Hierarchical structure of SERS substrates possessing the silver ring morphology

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Synthesis and rheological properties of star-shaped polydimethylsiloxanes based on carbosilane dendrimers

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Singlet Oxygen's Potential Role as a Nonoxidative Facilitator of Disulfide S–S Bond Rotation†

The role of singlet oxygen potentially mediating increased conformational flexibility of a disulfide was investigated. Density functional theory (DFT) calculations indicate that the singlet oxygenation of 1,2-dimethyldisulfane produces a peroxy intermediate. This intermediate adopts a structure with a longer S–S bond distance and a more planar torsional angle θ (C–S–S–C) compared with the nonoxygenated 1,2-dimethyldisulfane. The lengthened S–S bond enables a facile rotation about the torsional angle in the semicircle region 0° < θ < 210°, that is ~5 kcal mol⁻¹ lower in energy than the disulfane. The peroxy intermediate bears n_O → σ_S–S and n_O → σ*_S–S interactions that stabilize the S–O bond but destabilize the S–S bond, which contrasts with stabilizing n_S → σ*_S–S hyperconjugative effects in the disulfane S–S bond. Subsequent departure of O₂ from the disulfane peroxy intermediate is reminiscent of peroxy intermediates which also expel O₂, yet facilitate cis-trans isomerizations of stilbenes, hexadienes, cyanines, and carotenes. “Non-oxidative” ¹O₂ interactions with a variety of bond types are currently underappreciated. We hope to raise awareness of how these interactions can help elucidate the origins of molecular twisting.     

Uniform antibacterial cylindrical nanoparticles for enhancing the strength of nanocomposite hydrogels

Crystallization-driven self-assembly (CDSA) was employed for the preparation of monodisperse cationic cylindrical nanoparticles with controllable sizes, which were subsequently explored for their effect on antibacterial activity and the mechanical properties of nanocomposite hydrogels. Poly(ɛ-caprolactone)-block-poly(methyl methacrylate)-block-poly[2-(tert-butylamino) ethyl methacrylate] (PCL-b-PMMA-b-PTA) triblock copolymers were synthesized using combined ring-opening and RAFT polymerizations, and then self-assembled into polycationic cylindrical micelles with controllable lengths by epitaxial growth. The polycationic cylinders exhibited intrinsic cell-type-dependent antibacterial capabilities against gram-positive and gram-negative bacteria under physiological conditions, without quaternization or loading of any additional antibiotics. Furthermore, when the cylinders were combined into anionic alginate hydrogel networks, the mechanical response of the hydrogel composite was tunable and enhanced up to 51%, suggesting that cationic polymer fibers with controlled lengths are promising mimics of the fibrous structures in natural extracellular matrix to support scaffolds. Overall, this polymer fiber/hydrogel nanocomposite shows potential as an injectable antibacterial biomaterial, with possible application in implant materials as bacteriostatic agents or bactericides against various infections.     

Design and Development of a Non-Enzymatic Electrochemical Biosensor for the Detection of Glutathione

Glutathione (GSH-reduced form) is a tripeptide that plays a vital role as an antioxidant to remove xenobiotics in the human body and changes in GSH levels are a marker for the progression of various diseases. In this context, a highly sensitive non-enzymatic electrochemical biosensor for the detection of GSH has been developed using reduced graphene oxide Manganese oxide (rGMnO) nanocomposite as the nano-interface. Initially, graphene oxide was synthesized by Hummer's method and then thermally reduced in the presence of MnO₂ in a blast furnace to obtain rGMnO nanocomposite. The nanocomposite was characterized to validate its structure and morphological properties via Scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry and amperometry studies showed that upon the addition of GSH, the Pt/rGMnO modified working electrode exhibited a linear response in the range of 1–100 μM at an input voltage of −0.62 V. The developed sensor was found to have a sensitivity of 0.3256 μA μM⁻¹ and LOD of 970 nM with a recovery of 92–104 % in real blood serum samples.     

