A series of 1,4-benzoxazin-3-one derivatives containing an acylhydrazone moiety were designed, synthesized and evaluated for their in vitro antifungal activities against Gibberella zeae, Pellicularia sasakii, Phytophthora infestans, Capsicum wilt, and Phytophthora capsica. The structures of target compounds were characterized by 1H NMR, 13H NMR, 19F NMR and HRMS. The preliminary antifungal evaluation of all target compounds showed that some target compounds possessed moderate to good activities against G. zeae, P. sasakii, P. infestans and C. wilt. Among them, compounds 5L and 5o exhibited noticeable inhibition effects against G. zeae with the EC50 values (effective concentration for 50% activity) of 20.06 and 23.17 μg/ml, respectively, which were even nearly double effective than that of hymexazol (40.51 μg/ml). Meanwhile, compound 5q displayed a notable inhibitory effect toward P. sasakii, with the EC50 value of 26.66 μg/ml, which was better than that of hymexazol (32.77 μg/ml). In addition, compound 5r yielded the EC50 value of 15.37 μg/ml against P. infestans, which was less than those of hymexazol (18.35 μg/ml) and carbendazim (34.41 μg/ml). Eventually, compound 5p showed higher inhibitory effect against C. wilt, with EC50 value of 26.76 μg/ml, which was better than that of hymexazol (>50 μg/ml).

Synthesis of nanoparticles (NPs) for many different uses requires the development of environmentally friendly synthesis protocols. In this article, we present a simple and environmentally friendly method to synthesize lead oxide (PbO) NPs from the plant material of the Mangifera indica. Analytical techniques such as spectroscopy, X-ray diffraction, and microscopy were used to characterize the synthesized PbO NPs, and their photo-electrocatalytic and antifungal properties were also evaluated. H2O2 was used to investigate the efficacy of removing methylene blue dye. At a range of pH values, H2O2 was used to study the role of hydroxyl radicals in the breakdown of methylene blue dye. Methylene blue dyes are more easily eliminated due to increased generation of the *OH radical during removal. Dye degradation was also significantly affected by the aqueous medium’s pH. Additionally, the electrocatalytic properties of the PbO NPs adapted electrode were studied in CH3COONa aqueous solution using cyclic voltammetry. Excellent electrocatalytic properties of the PbO NPs are shown by the unity of the anodic and cathodic peaks of the modified electrode in comparison to the stranded electrode. Aspergillus flavus, Aspergillus niger, and Candida glabrata were some fungi tested with the PbO NPs. Against A. flavus (40%) and A. niger (50%), and C. glabrata (75%), the PbO NPs display an excellent inhibition zone. Finally, PbO NPs were used in antioxidant studies with the powerful antioxidant 2, 2 diphenyl-1-picrylhydrazyl (DPPH). This study presents a simple and environmentally friendly method for synthesizing PbO NPs with multiple uses, including photo-electrocatalytic and antimicrobial activity.

The NAO2GTO scheme provides an efficient way to evaluate the electron repulsion integrals (ERIs) over numerical atomic orbitals (NAOs) with auxiliary Gaussian-type orbitals (GTOs). However, the NAO2GTO fitting will significantly impact the accuracy and convergence of hybrid functional calculations. To address this issue, here we propose to use the fitted orbitals as a new numerical basis to properly handle the mismatch between NAOs and fitted GTOs. We present an efficient and linear-scaling implementation of analytical gradients of Hartree-Fock exchange (HFX) energy for periodic HSE06 calculations with fitted NAOs in the HONPAS package. In our implementation, the ERIs and their derivatives for HFX matrix and forces are evaluated analytically with the auxiliary GTOs, while other terms are calculated using numerically discretized GTOs. Several integral screening techniques are employed to reduce the number of required ERI derivatives. We benchmark the accuracy and efficiency of our implementation and demonstrate that our results of lattice constants, bulk moduli, and band gaps of several typical semiconductors are in good agreement with the experimental values. We also show that the calculation of HFX forces based on a master-worker dynamic parallel scheme has a very high efficiency and scales linearly with respect to system size. Finally, we study the geometry optimization and polaron formation due to an excess electron in rutile TiO2 by means of HSE06 calculations to further validate the applicability of our implementation.

