Long-Chain Hydrocarbons from Nonthermal Plasma-Driven Biogas Upcycling.

The burgeoning necessity to discover new methodologies for the synthesis of long-chain hydrocarbons and oxygenates, independent of traditional reliance on high-temperature, high-pressure, and fossil fuel-based carbon, is increasingly urgent. In this context, we introduce a nonthermal plasma-based strategy for the initiation and propagation of long-chain carbon growth from biogas constituents (CO and CH). Utilizing a plasma reactor operating at atmospheric room temperature, our approach facilitates hydrocarbon chain growth up to C40 in the solid state (including oxygenated products), predominantly when CH exceeds CO in the feedstock.

3D Printing of Monoliths Using TIFSIX-Ni-Based Formulations for the Electric Swing Adsorption of CO.

The hybrid ultraporous material TIFSIX-Ni ([Ni(pyrazine)(TiF)]) was incorporated into a composite ink for the first time for the three-dimensional (3D) printing of monoliths. The large-scale synthesis of TIFSIX-Ni was completed using two different Ni(II) salts, with CO uptakes of 1.90 mmol g achieved using mechanochemically assisted thermal synthesis.

Dysregulating PHO Signaling via the CDK Machinery Differentially Impacts Energy Metabolism, Calcineurin Signaling, and Virulence in Cryptococcus neoformans.

Fungal pathogens uniquely regulate phosphate homeostasis via the cyclin-dependent kinase (CDK) signaling machinery of the phosphate acquisition (PHO) pathway (Pho85 kinase-Pho80 cyclin-CDK inhibitor Pho81), providing drug-targeting opportunities. Here, we investigate the impact of a PHO pathway activation-defective Cryptococcus neoformans mutant (Δ) and a constitutively activated PHO pathway mutant (Δ) on fungal virulence. Irrespective of phosphate availability, the PHO pathway was derepressed in Δ with all phosphate acquisition pathways upregulated and much of the excess phosphate stored as polyphosphate (polyP).

Copper(I) Chloride Mediated Amination of Halobenzenes via Azides: Scope, Mechanistic Aspects, and C-C Cleavage Reactions.

Selective azidation-amination of long-chain alkanoyl halobenzenes with sodium azide, promoted by copper(I) chloride, is reported. The protocol is, apart from CuCl and NaN, additive free and allows the isolation of versatile amine-azides. Alkyl cleavage occurs as a side reaction through an unusual Schmidt-type azide insertion adjacent to the carbonyl group, forming alkyl nitriles possibly via radical pathways.

Quantifying exposure to chlorhexidine from decontamination of peripheral intravenous injection ports.

Background: Annually, almost 2 billion peripheral intravenous cannulas (PIVCs) are placed worldwide. In response to concerns of infectious complications, chlorhexidine is increasingly utilised for maintenance decontamination of PIVC injection ports. Concomitantly, the allergenic potential of chlorhexidine exposures has been highlighted by several case reports, implicating it as a trigger when used for this seemingly innocuous process.

Vanadium Chloro-Substituted Schiff Base Catecholate Complexes are Reducible, Lipophilic, Water Stable, and Have Anticancer Activities.

A hydrophobic Schiff base catecholate vanadium complex was recently discovered to have anticancer properties superior to cisplatin and suited for intratumoral administration. This [VO(HSHED)(DTB)] complex, where HSHED is -(salicylideneaminato)-'-(2-hydroxyethyl)-1,2-ethanediamine and the non-innocent catecholato ligand is di--butylcatecholato (DTB), has higher stability compared to simpler catecholato complexes. Three new chloro-substituted Schiff base complexes of vanadium(V) with substituted catecholates as co-ligands were synthesized for comparison with their non-chlorinated Schiff base vanadium complexes, and their properties were characterized.

Zinc toxicosis in a cat associated with ingestion of a metal screw nut.

Case Summary: A 3-year-old female neutered domestic shorthair cat was presented for vomiting, inappetence and weight loss. The cat developed moderately regenerative anaemia, moderately increased alanine transaminase and alkaline phosphatase activities, hyperbilirubinaemia and prolonged activated partial thromboplastin time. Abdominal ultrasound identified gastric wall thickening and changes suggestive of pancreatitis.

