BMS Derivatives C7-Linked to β-Cyclodextrin and Hyperbranched Polyglycerol Retain Activity against R5-HIV-1NLAD8 Isolates and Can Be Deemed Potential Microbicides

Amides from indole-3-glyoxylic acid and 4-benzoyl-2-methylpiperazine, which are related to entry inhibitors developed by Bristol-Myers Squibb (BMS), have been synthesized with aliphatic chains located at the C7 position of the indole ring. These spacers contain an azido group suitable for the well-known Cu(I)-catalyzed (3+2)-cycloaddition or an activated triple bond for the nucleophilic addition of thiols under physiological conditions. Reaction with polyols (β-cyclodextrin and hyperbranched polyglycerol) decorated with complementary click partners has afforded polyol-BMS-like conjugates that are not cytotoxic (TZM.bl cells) and retain the activity against R5-HIV-1_NLAD8 isolates. Thus, potential vaginal microbicides based on entry inhibitors, which can be called of 4^th generation, are reported here for the first time.     

Mushroom-Derived Medicine? Preclinical Studies Suggest Potential Benefits of Ergothioneine for Cardiometabolic Health

Medicinal use of mushrooms has been documented since ancient times, and in the modern world, mushrooms have a longstanding history of use in Eastern medicine. Recent interest in plant-based diets in Westernized countries has brought increasing attention to the use of mushrooms and mushroom-derived compounds in the prevention and treatment of chronic diseases. Edible mushrooms are the most abundant food sources of the modified amino acid, ergothioneine. This compound has been shown to accumulate in almost all cells and tissues, but preferentially in those exposed to oxidative stress and injury. The demonstrated cytoprotectant effect of ergothioneine has led many to suggest a potential therapeutic role for this compound in chronic conditions that involve ongoing oxidative stress and inflammation, including cardiovascular and metabolic diseases. However, the in vivo effects of ergothioneine and its underlying therapeutic mechanisms in the whole organism are not as clear. Moreover, there are no well-defined, clinical prevention and intervention trials of ergothioneine in chronic disease. This review highlights the cellular and molecular mechanisms of action of ergothioneine and its potential as a Traditional, Complementary and Alternative Medicine for the promotion of cardiometabolic health and the management of the most common manifestations of cardiometabolic disease.     

Upcycling by grafting onto semi-crystalline polymers using supercritical CO2

The creation of graft copolymers by selectively grafting a second polymer to the amorphous fraction of a semi-crystalline polymer in supercritical CO₂ is demonstrated herein. The graft copolymer is synthesized by free radical polymerization of a vinyl monomer within the semi-crystalline polymer below its melt temperature. Such conditions afford selective grafting on the amorphous regions (block “B”) while leaving the crystalline domains (block “A”) unmodified. Accordingly, unique A-B, A-B-A, A-B-A-B-A, and so forth. block structures are formed. In this work, styrene is polymerized within polyamide 6, polyethylene terephthalate, and isotactic polypropylene. Purification of these material is performed to remove the un-grafted homopolymer, allowing for determination of the graft yield, the portion of polymer which covalently bonds to the semi-crystalline matrix. Grafting yields achieved in polyamide 6, polyethylene terephthalate, and isotactic polypropylene were 98%, 59%, and 15%, respectively. Property enhancements were observed upon further characterization of polystyrene-polyamide 6 copolymers, including high glass transition temperatures, the ability to be remelted, and tunable grafting molecular weight. Additionally, hydrophobicity is controlled by varying polystyrene composition. The remarkable range of accessed properties demonstrates this as a potential route to upcycling plastics.     

Temperature and processing effects on lithium ion conductivity of solution-deposited lithium zirconium phosphate (LiZr2P3O12) thin films

Lithium zirconium phosphate (LiZr₂P₃O₁₂) thin films have been prepared on platinized silicon substrates via a chemical solution deposition approach with processing temperatures between 700°C and 775°C. Films that were subject to a single high-temperature anneal were found to crystallize at temperatures above 725°C. Crystallization was observed in films annealed after each deposited layer at 700°C and above. In both cases, grain size was found to increase with annealing temperature. Ion conductivity was found to increase with annealing temperature in singly annealed films. In per-layer annealed films ion conductivity was found to initially increase then decrease with increasing annealing temperature. A maximum ion conductivity of 1.6 × 10⁻⁶ S/cm was observed for the singly annealed 775°C condition, while a maximum ion conductivity of 5.8 × 10⁻⁷ S/cm was observed for the 725°C per-layer annealed condition. These results are consistent with an increasing influence of cross-plane, internal interface resistance and vapor phase carrier loss in the per-layer annealed samples. This work demonstrates that post-deposition processing methods can strongly affect the ion conducting properties of LiZr₂P₃O₁₂ thin films.     