Nanoplasmonic biosensors have a huge boost for precision medicine, which allows doctors to better understand diseases at the molecular level and to improve the earlier diagnosis and develop treatment programs. Unlike traditional biosensors, nanoplasmonic biosensors meet the global health industry’s need for low-cost, rapid and portable aspects, while offering multiplexing, high sensitivity and real-time detection. In this review, we describe the common detection schemes used based on localized plasmon resonance (LSPR) and highlight three sensing classes based on LSPR. Then, we present the recent applications of nanoplasmonic in other sensing methods such as isothermal amplification, CRISPR/Cas systems, lab on a chip and enzyme-linked immunosorbent assay. The advantages of nanoplasmonic-based integrated sensing for multiple methods are discussed. Finally, we review the current applications of nanoplasmonic biosensors in precision medicine, such as DNA mutation, vaccine evaluation and drug delivery. The obstacles faced by nanoplasmonic biosensors and the current countermeasures are discussed.

In this study, a new series of quinoxalinone derivatives (5a–5p, 6a–6n) was designed and its hypoglycemic activity was evaluated. The results showed that compounds 5i and 6b exhibited stronger hypoglycemic effects than the lead compounds and were comparable to the positive control Pioglitazone. 5i and 6b may exert hypoglycemic effects by alleviating cellular OS and modulating the interactions among GLUT4, SGLT2, and GLUT1 proteins. The alleviating cellular OS of compound 6b was better than that of 5i, and 6b was found to bind better than 5i for most of the screening targets. In summary, compound 6b is a potential lead compound with hypoglycaemic activity.3

Long-lived singlet spin order offers the possibility to extend the spin memory by more than an order of magnitude. This enhancement can be used, among other applications, to assist NMR diffusion experiments in porous media where the extended lifetime of singlet spin order can be used to gain information about structural features of the medium as well as the dynamics of the imbibed phase. Other than offering the possibility to explore longer diffusion times of the order of many minutes that, for example, gives unprecedented access to tortuosity in structures with interconnected pores, singlet order has the important advantage to be immune to the internal field gradients generated by magnetic susceptibility inhomogeneities. These inhomogeneities, however, are responsible for very short T2 decay constants in high magnetic field and this precludes access to the singlet order in the first instance. To overcome this difficulty and take advantage of singlet order in diffusion experiments in porous media, we have here developed a dual-core system with radiofrequency and 3-axis pulsed field gradients facilities in low magnetic field, for preparation and manipulation of singlet order and a probe, in high magnetic field, for polarisation and detection. The system operates in field-cycling and can be used for a variety of NMR experiments including diffusion tensor imaging (both singlet assisted and not). In this paper we present and discuss the new hardware and its calibration, and demonstrate its capabilities through a variety of examples.

A single crystal X-ray diffraction analysis was performed on two positional isomers (m-tolyl and p-tolyl) of acrylonitrile derivatives, namely, (Z)-3-(4-(pyridin-2-yl) phenyl)-2-(m-tolyl) acrylonitrile (1) and (Z)-3-(4-(pyridin-2-yl)phenyl)-2-(p-tolyl) acrylonitrile (2). Compound 1 crystallized in the monoclinic P21/n space group with two crystallographically independent molecules. Compound 2 also possesses two crystallographically independent molecules and crystallized in the triclinic P-1 space group. The Hirshfeld surface analysis revealed that, in both isomers, intermolecular H⋅⋅⋅H/C/N contacts contribute significantly to the crystal packing. More than 40% of the contribution arises from intermolecular C–H⋅⋅⋅C(π) contacts. In both compounds, the relative contribution of these contacts is comparable, indicating that the positional isomeric effects are marginal. The structures in which these isomers are arranged in the solid state are very similar, and the lattice energies are also comparable between the isomers. The Coulomb-London-Pauli-PIXEL (CLP-PIXEL) energy analysis identified the energetically significant dimers. The strength of the intra- and intermolecular interactions was evaluated using the quantum theory of atoms in molecules approach. The UV-Vis absorbance in three different solvents (chloroform, ethanol, and ethyl acetate) for isomers 1 and 2 are very similar. This result is in good agreement with the time-dependent density-functional theory (TD-DFT) calculations.