Site-selective photocatalytic functionalization of peptides and proteins at selenocysteine.

The importance of modified peptides and proteins for applications in drug discovery, and for illuminating biological processes at the molecular level, is fueling a demand for efficient methods that facilitate the precise modification of these biomolecules. Herein, we describe the development of a photocatalytic method for the rapid and efficient dimerization and site-specific functionalization of peptide and protein diselenides. This methodology, dubbed the photocatalytic diselenide contraction, involves irradiation at 450 nm in the presence of an iridium photocatalyst and a phosphine and results in rapid and clean conversion of diselenides to reductively stable selenoethers.

The effect of thermal pasteurization, freeze-drying, and gamma irradiation on donor human milk.

The availability of donor human milk (DHM) is currently limited by the volumes that can be thermally pasteurized and kept in long-term cold storage. This study assesses the application of freeze-drying followed by low-dose gamma irradiation of DHM for simplified, safe long-term storage. Solid-phase microextraction (SPME) GC-MS, SDS and native PAGE gel electrophoresis demonstrated that the overall changes in volatile and protein profiles in Holder pasteurized and freeze-dried DHM was negligible compared to the natural variations in DHM.

A cofacial metal-organic framework based photocathode for carbon dioxide reduction.

Innovative and robust photosensitisation materials play a cardinal role in advancing the combined effort towards efficient solar energy harvesting. Here, we demonstrate the photocathode functionality of a Metal-Organic Framework (MOF) featuring cofacial pairs of photo- and electro-active 1,4,5,8-naphthalenediimide (NDI) ligands, which was successfully applied to markedly reduce the overpotential required for CO reduction to CO by a well-known rhenium molecular electrocatalyst. Reduction of [Cd(DPNDI)(TDC)] (DPNDI = ,'-di(4-pyridyl)-1,4,5,8-naphthalenediimide, HTDC = thiophene-2,5-dicarboxylic acid) to its mixed-valence state induces through-space Intervalence Charge Transfer (IVCT) within cofacial DPNDI units.

Synthesis of Long-Chain Alkanoyl Benzenes by an Aluminum(III) Chloride-Catalyzed Destannylative Acylation Reaction.

This paper describes the facile synthesis of haloaryl compounds with long-chain alkanoyl substituents by the destannylative acylation of haloaryls bearing tri--butyltin (BuSn) substituents. The method allows the synthesis of many important synthons for novel functional materials in a highly efficient manner. The halo-tri--butyltin benzenes are obtained by the lithium-halogen exchange of commercially available bis-haloarenes and the subsequent reaction with BuSnCl.

Pancreatic adenocarcinoma preferentially takes up and is suppressed by synthetic nanoparticles carrying apolipoprotein A-II and a lipid gemcitabine prodrug in mice.

We hypothesised that synthetic HDL nanoparticles carrying a gemcitabine prodrug and apolipoprotein A-II (sHDLGemA2) would target scavenger receptor-B1 (SR-B1) to preferentially and safely deliver gemcitabine into pancreatic ductal adenocarcinoma (PDAC). We designed, manufactured and characterised sHDLGemA2 nanoparticles sized ~130 nm, incorporating 20 mol% of a gemcitabine prodrug within the lipid bilayer, which strengthens on adding ApoA-II. We measured their ability to inhibit growth in cell lines and cell-derived and patient-derived murine PDAC xenografts.

Ibudilast for prevention of oxaliplatin-induced acute neurotoxicity: a pilot study assessing preliminary efficacy, tolerability and pharmacokinetic interactions in patients with metastatic gastrointestinal cancer.

Purpose: This prospective, open-label, sequential 'before vs. after' pilot study was conducted to provide preliminary efficacy and tolerability data for ibudilast in the prevention of oxaliplatin-induced neurotoxicity in patients with metastatic upper gastrointestinal or colorectal cancer. Any potential impact of ibudilast on oxaliplatin and 5-fluorouracil pharmacokinetics was also explored.

Studies of the labile lead pool using a rhodamine-based fluorescent probe.

Lead is a heavy metal which has long been known to have toxic effects on the body. However, much remains to be learnt about the labile lead pool and cellular uptake of lead. We report here RPb1 that undergoes a 100-fold increase in fluorescence emission in the presence of Pb2+, and which can be applied to study the labile lead pool within cells.

