Carbohydrate-based nanostructured catalysts: applications in organic transformations

The requirement of green and sustainable materials to prepare heterogeneous catalysts has intensified for practical reasons over the past few decades. Carbohydrates are possibly the most plentiful and renewable organic materials in nature with inimitable physiochemical properties, plausible low-cost and large-scale production, and sustainability features could be exploited in the generation of nanostructured heterogeneous catalysts. This review article outlines the organic transformations catalyzed by diverse carbohydrate-based nanostructured catalysts in greener and environmentally friendly processes. Selected examples are highlighted for a variety of organic reactions exploiting the proposed catalysts’ reactivity and reusability, and interactions with the intrinsic nature of the applied carbohydrate supports; advantages and speculated challenges of the introduced catalysts are deliberated as well.     

Solid‐phase microextraction Arrow for the volatile organic compounds in soy sauce

A novel solid‐phase microextraction Arrow was used to separate volatile organic compounds from soy sauce, and the results were verified by using gas chromatography with mass spectrometry. Solid‐phase microextraction Arrow was optimized in terms of three extraction conditions: type of fiber used (polydimethylsiloxane, polyacrylate, carbon wide range/polydimethylsiloxane, and divinylbenzene/polydimethylsiloxane), extraction temperature (40, 50, and 60°C), and extraction time (10, 30, and 60 min). The optimal solid‐phase microextraction Arrow conditions were as follows: type of fiber = polyacrylate, extraction time = 60 min, and extraction temperature = 50°C. Under the optimized conditions, the solid‐phase microextraction Arrow was compared with conventional solid‐phase microextraction to determine extraction yields. The solid‐phase microextraction Arrow yielded 6–42‐fold higher levels than in solid‐phase microextraction for all 21 volatile organic compounds detected in soy sauce due to the larger sorption phase volume. The findings of this study can provide practical guidelines for solid‐phase microextraction Arrow applications in food matrixes by providing analytical methods for volatile organic compounds.     

Reversible Shape‐Morphing and Fluorescence‐Switching in Supramolecular Nanomaterials Consisting of Amphiphilic Cyanostilbene and Cucurbit[7]uril

We demonstrate a reversible shape‐morphing with concurrent fluorescence switching in the nanomaterials which are complexed with cucurbit[7]uril (CB[7]) in water. The cyanostilbene derivative alone forms ribbon‐like two‐dimensional (2D) nanocrystals with bright yellow excimeric emission in water (λ_em=540 nm, Φ_F=42 %). Upon CB[7] addition, however, the ribbon‐like 2D nanocrystals immediately transform to spherical nanoparticles with significant fluorescence quenching and blue‐shifting (λ_em=490 nm, Φ_F=1 %) through the supramolecular complexation of the cyanostilbene and CB[7]. Based on this reversible fluorescence switching and shape morphing, we could demonstrate a novel strategy of turn‐on fluorescence sensing of spermine and also monitoring of lysine decarboxylase activity.     

Influence of Morphological Homogeneity of Superspherical Gold Nanoparticles on Plasmonic Photothermal Heat Generation

The plasmonic photothermal (PPT) characteristics of gold nanostructures have been extensively investigated theoretically and experimentally due to their potential for use materials science and industry. The management of the size and shape of gold nanoparticles has been a key issue in the development of better solutions for PPT heat generation because their size and shape determine their resultant photothermal properties. However, the light absorption of gold nanostructures is mainly dependent on the wavelength and orientation of the incident light; hence, maintaining uniform size and shape is critical for achieving maximum photothermal energy. Morphologically homogeneous spherical gold nanoparticles, or super gold nanospheres prepared by slowly etching uniform octahedral gold nanoparticles, demonstrate better PPT heat generation compared with commercially available nonsmooth gold nanoparticles (GNSs). The PPT heating experiments show a maximum temperature difference of 5.7 °C between the super and ordinary GNSs with the same average maximum Feret's diameters, which result from the more efficient PPT heat power generation (20.6%) of the super GNSs. In an electromagnetic‐wave simulation, the super GNSs show lower polarization dependence and a 24.6% higher absorption cross‐section than ordinary GNSs.     

Modulation of Foreign Body Reaction against PDMS Implant by Grafting Topographically Different Poly(acrylic acid) Micropatterns

The surface of poly(dimethylsiloxane) (PDMS) is grafted with poly(acrylic acid) (PAA) layers via surface‐initiated photopolymerization to suppress the capsular contracture resulting from a foreign body reaction. Owing to the nature of photo‐induced polymerization, various PAA micropatterns can be fabricated using photolithography. Hole and stripe micropatterns ≈100‐µm wide and 3‐µm thick are grafted onto the PDMS surface without delamination. The incorporation of PAA micropatterns provides not only chemical cues by hydrophilic PAA microdomains but also topographical cues by hole or stripe micropatterns. In vitro studies reveal that a PAA‐grafted PDMS surface has a lower proliferation of both macrophages (Raw 264.7) and fibroblasts (NIH 3T3) regardless of the pattern presence. However, PDMS with PAA micropatterns, especially stripe micropatterns, minimizes the aggregation of fibroblasts and their subsequent differentiation into myofibroblasts. An in vivo study also shows that PDMS samples with stripe micropatterns polarized macrophages into anti‐inflammatory M2 macrophages and most effectively inhibits capsular contracture, which is demonstrated by investigation of inflammation score, transforming‐growth‐factor‐β expression, number of macrophages, and myofibroblasts as well as the collagen density and capsule thickness.     