Breast cancer covers a large area of research because of its prevalence and high frequency all over the world. This study is based on drug discovery against breast cancer from a series of imidazole derivatives. A 3D-QSAR and activity atlas model was developed by exploring the dataset computationally, using the machine learning process of Flare. The dataset of compounds was divided into active and inactive compounds according to their biological and structural similarity with the reference drug. The obtained PLS regression model provided an acceptable r2 = 0.81 and q2 = 0.51. Protein-ligand interactions of active molecules were shown by molecular docking against six potential targets, namely, TTK, HER2, GR, NUDT5, MTHFS, and NQO2. Then, toxicity risk parameters were evaluated for hit compounds. Finally, after all these screening processes, compound C10 was recognized as the best-hit compound. This study identified a new inhibitor C10 against cancer and provided evidence-based knowledge to discover more analogs.

Large (120 nm) hexagonal NaYF4:Yb, Er nanoparticles (UCNPs) were synthesized by high-temperature coprecipitation method and coated with poly(ethylene glycol)-alendronate (PEG-Ale), poly (N,N-dimethylacrylamide-co-2-aminoethylacrylamide)-alendronate (PDMA-Ale) or poly(methyl vinyl ether-co-maleic acid) (PMVEMA). The colloidal stability of polymer-coated UCNPs in water, PBS and DMEM medium was investigated by dynamic light scattering; UCNP@PMVEMA particles showed the best stability in PBS. Dissolution of the particles in water, PBS, DMEM and artificial lysosomal fluid (ALF) determined by potentiometric measurements showed that all particles were relatively chemically stable in DMEM. The UCNP@Ale-PEG and UCNP@Ale-PDMA particles were the least soluble in water and ALF, while the UCNP@PMVEMA particles were the most chemically stable in PBS. Green fluorescence of FITC-Ale-modified UCNPs was observed inside the cells, demonstrating successful internalization of particles into cells. The highest uptake was observed for neat UCNPs, followed by UCNP@Ale-PDMA and UCNP@PMVEMA. Viability of C6 cells and rat mesenchymal stem cells (rMSCs) growing in the presence of UCNPs was monitored by Alamar Blue assay. Culturing with UCNPs for 24 h did not affect cell viability. Prolonged incubation with particles for 72 h reduced cell viability to 40%–85% depending on the type of coating and nanoparticle concentration. The greatest decrease in cell viability was observed in cells cultured with neat UCNPs and UCNP@PMVEMA particles. Thanks to high upconversion luminescence, high cellular uptake and low toxicity, PDMA-coated hexagonal UCNPs may find future applications in cancer therapy.

The Euphorbiaceae plant Euphorbia neriifolia L. is distributed widely in India, Thailand, Southeastern China, and Taiwan and used as a carminative and expectorant to treat several inflammation-related diseases, such as gonorrhoea, asthma, and cancer. In the course of our search for potential anti-inflammatory agents from the titled plant, 11 triterpenes from the stem of E. neriifolia were isolated and reported in our previous endeavor. Given its rich abundance in triterpenoids, the ethanolic extract in this follow-up exploration has led to the isolation of additional eight triterpenes, including six new euphanes—neritriterpenols H and J–N (1 and 3–7)—one new tirucallane, neritriterpenol I (2), and a known compound, 11-oxo-kansenonol (8). Their chemical structures were elucidated on the basis of spectroscopic data, including 1D- and 2D NMR, and HRESIMS spectra. The absolute stereochemistry of neritriterpenols was determined by single-crystal X-ray diffraction analysis, ICD spectra, and DP4+ NMR data calculations. Compounds 1–8 were also evaluated for their anti-inflammatory activity by using lipopolysaccharide (LPS)-stimulated IL-6 and TNF-α on RAW 264.7 macrophage cells. Intriguingly, the euphane-type triterpenes (1 and 3–8) showed an inhibitory effect on LPS-induced IL-6 but not on TNF-α, while tirucallane-type triterpene 2 showed strong inhibition on both IL-6 and TNF-α.