Bengamides display potent activity against drug-resistant Mycobacterium tuberculosis.

Mycobacterium tuberculosis infects over 10 million people annually and kills more people each year than any other human pathogen. The current tuberculosis (TB) vaccine is only partially effective in preventing infection, while current TB treatment is problematic in terms of length, complexity and patient compliance. There is an urgent need for new drugs to combat the burden of TB disease and the natural environment has re-emerged as a rich source of bioactive molecules for development of lead compounds.

Metabolic Engineering of the MEP Pathway in for Increased Biosynthesis of Menaquinone-7.

Vitamin K is essential for blood coagulation and plays important roles in bone and cardiovascular health. Menaquinone-7 (MK-7) is one form of vitamin K that is especially useful due to its long half-life in the circulation. MK-7 is difficult to make organic synthesis, and is thus commonly produced by fermentation.

Changes in the in vitro activity of platinum drugs when administered in two aliquots.

Background: The management of ovarian cancer remains a challenge. Because of the lack of early symptoms, it is often diagnosed at a late stage when it is likely to have metastasized beyond ovaries. Currently, platinum based chemotherapy is the primary treatment for the disease.

Follow your nose: leaf odour as an important foraging cue for mammalian herbivores.

Studies of odour-driven foraging by mammals focus on attractant cues emitted by flowers, fruits, and fungi. Yet, the leaves of many plant species worldwide produce odour, which could act as a cue for foraging mammalian herbivores. Leaf odour may thus improve foraging efficiency for such herbivores in many ecosystems by reducing search time, particularly but not only, for plants that are visually obscured.

CHR-insertion (R=H, CH3) into cyclohexyl-substituted silsesquioxanes: reactivity and decomposition studies.

Amorphous silica plays an important role in heterogeneous catalysis as a support and is frequently presumed to be "inert". The structure of the supported catalyst is key to understanding the stability and reactivity of catalytic systems. To provide vital insights into the surface reactivity of silica, Polyhedral oligomeric silsesquioxanes (POSSs) can act as realistic homogeneous molecular models for silica surfaces.

Aging effects on macadamia nut oil studied by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

High-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry is successfully used in the detailed molecular analysis of aged macadamia nut oils. The results are consistent with peroxide values, the current industry measure for rancidity, and provide detailed molecular information on the oxidative and hydrolytic degeneration of such oils. Mass analysis of macadamia oil samples stored for extended periods at 6 °C revealed that oils obtained by the cold press method are more susceptible to aging than those obtained using modified Soxhlet or accelerated solvent extraction methods.

Effect of phospholipid deposits on adhesion of bacteria to contact lenses.

Purpose: Protein and lipid deposits on contact lenses may contribute to clinical complications. This study examined the effect of phospholipids on the adhesion of bacteria to contact lenses.

Methods: Worn balafilcon A (n = 11) and senofilcon A (n = 11) were collected after daily wear and phospholipids were extracted in chloroform:methanol.

Phagocytosis of IgG-coated polystyrene beads by macrophages induces and requires high membrane order.

The biochemical composition and biophysical properties of cell membranes are hypothesized to affect cellular processes such as phagocytosis. Here, we examined the plasma membranes of murine macrophage cell lines during the early stages of uptake of immunoglobulin G (IgG)-coated polystyrene particles. We found that the plasma membrane undergoes rapid actin-independent condensation to form highly ordered phagosomal membranes, the biophysical hallmark of lipid rafts.

Mass and relative elution time profiling: two-dimensional analysis of sphingolipids in Alzheimer's disease brains.

Current lipidomic profiling methods rely mainly on MS to identify unknown lipids within a complex sample. We describe a new approach, involving LC×MS/MS (liquid chromatography×tandem MS) analysis of sphingolipids based on both mass and hydrophobicity, and use this method to characterize the SM (sphingomyelin), ceramide and GalCer (galactosylceramide) content of hippocampus from AD (Alzheimer's disease) and control subjects. Using a mathematical relationship we exclude the influence of sphingolipid mass on retention time, and generate two-dimensional plots that facilitate accurate visualization and characterization of the different ceramide moieties within a given sphingolipid class, because related molecules align horizontally or vertically on the plots.