Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold

Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal-rich silicon phosphides RuSi₄P₄ and IrSi₃P₃ are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X-ray diffraction and ²⁹Si and ³¹P magic angle spinning NMR. In agreement with previous report RuSi₄P₄ crystallizes in NCS space group P1, while IrSi₃P₃ is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi₄P₄ and IrSi₃P₃ to be wide bandgap (E_g) semiconductors, E_g = 1.9 and 1.8 eV, respectively. RuSi₄P₄ and IrSi₃P₃ outperform the current state-of-the-art infrared SHG material, AgGaS₂, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi₄P₄ and IrSi₃P₃ are promising candidates for longer wavelength NLO materials.     

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.     

Investigation of Thermal Gradient Mechanical Fatigue Test Methods for Nickel-based Superalloys

Experimental Mechanics - Temperature gradients significantly affect the material fatigue process. A reliable and robust test procedure is needed for quantifying the effects of temperature gradients...     

Investigation of Relationships between Grain Structure and Inhomogeneous Deformation by Means of Laboratory-Based Multimodal X-Ray Tomography: Strain Accuracy Analysis

Experimental Mechanics - The internal strain distribution developing during plastic deformation is important for understanding the mechanical properties of polycrystalline materials. Such...     

Organic Semiconducting Luminophores for Near-Infrared Afterglow,Chemiluminescence, and Bioluminescence Imaging

Optical imaging has played a pivotal role in deciphering in vivo bioinformatics but is limited by shallow penetration depth and poor imaging performance owing to interfering tissue autofluorescence induced by concurrent photoexcitation. The emergence of near-infrared (NIR) self-luminescence imaging independent of real-time irradiation has timely addressed these problems. There are two main kinds of self-luminescent agents, namely inorganic and organic luminophores. Inorganic luminophores usually suffer from long-term biotoxicity concerns resulting from potential heavy-metal ions leakage and nonbiodegradability, which hinders their further translational application. In contrast, organic luminophores, especially organic semiconducting luminophores (OSLs) with good biodegradable potential, tunable design, and outstanding optical properties, are preferred in biological applications. This review summarizes the recent progress of OSLs used in NIR afterglow, chemiluminescence, and bioluminescence imaging. Molecular manipulation and nanoengineering approaches of OSLs are discussed, with emphasis on strategies that can extend the emission wavelength from visible to NIR range and amplify luminescence signals. This review concludes with a discussion of current challenges and possible solutions of OSLs in the self-luminescence field.     

Designing Semipermeable Hydrogel Shells with Controlled Thickness through Internal Osmosis in Triple-Emulsion Droplets

Hydrogel shells that compartmentalize the water core from the aqueous surrounding provide molecular selectivity on size and charge in transmembrane transport. It is highly demanding to produce thin hydrogel shells to minimize diffusion length and maximize core volume. Here, internal osmosis in water-in-oil-in-water-in-oil (W/O/W/O) triple-emulsion droplets is used to produce thin hydrogel shells enclosing a large water core. The triple-emulsion droplets are prepared to have an ultrathin middle oil layer using a capillary microfluidic device. The innermost water droplet has a higher osmolarity than the outer water layer containing photopolymerizable hydrogel precursors, which pumps water from the outer layer to the core through the ultrathin oil layer by the osmosis. Therefore, the outer layer gets thinner and hydrogel precursors are enriched while the size of the triple-emulsion droplets remains unchanged. Through photopolymerization of precursors and phase transfer from oil to water, hydrogel shells enclosing water core are produced in the water environment; the oil layer is ruptured for molecular exchange through the shells. The thickness and composition of the hydrogel shells are precisely controllable by the osmotic conditions. The shells show a high permeation rate due to the thinness as well as controlled cut-off threshold of permeation for neutral and charged molecules.     

Nanovaccine-Mediated Cell Selective Delivery of Neoantigens Potentiating Adoptive Dendritic Cell Transfer for Personalized Immunization

Neoantigen vaccines and adoptive dendritic cell (DC) transfer are major clinical approaches to initiate personalized immunity in cancer patients. However, the immunization efficacy is largely limited by the in vivo trajectory including neoantigens’ access to resident DCs and DCs’ access to lymph nodes (LNs). Herein, an innovative strategy is proposed to improve personalized immunization through neoantigen-loaded nanovaccines synergized with adoptive DC transfer. It is found that it enables selective delivery of neoantigens to resident DCs and macrophages by coating cancer cell membranes onto neoantigen-loaded nanoparticles. In addition, the nanovaccines promote the secretion of chemokine C-C motif ligand 2 (CCL2), CCL3, and C-X-C motif ligand 10 from macrophages, thus potentiating the access of transferred DCs to LNs. This immunization strategy enables coordinated delivery of identified neoantigens and autologous tumor lysate-derived undefined antigens, leading to initiation of antitumor T cell immunity in a personalized manner. It significantly inhibits tumor growth in prophylactic and established mouse tumor models. The findings provide a new vision for potentiating adoptive cell transfer by nanovaccines, which may open the door to a transformative possibility for improving personalized immunization.     

Understanding the solubility and crystallization of molybdenum in high-sodium borosilicate glasses: effect of lanthanum oxide

Journal of Radioanalytical and Nuclear Chemistry - The simplified 8-oxide system (SiO2-B2O3-Na2O-Al2O3-CaO-TiO2-MoO3-La2O3) has been prepared under two types of cooling methods, and analyzed with...     

Anti-fibrosis attributes: UHPLC-MS/MS-based pharmacokinetics profiling of a novel autotaxin inhibitor with excellent in vivo efficacy in rat

3,4-Difluorobenzyl(1-ethyl-5-(4-((4-hydroxypiperidin-1-yl)-methyl)thiazol-2-yl)-1H-indol-3-yl)carbamate (NAI59), a small molecule with outstanding therapeutic effectiveness to anti-pulmonary fibrosis, was developed as an autotaxin inhibitor candidate compound. To evaluate the pharmacokinetics and plasma protein binding of NAI59, a UPLC–MS/MS method was developed to quantify NAI59 in plasma and phosphate-buffered saline. The calibration curve linearity ranged from 9.95 to 1990.00 ng/mL in plasma. The accuracy was −6.8 to 5.9%, and the intra- and inter-day precision was within 15%. The matrix effect and recovery, as well as dilution integrity, were within the criteria. The chromatographic and mass spectrometric conditions were also feasible to determine phosphate-buffered saline samples, and it has been proved that this method exhibits good precision and accuracy in the range of 9.95–497.50 ng/mL in phosphate-buffered saline. This study is the first to determine the pharmacokinetics, absolute bioavailability, and plasma protein binding of NAI59 in rats using this established method. Therefore, the pharmacokinetic profiles of NAI59 showed a dose-dependent relationship after oral administration, and the absolute bioavailability in rats was 6.3%. In addition, the results of protein binding showed that the combining capacity of NAI59 with plasma protein attained 90% and increased with the increase in drug concentration.     

A New Quassinoid from Brucea javanica

Chemistry of Natural Compounds - A new quassinoid, dehydrobruceantinol B (1), was isolated from the seeds of Brucea javanica, together with two known compounds, bruceantinol (2) and bruceine A (3)....