Hybrid Polyoxotungstates as Functional Comonomers in New Cross‐Linked Catalytic Polymers for Sustainable Oxidation with Hydrogen Peroxide

Anchoring terminal octenyl tails on molecular polyoxotungstates yield polymerizable organic–inorganic monomers with formula [{CH₂?CH(CH₂)₆Si}_xO_ySiW_wO_z]^4? [x=2, w=11, y=1, z=39 ( 1 ); x=2, w=10, y=1, z=36 ( 2 ); and x=4, w=9, y=3, z=34 ( 3 )]. These molecular hybrids can use aqueous hydrogen peroxide to catalyze the selective oxidation of organic sulfides in CH₃CN. Copolymerization of 1 – 3 with methyl methacrylate and ethylene glycol dimethacrylate leads to porous materials with a homogeneous distribution of the functional monomers, as indicated by converging evidence from FTIR spectroscopy and electronic microscopy. The catalytic polymers activate hydrogen peroxide for oxygen transfer, as demonstrated by the quantitative and selective oxidation of methyl p‐tolyl sulfide, which was screened as model substrate. The hybrid material containing monomer 2 was also tested in n‐octane to evaluate its potential for the oxidation and removal of dibenzothiophene, a well‐known gasoline contaminant.     

Gender effect on neurodegeneration and myelin markers in an animal model for multiple sclerosis

Background  

Multiple sclerosis (MS) varies considerably in its incidence and progression in females and males. In spite of clinical evidence, relatively few studies have explored molecular mechanisms possibly involved in gender-related differences. The present study describes possible cellular- and molecular-involved markers which are differentially regulated in male and female rats and result in gender-dependent EAE evolution and progression. Attention was focused on markers of myelination (MBP and PDGFαR) and neuronal distress and/or damage (GABA synthesis enzymes, GAD65 and GAD67, NGF, BDNF and related receptors), in two CNS areas, i.e. spinal cord and cerebellum, which are respectively severely and mildly affected by inflammation and demyelination. Tissues were sampled during acute, relapse/remission and chronic phases and results were analysed by two-way ANOVA.     

Optimization of a SPME/GC/MS Method for the Simultaneous Determination of Pharmaceuticals and Personal Care Products in Waters

A headspace solid phase microextraction (HS-SPME) method coupled with gas chromatography and MS detection (GC/MS) was optimized for the simultaneous determination of 21 target Pharmaceuticals and Personal Care Products (PPCPs) in water samples. The analytes included fragrances, UV-filters, antiseptics, estrogens, anti-inflammatory drugs, and pesticides. An on-fiber SPME derivatization, using silyl reagents, was performed for the analysis of more polar acidic compounds. An experimental design approach was applied to systematically investigate and optimize the operative parameters affecting the extraction recovery, namely: extraction temperature and time, derivatization time, desorption temperature and time. The optimum operating conditions were: extraction time of 125?min at a temperature of 40?°C; derivatization time of 30.5?min; desorption time of 2?min at a temperature of 300?°C. Under these conditions, good reproducibility was assessed as RDS% values ≤10% for underivatized PPCPs and ≤20% for derivatized compounds. The method detection limits (LOD) were between 0.7 and 9.0?ng?L^?1, with the highest values in the range 2.5–9.0?ng?L^?1 for the derivatized analytes. Method accuracy was evaluated on spiked tap water samples: recoveries varied from 85 to 103% and from 75 to 110% for non-derivatized and derivatized compounds, respectively.     

S3O and S3O+ in the Gas Phase: Ring and Open‐Chain Structures.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Insights on the Modulation of SIRT5 Activity: A Challenging Balance

SIRT5 is a member of the Sirtuin family, a class of deacetylating enzymes consisting of seven isoforms, involved in the regulation of several processes, including gene expression, metabolism, stress response, and aging. Considering that the anomalous activity of SIRT5 is linked to many pathological conditions, we present herein an overview of the most interesting modulators, with the aim of contributing to further development in this field.     

On the Spatial Distribution of Temporal Complexity in Resting State and Task Functional MRI

Measuring the temporal complexity of functional MRI (fMRI) time series is one approach to assess how brain activity changes over time. In fact, hemodynamic response of the brain is known to exhibit critical behaviour at the edge between order and disorder. In this study, we aimed to revisit the spatial distribution of temporal complexity in resting state and task fMRI of 100 unrelated subjects from the Human Connectome Project (HCP). First, we compared two common choices of complexity measures, i.e., Hurst exponent and multiscale entropy, and observed a high spatial similarity between them. Second, we considered four tasks in the HCP dataset (Language, Motor, Social, and Working Memory) and found high task-specific complexity, even when the task design was regressed out. For the significance thresholding of brain complexity maps, we used a statistical framework based on graph signal processing that incorporates the structural connectome to develop the null distributions of fMRI complexity. The results suggest that the frontoparietal, dorsal attention, visual, and default mode networks represent stronger complex behaviour than the rest of the brain, irrespective of the task engagement. In sum, the findings support the hypothesis of fMRI temporal complexity as a marker of cognition.     

Fluorinated PLGA Nanoparticles for Enhanced Drug Encapsulation and 19F NMR Detection

In the continuous search for multimodal systems with combined diagnostic and therapeutic functions, several efforts have been made to develop multifunctional drug delivery systems. In this work, through a covalent approach, a new class of fluorinated poly(lactic-co-glycolic acid) co-polymers (F-PLGA) were designed that contain an increasing number of magnetically equivalent fluorine atoms. In particular, two novel compounds, F₃-PLGA and F₉-PLGA, were synthesized and their chemical structure and thermal stability were analyzed by solution NMR, DSC, and TGA. The obtained F-PLGA compounds were proven to form in aqueous solution colloidal stable nanoparticles (NPs) displaying a strong ¹⁹F NMR signal. The fluorinated NPs also showed an enhanced ability to load hydrophobic drugs containing fluorine atoms compared to analogous pristine PLGA NPs. Preliminary in vitro studies showed high cell viability and the NP ability to intracellularly deliver and release a functioning drug.     

Tin,Titanium, Tantalum,Vanadium and Niobium Oxide Based Sensors to Detect Colorectal Cancer Exhalations in Blood Samples

User-friendly, low-cost equipment for preventive screening of severe or deadly pathologies are one of the most sought devices by the National Health Services, as they allow early disease detection and treatment, often avoiding its degeneration. In recent years more and more research groups are developing devices aimed at these goals employing gas sensors. Here, nanostructured chemoresistive metal oxide (MOX) sensors were employed in a patented prototype aimed to detect volatile organic compounds (VOCs), exhaled by blood samples collected from patients affected by colorectal cancer and from healthy subjects as a control. Four sensors, carefully selected after many years of laboratory tests on biological samples (cultured cells, human stools, human biopsies, etc.), were based here on various percentages of tin, tungsten, titanium, niobium, tantalum and vanadium oxides. Sensor voltage responses were statistically analyzed also with the receiver operating characteristic (ROC) curves, that allowed the identification of the cut-off discriminating between healthy and tumor affected subjects for each sensor, leading to an estimate of sensitivity and specificity parameters. ROC analysis demonstrated that sensors employing tin and titanium oxides decorated with gold nanoparticles gave sensitivities up to 80% yet with a specificity of 70%.