Nowadays biomass has become important sources for the synthesis of different carbon nanomaterials due to their low cost, easy accessibility, large quantity, and rapid regeneration properties. Although researchers have made great effort to convert different biomass into carbons for oxygen reduction reaction (ORR), few of these materials demonstrated good electrocatalytical performance in acidic medium. In this work, fresh daikon was selected as the precursor to synthesize three dimensional (3D) nitrogen doped carbons with hierarchical porous architecture by simple annealing treatment and NH3 activation. The daikon-derived material Daikon-NH3-900 exhibits excellent electrocatalytical performance towards oxygen reduction reaction in both alkaline and acidic medium. Besides, it also shows good durability, CO and methanol tolerance in different electrolytes. Daikon-NH3-900 was further applied as the cathode catalyst for proton exchange membrane (PEM) fuel cell and shows promising performance with a peak power density up to 245 W/g.

In comparison with all-carbon parent compounds, the incorporation of Si-element into carboskeletons generally endows the corresponding sila-analogues with unique biological activity and physical-chemical properties. Silacycles have recently shown promising application potential in biological chemistry, pharmaceuticals industry, and material chemistry. Therefore, the development of efficient methodology to assemble versatile silacycles has aroused increasing concerns in the past decades. In this review, recent advances in the synthesis of silacycle-system are briefly summarized, including transition metal-catalytic and photocatalytic strategies by employing arylsilanes, alkylsilane, vinylsilane, hydrosilanes, and alkynylsilanes, etc. as starting materials. Moreover, a clear presentation and understanding of the mechanistic aspects and features of these developed reaction methodologies have been high-lighted.

In this investigation, we report the effect on the microscopic dynamics and interactions of the cytokine interferon gamma (IFN-γ) and antibodies to IFN-γ (anti-IFN-γ) and to the interferon gamma receptor 1 (anti-IFNGR1) prepared in highly dilute (HD) solutions of initial proteins. THz spectroscopy measurements have been conducted as a means to analyze and characterize the collective dynamics of the HD samples. MD simulations have also been performed that have successfully reproduced the observed signatures from experimental measurement. Using this joint experimental-computational approach we determine that the HD process associated with the preparation of the highly diluted samples used in this investigation induces a dynamical transition that results in collective changes in the hydrogen-bond network of the solvent. The dynamical transition in the solvent is triggered by changes in the mobility and hydrogen-bonding interactions of the surface molecules in the HD samples and is characterized by dynamical heterogeneity. We have uncovered that the reorganization of the sample surface residue dynamics at the solvent-protein interface leads to both structural and kinetic heterogeneous dynamics that ultimately create interactions that enhance the binding probability of the antigen binding site. Our results indicate that the modified interfacial dynamics of anti-IFN-γ and anti-IFGNR1 that we probe experimentally are directly associated with alterations in the complementarity regions of the distinct antibodies that designate both antigen-antibody affinity and recognition.

With the use of proton-NMR and powder XRD (XRPD) studies, the suitability of specific Au-focused electron beam induced deposition (FEBID) precursors has been investigated with low electron energy, structure, excited states and resonances, structural crystal modifications, flexibility, and vaporization level. 4,5-Dichloro-1,3-diethyl-imidazolylidene trifluoromethyl gold(I) is a compound that is a uniquely designed precursor to meet the needs of focused electron beam-induced deposition at the nanostructure level, which proves its capability in creating high purity structures, and its growing importance in other AuImx and AuClnB (where x and n are the number of radicals, B = CH, CH3, or Br) compounds in the radiation cancer therapy increases the efforts to design more suitable bonds in processes of SEM (scanning electron microscopy) deposition and in gas-phase studies. The investigation performed of its powder shape using the XRPD XPERT3 panalytical diffractometer based on CoKα lines shows changes to its structure with change in temperature, level of vacuum, and light; the sensitivity of this compound makes it highly interesting in particular to the radiation research. Used in FEBID, though its smaller number of C, H, and O atoms has lower levels of C contamination in the structures and on the surface, it replaces these bonds with C–Cl and C–N bonds that have lower bond-breaking energy. However, it still needs an extra purification step in the deposition process, either H2O, O2, or H jets.