Hot isostatic pressed pyrochlore glass-ceramics: Revealing structure insides at the reaction interface

As potential waste forms for immobilizing actinide-rich radioactive wastes, Eu₂Ti₂O₇ (Eu as a surrogate for minor actinides) pyrochlore glass-ceramics were fabricated via hot isostatic pressing (HIPing) at 1200°C. The structure and microstructure at the reaction interface between the glass-ceramic waste form and the stainless steel (SS) canister under HIPing conditions were carefully investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and synchrotron single crystal X-ray diffraction (SC-XRD). The interactions at the reaction interface led to the formations of a ~10-µm-thick Cr₂O₃ layer as the oxidation front of the SS and a layer of a mixed oxide phase (Eu_1.25SiCr_0.8Ti_1.2O_7.5) on the glass-ceramic side of the reaction interface. The crystal structure of such a unique mixed oxide phase was revealed indubitably with a combination of synchrotron SC-XRD and TEM assisted with a focused ion beam (FIB) SEM system. The improved structural understanding of the reaction interface will help to support the utilization of HIPing as a versatile hot consolidation process for the treatment of radioactive wastes.     

Covalent surface functionalization of nonwoven fabrics with controlled hydrophobicity,water absorption,and pH regulation properties

A modular method for functionalization of nonwoven fabrics was developed using a two-step process. In the first step, the fabrics were grafted with a linker molecule, 10-undecenoyl chloride, via esterification, followed by attachment of a functional material under UV irradiation. Perfluorodecanethiol and 3-mercaptopropionic acid (MPA) were connected to the linker-modified fabrics using thiol-ene click chemistry. Perfluorodecanethiol modified fabrics exhibited hydrophobicity with water contact angle of about 140° while MPA-modified fabrics were able to lower the pH of a solution by about 1.6. We additionally demonstrated the possibility to connect functional polymers to the linker-modified fabrics by radical graft polymerization of acrylic acid; this produced a thin layer of the polymer on the surface of the fabric. Fabrics modified with poly(acrylic acid) exhibited increased hydrophilicity with water contact angle of 0° for both cotton and viscose-polyester fabrics, while the water absorption capability for polypropylene fabrics increased from about 50 to 1200%.     

Application potential of coarse-grained diamond grinding wheels for precision grinding of optical materials

Fine-grained resin bonded diamond tools are often used for ultra-precision machining of brittle materials to achieve optical surfaces. A well-known drawback is the high tool wear. Therefore, grinding processes need to be developed exhibiting less wear and higher profitability. Consequently, the presented work focuses on conditioning a mono-layered, coarse-grained diamond grinding wheel with a spherical profile and an average grain size of 301 µm by combining a thermo-chemical and a mechanical-abrasive dressing technique. This processing leads to a run-out error of the grinding wheel in a low-micrometer range. Additionally, the thermo-chemical dressing leads to flattened grains, which supports the generation of hydrostatic pressure in the cutting zone and enables ductile-mode grinding of hard and brittle materials. After dressing, the application characteristics of coarse-grained diamond grinding wheels were examined by grinding optical glasses, fused silica and glass–ceramics in two different kinematics, plunge-cut surface grinding and cross grinding. For plunge-cut surface grinding, a critical depth of cut and surface roughness were determined and for cross-grinding experiments the subsurface damage was analyzed additionally. Finally, the identified parameters for ductile-machining with coarse-grained diamond grinding wheels were used for grinding a surface of 2000 mm² in glass–ceramics.     

Ontogeny and Season Constrain the Production of Herbivore-Inducible Plant Volatiles in the Field

Herbivores may induce plants to produce an array of volatile organic compounds (herbivore-induced plant volatiles, or HIPVs) after damage, and some natural enemies of herbivores are attracted by those HIPVs. The production of HIPVs by the undomesticated species Datura wrightii was quantified in response to damage by its natural community of herbivores or the plant hormone methyl jasmonate (MeJA) over plant’s 6-month growing season. Patterns of HIPV production were compared to the seasonal abundance of D. wrightii’s two most abundant herbivores, the chrysomelid beetle Lema daturaphila and the mirid bug Tupiocoris notatus, and their shared generalist predator, the lygaeid bug Geocoris pallens. HIPV production was especially high in the spring, when plants were growing vegetatively, but HIPV production declined after plants began to flower and produce fruit, and these volatiles no longer were inducible by September. The composition of the HIPV blends also changed seasonally. HIPV production and composition were partially restored by “rejuvenating” plants back to the vegetative growth stage independently of season by cutting them back and allowing them to resprout and regrow vegetatively. HIPV production of D. wrightii in the field is limited to the earlier ontogenetic stages of growth, despite the fact that both herbivores and their shared natural enemy inhabited plants throughout the full season. The adaptive value of HIPV production in D. wrightii may be constrained by plant ontogeny to the vegetative stages of plant growth.