Effect of different starch contents on physical,morphological, mechanical,barrier, and biodegradation properties of tapioca starch and poly(butylene adipate-co-terephthalate) blend film

Study on degradation behaviors of biodegradable poly(butylene adipate-co-terephthalate) (PBAT) blended with different compositions of thermoplastic starch (TPS) under soil burial and natural weathering environments is vital in order to predict the product service-life and planning for in situ biodegradation after product disposal. In this article, different compositions of TPS (0%, 20%, 40%, 50%, and 60%) were compounded with PBAT using single screw extruder. The samples were characterized for their tensile properties, fractured surface morphology, water barrier and surface hydrophorbicity properties in order to investigate the effect of starch fractions in PBAT blends. The degradation behavior under natural weathering and soil burial conditions was also determined during the 9 months duration by observing the change of physical appearance, weight loss, surface morphology, chemical structural, and tensile properties. The findings showed that the addition of TPS (20%, 40%, 50%, and 60%) had led to a reduction in tensile strength (41.47%, 60.53%, 63.43%, and 68.53%), and reduction in elongation at break (42.92%, 92.1%, 92.23%, and 93.22%, respectively) and water barrier properties. The findings also showed that there were distinct degradation behavior under both conditions. Upon exposure to natural weathering, photodegradation and Norrish type I & II occurred whereas under the soil burial condition, hydrolytic, and enzymatic degradation take places. Sample with the highest starch contents underwent the highest weight loss and reduction in tensile properties under both environments. The findings in this study are useful in order to investigate the feasibility of PBAT/Tapioca starch blends for biodegradable plastic film for various industrial applications especially in packaging and agricultural mulch.     

SMART: A data reporting standard for mass spectrometry imaging By Ying Xi,Alexandria L. Sohn,Alena N. Joignant,Stephanie M. Cologna,Boone M. Prentice and David C. Muddiman

Mass spectrometry imaging (MSI) is an important analytical technique that simultaneously reports the spatial location and abundance of detected ions in biological, chemical, clinical, and pharmaceutical studies. As MSI grows in popularity, it has become evident that data reporting varies among different research groups and between techniques. The lack of consistency in data reporting inherently creates additional challenges in comparing intra- and inter-laboratory MSI data. In this tutorial, we propose a unified data reporting system, SMART, based on the common features shared between techniques. While there are limitations to any reporting system, SMART was decided upon after significant discussion to more easily understand and benchmark MSI data. SMART is not intended to be comprehensive but rather capture essential baseline information for a given MSI study; this could be within a study (e.g., effect of spot size on the measured ion signals) or between two studies (e.g., different MSI platform technologies applied to the same tissue type). This tutorial does not attempt to address the confidence with which annotations are made nor does it deny the importance of other parameters that are not included in the current SMART format. Ultimately, the goal of this tutorial is to discuss the necessity of establishing a uniform reporting system to communicate MSI data in publications and presentations in a simple format to readily interpret the parameters and baseline outcomes of the data.     

Salt Metathesis: Tetrafluoroborate Anion Rapidly Fluoridates Organoboronic Acids to give Organotrifluoroborates

Tetrafluoroborate (BF₄⁻) has long been used as a spectator counter anion. Herein, we report an unprecedented salt metathesis between a variety of BF₄⁻ salts and a series of organoboronic acids yielding the corresponding organotrifluoroborates. We identified conditions for fast and efficient fluoridation (<1 h) with minimal workup. Fundamentally, this work discloses the proclivity of BF₄⁻ to exchange fluoride atoms with organoboronates, highlighting the lability of BF₄⁻.     

Ruthenium-Catalyzed C−C Coupling of Terminal Alkynes with Primary Alcohols or Aldehydes: α,β-Acetylenic Ketones (Ynones) via Oxidative Alkynylation

The first metal-catalyzed oxidative alkynylations of primary alcohols or aldehydes to form α,β-acetylenic ketones (ynones) are described. Deuterium labelling studies corroborate a novel reaction mechanism in which alkyne hydroruthenation forms a transient vinylruthenium complex that deprotonates the terminal alkyne to form the active alkynylruthenium nucleophile.     

Catalytic Homologation-Allylboration Sequence for Diastereo- and Enantioselective Synthesis of Densely Functionalized β-Fluorohydrins with Tertiary Fluoride Stereocenters

Homologation of trisubstituted fluoroalkenes followed by allylboration of aldehyde, ketone and imine substrates is suitable for synthesis of β-fluorohydrin and amine products. In the presence of (R)-iodo-BINOL catalyst enantioselectivities up to 99 % can be achieved by formation of a single stereoisomer with adjacent stereocenters, of which one is a tertiary C−F center.