Nitroguaiacols are typical constituents of biomass-burning emissions, including absorbing aerosols which contribute to climate change. Although they are also harmful to humans and plants, their atmospheric fate and lifetimes are still very speculative. Therefore, in this work, the photolysis kinetics of aqueous-phase 4-nitroguaiacol (4NG) and 5-nitroguaiacol (5NG), and the resulting photo-formed products were investigated under artificial sunlight, observing also the effect of sunlight on the absorption properties of the solutions. We found the photolysis of 5NG slower than that of 4NG, whereas the absorbance in the visible range prevailed in the 5NG solutions at the end of experiments. Although we identified dinitroguaiacol as one of the 4NG photolysis products, which increased light absorption of 4NG-containing solutions, considerably more chromophores formed in the 5NG photolyzed solutions, implying its stronger potential for secondary BrC formation in the atmosphere. In general, denitration, carbon loss, hydroxylation, nitration, and carbon gain were characteristic of 4NG phototransformation, while carbon loss, hydroxylation, and carbon gain were observed in the case of 5NG. The photolysis kinetics was found of the first order at low precursor concentrations (<0.45 mM), resulting in their lifetimes in the order of days (125 and 167 h illumination for 4NG and 5NG, respectively), which suggests long-range transport of the investigated compounds in the atmosphere and proposes their use as biomass-burning aerosol tracer compounds.

Low-cost clean primary production of magnesium metal is important for its use in many applications, from light-weight structural components to energy technologies. This work describes new experiments and cost and emissions analysis for a magnesium metal production process. The process combines molten salt electrolysis of MgO using MgF₂-CaF₂ electrolyte and a reactive liquid tin cathode, with gravity-driven multiple effect thermal system (G-METS) distillation to separate out the magnesium product, and re-use of the tin. Electrolysis experiments with carbon anodes showed current yield above 90%, while a yttria-stabilized zirconia solid oxide membrane (SOM) anode experiment showed 84% current yield. G-METS distillation is an important component of the envisioned process. It can potentially lower costs and energy use considerably compared with conventional magnesium distillation. Techno-economic analysis including detailed mass and energy balances shows that this electrolyte composition could lower costs by utilizing CaO, which is the primary impurity in MgO, as the Hall-Héroult process uses the sodium impurity in alumina. Analysis options include: raw material types (magnesite rock vs. brine or seawater), drying and calcining using electricity vs. natural gas, and carbon vs. SOM anode type. Using SOM inert anodes results in a cost premium around 10%–15%, mostly due to higher electrical energy usage resulting from membrane resistance, and reduces GHG emissions by approximately 1 kg CO₂/kg Mg product. Capital and operating cost estimates, and cradle to gate greenhouse gas (GHG) emissions analysis under several raw material and process technology scenarios, show comparable costs and emissions to those of aluminum production.

In this article, we describe a proof of concept of the potential use of a biocatalytic process for the functionalization of technical soda lignins from wheat straw through the selective acylation of primary hydroxy groups of lignin oligomers by acetate or hexanoate, thus preserving their free, unreacted phenols. The selectivity and efficiency of the method, although they depend on the structural complexity of the starting material, have been proven on model compounds. Applied to technical lignins, the acylation yield is only moderate, due to structural and chemical features induced by the industrial mode of preparation of the lignins rather than to the lack of efficiency of the method. However, most of the physicochemical properties of the lignins, including their antioxidant potential, are preserved, advocating the potential use of these modified lignins for industrial applications.

Due to its excellent properties, poly(ethylene terephthalate) (PET) is one of the most produced and consumed polymers. Among plastics, it represents the main contributor to environmental pollution. Following the circular economy model, the chemical upcycling of PET reduces the amount of waste generated and transforms it into high-value products. The depolymerization of poly(ethylene terephthalate) into oligomers or monomers leads to forming a library of reactive molecules involved in different polymerization processes to obtain compounds with improved properties. Herein, several β-hydroxy amines were synthesized and used for the chemical recycling of water bottle waste by an environmental benefit aminolysis process to get very useful new terephthalamide diol monomers. The recycled diol monomers were subsequently exploited to synthesize poly(urethane acrylates) (PUAs) UV-curable coatings, and their chemical, thermal and mechanical characterizations were performed. The results show the great potential of the developed synthesis protocols to obtain PUAs with final properties that can be modulated to meet the requirements of different applications.