Catalytic Asymmetric Synthesis of Cyclohexanes by Hydrogen Borrowing Annulations

Hydrogen borrowing catalysis serves as a powerful alternative to enolate alkylation, enabling the direct coupling of ketones with unactivated alcohols. However, to date, methods that enable control over the absolute stereochemical outcome of such a process have remained elusive. Here we report a catalytic asymmetric method for the synthesis of enantioenriched cyclohexanes from 1,5‐diols via hydrogen borrowing catalysis. This reaction is mediated by the addition of a chiral iridium(I) complex, which is able to impart high levels of enantioselectivity upon the process. A series of enantioenriched cyclohexanes have been prepared and the mode of enantioinduction has been probed by a combination of experimental and DFT studies.     

Simultaneous determination of 75 abuse drugs including amphetamines,benzodiazepines, cocaine,opioids, piperazines,zolpidem and metabolites in human hair samples using liquid chromatography–tandem mass spectrometry

A liquid chromatography–tandem mass spectrometric method for the simultaneous determination of 75 abuse drugs and metabolites, including 19 benzodiazepines, 19 amphetamines, two opiates, eight opioids, cocaine, lysergic acid diethylamide, zolpidem, three piperazines and 21 metabolites in human hair samples, was developed and validated. Ten‐milligram hair samples were decontaminated, pulverized using a ball mill, extracted with 1 mL of methanol spiked with 28 deuterated internal standards in an ultrasonic bath for 60 min at 50°C, and purified with Q‐sep dispersive solid‐phase extraction tubes. The purified extracts were evaporated to dryness and the residue was dissolved in 0.1 mL of 10% methanol. The 75 analytes were analyzed on an Acquity HSS T3 column using gradient elution of methanol and 0.1% formic acid and quantified in multiple reaction monitoring mode with positive electrospray ionization. Calibration curves were linear (r ≥ 0.9951) from the lower limit of quantitation (2–200 pg/mg depending on the drug) to 2000 pg/mg. The coefficients of variation and accuracy for intra‐ and inter‐assay analysis at three QC levels were 4.3–12.9% and 89.2–109.1%, respectively. The overall mean recovery ranged from 87.1 to 105.3%. This method was successfully applied to the analysis of 11 forensic hair samples obtained from drug abusers.     

Oxygen Vacancy Diffusion and Condensation in Lithium‐Ion Battery Cathode Materials

Oxygen vacancies (OV) are native defects in transition metal (TM) oxides and their presence has a critical effect on the physicochemical properties of the oxide. Metal oxides are commonly used in lithium‐ion battery (LIB) cathodes and there is still a lack of understanding of the role of OVs in LIB research field. Here, we report on the behavior of OVs in a single‐crystal LIB cathode during the non‐equilibrium states of charge and discharge. We found that microcrack evolution in a single crystal occurs due to OV condensation in specific crystallographic orientations generated by the continuous migration of OVs and TM ions. Moreover, understanding the effects of the presence and diffusion of OVs in metal oxides enables the elucidation of most of the conventional mechanisms of capacity fading in LIBs and provides new insights for new electrochemical applications.     

Origin of Antibacterial Activity of ZnO Nanoparticles: The Roles of Protonic and Electronic Conductions

To elucidate the origin of antibacterial activity of ZnO nanoparticles, a reactive oxygen species (ROS) mechanism is systematically investigated based on electronic and protonic conductions. While the enhancement of antibacterial activity by an increase in electronic conductivity is marginal, an apparent improvement is observed by in the increase of protonic conductivity in terms of the surface basicity. This study first demonstrates that antibacterial activity can be enhanced by controlling the surface basicity of solid particles. The basicity of ZnO can be modulated by doping alkaline‐earth oxides such as MgO and CaO, and it results in the increase of hydroxyl defects on the surface of solid particles. The basicity shows a strong dependency on mobile OH concentrations. The increase of ROS hydroxyl radicals is confirmed by Mg (ZMO) or Ca‐doping (ZCO), which shows high antibacterial activity, and Ca‐doped ZnO exhibits the highest performance. It is clearly observed that the antibacterial activity is proportional to the basicity, which is controlled by the mobile OH formation. While both electrons and hydroxyl species are required for ROS reactions, it is concluded that the formation of hydroxyl species is a key factor in improving the antibacterial activity in ZnO.