffusion anisotropy measurements showed that splenium CC had the highest FA value in both the control subjects and SLE patients. Overall, SLE patients had lower FA values in the genu and splenium CC as compared with the control subjects. In the group of patients with normal MRI findings, the FA values of the genu and splenium CC as well as the anterior IC were also lower than those in the control subjects. Pearson's correlation statistics revealed robust correlations between the measurements of D(av) and FA values in the SLE patient group. CONCLUSION: Quantitative diffusion imaging and diffusion anisotropy showed early changes in the brains of the SLE patients. Increased BD(av) and D(av) values of the frontal lobe as well as decreased anisotropy in the genu CC and anterior IC may represent preclinical signs of central nervous system involvement of SLE even when the routine MRI findings are negative or nonspecific. Quantitative diffusion analysis may prove to be useful in detecting the initial brain involvement of SLE and may enable monitoring of early disease progression and treatment efficacy.