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.     

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.     

Electrostatic-thermodynamic-kinetic (ELTHEKI) modeling of the coupled $$\text {Ni}$$ / $$\text {Ni}\text {O}$$ /water system,under physico-chemical conditions of pressurized water reactors

Journal of Solid State Electrochemistry - In the present paper, we develop an electrostatic-thermodynamic-kinetic (ELTHEKI) model for studying the behavior of the specific $$\text {Ni}$$ / $$\text...     

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.     

Dynamic Kinetic Resolution of 2-(Quinolin-8-yl)Benzaldehydes: Atroposelective Iridium-Catalyzed Transfer Hydrogenative Allylation

An atroposelective Ir-catalyzed dynamic kinetic resolution (DKR) of 2-(quinolin-8-yl)benzaldehydes/1-naphthaldehydes by transfer hydrogenative coupling of allyl acetate is disclosed. The allylation reaction takes place with simultaneous installation of central and axial chirality, reaching high diastereoselectivities and excellent enantiomeric excesses when ortho-cyclometalated iridium-DM-BINAP is used as the catalyst. The racemization of the substrates occurs through a designed transient Lewis acid-base interaction between the quinoline nitrogen atom and the aldehyde carbonyl group.     

Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores

The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR ( pGNR ) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor ( P1 ) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds ( 1 a , 1 b ) containing the same pore size as the shortcuts of pGNR , are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π–π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability.