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Improving the fast-charging capabilities and energy storage capacity of electric vehicles presents a feasible strategy for mitigating the prevalent concern of range anxiety in the market. Nanostructure electrode materials play a crucial role in this process. However, the current method of preparation is arduous and yields restricted quantities. In view of this, we have devised an innovative approach that provides convenience and efficacy, facilitating the large-scale synthesis of CoS2 nanoparticles, which exhibited exceptional performance. When the current density was 1000 mA g−1, the discharging capacity reached 760 mAh g−1 after 400 cycles. Remarkably, even at an increased current density of 5000 mA g−1, the discharging capacity of CoS2 remained at 685.5 mAh g−1. The ultra-high performance could be attributed to the specific surface area, which minimized the diffusion distance of sodium-ions during the charging and discharging processes and mitigated the extent of structural damage. Our straightforward preparation techniques facilitate the mass production and present a novel approach for the development of cost-effective and high-performing anode materials for sodium-ion batteries. [ABSTRACT FROM AUTHOR]

This work reports the construction of a miniaturized Ag/AgCl nanoelectrode on a nanopipette, which is capable of dual-functions of single-cell drug infusion and chloride detection and is envisioned to promote the study of chloride-correlated therapeutic effects. [ABSTRACT FROM AUTHOR]

Twenty new zinc(II) complexes with 8-hydroxyquinoline (H-Q1–H-Q6) in the presence of 1,10-phenanthroline derivatives (D1–D10) were synthesized and formulated as [Zn(Q1)2(D1)] (DQ1), [Zn(Q2)2(D2)]·CH3OH (DQ2), [Zn(Q1)2(D3)] (DQ3), [Zn(Q1)2(D4)] (DQ4), [Zn(Q3)2(D5)] (DQ5), [Zn(Q3)2(D4)] (DQ6), [Zn(Q4)2(D5)]·CH3OH (DQ7), [Zn(Q4)2(D6)] (DQ8), [Zn(Q4)2(D3)]·CH3OH (DQ9), [Zn(Q4)2(D1)]·H2O (DQ10), [Zn(Q5)2(D4)] (DQ11), [Zn(Q6)2(D6)]·CH3OH (DQ12), [Zn(Q5)2(D2)]·5CH3OH·H2O (DQ13), [Zn(Q5)2(D7)]·CH3OH (DQ14), [Zn(Q5)2(D8)]·CH2Cl2 (DQ15), [Zn(Q5)2(D9)] (DQ16), [Zn(Q5)2(D1)] (DQ17), [Zn(Q5)2(D5)] (DQ18), [Zn(Q5)2(D10)]·CH2Cl2 (DQ19) and [Zn(Q5)2(D3)] (DQ20). They were characterized using multiple techniques. The cytotoxicity of DQ1–DQ20 was screened using human cisplatin-resistant SK-OV-3/DDP ovarian cancer (SK-OV-3CR) cells and normal hepatocyte (HL-7702) cells. Complex DQ6 showed low IC50 values (2.25 ± 0.13 μM) on SK-OV-3CR cells, more than 3.0–8.0 times more cytotoxic than DQ1–DQ5 and DQ7–DQ20 (≥6.78 μM), and even 22.2 times more cytotoxic than the standard cisplatin, the corresponding free H-Q1–H-Q6 and D1–D10 alone (>50 μM). As a comparison, DQ1–DQ20 displayed nontoxic rates against healthy HL-7702 cells. Furthermore, DQ6 and DQ11 induced significant apoptosis via mitophagy pathways. DQ6 also significantly inhibited tumor growth in an in vivo SK-OV-3-xenograft model (ca. 49.7%). Thus, DQ6 may serve as a lead complex for the discovery of new antitumor agents. [ABSTRACT FROM AUTHOR]

Three mononuclear, dinuclear and one-dimensional dysprosium(III) complexes based on 3-azotriazolyl-2,6-dihydroxybenzoic acid (H4ATB) of [Dy(H3ATB)3]·3H2O (1), [Dy2(H2ATB)2(H2DHB)2(H2O)4]·2CH3CN·5H2O (2), and [Dy2(H2ATB)2(DCB)(DMF)2(H2O)2]·4DMF (3) were synthesized and structurally characterized by X-ray single crystal diffraction (H3DHB = 2,6-dihydroxybenzoic acid, H2DCB = 1,4-dicarboxybenzene). Complex 1 was used as a precursor to synthesize complexes 2 and 3, and 2 was further used to synthesize 3. Complex 1 is a mononuclear complex, in which the Dy(III) ion is in a nine-coordinated structure surrounded by three tridentate chelate H3ATB− ligands. Complex 2 displays a dinuclear structure bridged by two μ2 carboxyl groups of two H2DHB− ligands and two μ1,1-O atoms from the phenolic hydroxyl groups of two H2ATB2− ligands. Complex 3 shows a one-dimensional structure formed by two bridging DCB2− ligands. The magnetic measurements were performed on three complexes 1–3, and they showed different magnetic behavior. Complex 1 shows a field-induced slow magnetic relaxation. Complexes 2 and 3 display distinct slow magnetic relaxation under zero dc field with energy barriers (Ueff) of 26(2) cm−1 and 11(1) cm−1, respectively. The magnetic behavior of three complexes 1–3 was investigated by ab initio calculations. [ABSTRACT FROM AUTHOR]

Six new and novel polynuclear Ln III5 clusters, formulated as [Ln5(L)4(acac)7]·solvents (Ln(III) = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5) and Ho (6), Hacac = acetylacetone, and H2L = 2-[(2-(hydroxyimino)propanehydrazide)methyl]-5-hydroxymethyl-2-furancarboxylic acid) have been successfully obtained through the reaction of a polydentate Schiff base ligand (H2L) and Ln(acac)3·2H2O. Single crystal X-ray diffraction data indicate that clusters 1–6 are isostructural and their central Ln(III) ions have a Ln(III)5 chain arrangement. Magnetic property investigations show that the Gd(III)-based cluster (3) exhibits a significant and larger MCE with the maximum −ΔSm value of 34.02 J kg−1 K−1 (ΔH = 7.0 T and T = 2.0 K). Alternating current (ac) susceptibility measurements of the Dy(III)-based cluster (5) display remarkable slow magnetic relaxation behaviors at zero applied direct current (dc) magnetic field (ΔE/kB = 17.47 K and τ0 = 1.52 × 10−6 s). Furthermore, studies on the solid-state fluorescence properties show that clusters 2, 4, and 5 display the characteristic lanthanum luminescence at room temperature. [ABSTRACT FROM AUTHOR]

A new excited-state intramolecular proton transfer (ESIPT) based and polarity-sensitive fluorescent probe M-HA was easily developed by conjugated connection of indole and 2′-hydroxyacetophenone through (E)-2-chloro-3-(hydroxymethylene)cyclohex-1-enecarbaldehyde. M-HA shows near-infrared fluorescence, high molar absorption coefficient and a large Stokes shift in various common solvents. In particular, M-HA exhibits red-shifted maximum emission wavelength, and extraordinarily high fluorescence intensity and quantum yield in high-polarity solvents. The theoretical calculation results indicate that the reduced electron-vibration coupling related to out-of-plane motions of benzene units in more polar solvents is mainly responsible for such unusual photophysical properties. For further application, M-HA was utilized to image live cells. The confocal fluorescence imaging results demonstrate that M-HA possesses excellent membrane permeability and can fluoresce brightly in the cytoplasm. Overall, M-HA, as a polarity-sensitive fluorescent probe, will serve as an excellent tool for quantitative determination of polarity in vitro and in-depth study of the polarity biology in physiopathology in future. [ABSTRACT FROM AUTHOR]

A new electrochemically induced three-component annulation-halosulfonylation of 1,6-enynes has been developed for stereoselective synthesis of 33 examples of 1-indanones with generally good yields under environmentally benign conditions. This electrochemical strategy can proceed in a simple undivided cell, avoiding any transition metal catalysts, chemical oxidants and additives. This reaction tolerates a wide scope of substrates, which provides a new and green access to fabricate important bioactive 1-indanone scaffolds. Notably, readily available and low-cost halogen salts play triple roles of an electrolyte and a redox catalyst as well as a halogenating reagent. [ABSTRACT FROM AUTHOR]

Two new borates, NaK1.5[B{B5O9(OH)}{B5O8(OH)2}1/2] (1) and Na3.5[Al{B3O6(OH)}{B5O10}1/2{BO(OH)}] (2), have been made by a solvothermal method. Structure 1 is made of two types of oxoboron clusters ([B5O9(OH)]4− and [B5O8(OH)2]3−) and BO4 tetrahedra to form a 3D porous layer, in which the [B5O9(OH)]4− clusters are bridged by BO4 groups to produce a 2D B–O layer with 11-membered ring (MR) windows, while the [B5O8(OH)2]3− clusters as 2-connected pillars join the adjacent B–O layers to make a 3-D porous layer. Structure 2 is built from two types of oxoboron clusters ([B3O6(OH)]4− and [B5O12]9−), AlO4 units and BO2(OH) triangles to produce 3D pillar-layered aluminoborate (ABO), in which the [B5O12]9− clusters are linked together to form a 2-D B–O layer; the [B3O6(OH)]4− clusters and AlO4 groups join each other to form 1D tubular ABO; and the BO2(OH) triangles act as linkers to connect the adjacent B–O layer and the ABO tubes, resulting in 3D pillar-layered ABO. Interestingly, the ABO tubes decorated with the BO2(OH) triangles act as pillars to make a 3D layer-pillared structure. UV-vis diffuse spectra indicate that both have cut-off edges below 190 nm, and the calculated band gaps are 5.75 and 5.78 eV, respectively. [ABSTRACT FROM AUTHOR]

A new radical-induced dehydrogenative heterocyclization of arylamines with α-diazo carbonyls has been established under metal-free oxidative conditions, enabling two-fold C(sp2)–H bond amination to access a wide range of functionalized 1,2,4-triazine derivatives with generally good yields by combining KI/tert-butyl peroxide (TBHP). The present protocol features wide substrate scope, commercial accessibility, and mild reaction conditions. Mechanistic details of this radical process are rendered by conducting systematic theoretical calculations. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) boron nitride nanosheets (BNNSs) were chemically exfoliated from bulk boron nitride and coated onto the surface of a poly(ethylene oxide) (PEO)-based electrolyte through a dry-pressing transfer process. The fabricated BNNSs coating formed a robust interfacial layer to improve the chemical and mechanical stability of the PEO-based electrolyte, leading to the enhanced performance of solid-state Li metal batteries. [ABSTRACT FROM AUTHOR]

Piezoelectricity, one of the most desirable properties of non-centrosymmetric crystalline materials, has long been blooming in academic research, industrial manufacturing, and daily applications owing to its unique electromechanical transformation capability. Compared with inorganic piezoelectric ceramics dominating the market, molecule-based piezoelectric materials exhibit advantages of light weight, mechanical flexibility, and environment friendliness and have attracted widespread interest recently. However, investigations on molecular materials with large piezoelectric coefficients are mainly focused on organic–inorganic hybrids, while pure organic homochiral piezoelectrics holding large piezoelectric coefficients remain scarce. Herein, by precise molecular modification on (S)-2-methylpiperazin-1-ium perchlorate ([(S)-MPP][ClO4]) with polar cyanomethyl groups, a homochiral pure organic compound (3S)-3-methyl-1,4-di(cyanomethyl)piperazin-1-ium perchlorate [DCM-(S)-MPP][ClO4] with large d22 of 18 pC/N was achieved, along with changes in the space group from nonpolar to polar, giving rise to second harmonic generation and phase transition behaviors. The modification strategy proposed here will benefit piezoelectricity enhancement in more chiral compounds, promoting their application potential in biological medicine, flexible devices, and green chemistry. [ABSTRACT FROM AUTHOR]

Three three-dimensional (3D) supramolecular lanthanide complexes, {[Ln2(tdc)3(H2O)](H2O)2}n (Ln = La 1, Ce 2, Pr 3; H2tdc = 3,4-thiophenedicarboxylic acid), have been synthesized by hydrothermal reactions of H2tdc and the corresponding lanthanide nitrate. Crystallographic data show that 1–3 are isomorphous and crystallize in the triclinic P1̅ space group. Each of them exhibits an interesting pillared layered supramolecular network comprising polymeric layers and up-up-down-down (uudd) cyclic tetrameric water pillars. Furthermore, in these compounds, tdc2− anions unprecedentedly display three coordination modes in the polymeric layers. Elemental analyses (EA), infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA) were also employed, and the materials exhibit a reversible de- and rehydration behavior. [ABSTRACT FROM AUTHOR]

A linear supramolecular ternary polymer was fabricated by iteratively threading cyclodextrin with suberyl dicholine and end-capping with bis-calixarenes, showing desired cholinesterase response. [ABSTRACT FROM AUTHOR]

Herein, we have developed a distinctive electrochemical sensing platform for miRNA assay. Target miRNA initiates two cycles of polymerization, nicking, and displacement reactions, which lead to the variation of the distance between redox molecules and the electrode surface. In addition, a reductant is employed for further electrochemical amplification. [ABSTRACT FROM AUTHOR]

The first thiazolium salt-catalyzed C–C triple bond cleavage of benzene-linked allene-ynes has been established. The reaction pathway involves [2+2] cycloaddition and ring-opening of in situ generated cyclobutenes with H2O under mild and convenient conditions, and provides practical access to substituted 1-naphthols with potentially valuable applications. [ABSTRACT FROM AUTHOR]

Atomic cobalt–nitrogen–carbon (Co–NC) material was synthesized using spent LiCoO2, and contained a heavy Co–N4 loading (1.42 at%). The synthesized Co–NC exhibited high oxygen reduction reaction activity (with onset and half-wave potentials of 0.97 V and 0.87 V, respectively) and robust Al–air battery performance, delivering a specific power of 121.3 mW cm−2. [ABSTRACT FROM AUTHOR]

Tetraphenylpyrazine (TPP) is a conspicuous heterocyclic fluorophore with an aggregation-enhanced emission (AEE) character. In general, the TPP building block is considered either a molecular rotor or an electron acceptor in the construction of its derivatives. Therefore, a faint-blue emission is expected in its solution. Herein, we concentrated on a series of unusual DTPP-A type analogues, where two TPP units (DTPP) were connected using the electron-accepting group (A), i.e., benzodiazine (BQ), benzothiadiazole (BZ), thienyldioxide (TO), naphthothiadiazole (NZ) and benzobisthiadiazole (B2Z). The excited-state properties of two experimentally available compounds (DTPP-BZ and DTPP-TO) and three theoretically designed molecules (DTPP-BQ, DTPP-NZ and DTPP-B2Z) were studied by employing time-dependent density functional theory coupled with thermal vibration correlation function formalism. The tetrahydrofuran solvent environment was mimicked through the polarizable continuum model. It was found that the TPP components turned into electronic donors in these DTPP-A type systems, and the emission color widened from blue to red and even to near-infrared upon increasing the electron-accepting ability of the central bridge. The excitons localized on the central "acceptor" bridge offer sufficient orbital overlaps and contribute to the effective radiative transition. The rotation behaviors of the phenyls in the TPP components are also restricted upon such linkage, which could reduce the relaxation energy and give rise to a much slower non-radiative decay process. Thus, the emission of the bridged systems is boosted in solution though TPP itself is an AEE element. The present study provides a valuable strategy for the molecular design of heterocycle-containing emitters with whole visible light and near-infrared emission. [ABSTRACT FROM AUTHOR]

A novel three-component carbo-oxygenation of α-diazo carbonyls for flexible synthesis of unprecedented α-aminooxy-β-amino ketones has been established through metal-free C(sp3)–H functionalization from readily accessible N,N-dimethylanilines and N-hydroxyphthalimide. The reaction pathway involves an in situ-generated phthalimide N-oxyl radical-triggered dediazotization/radical coupling sequence, leading to C–O and C–C bond formation. [ABSTRACT FROM AUTHOR]

Recent years have witnessed increasingly rapid advances in nanocarrier-based biomedicine aimed at improving treatment paradigms for cancer. Nanogels serve as multipurpose and constructed vectors formed via intramolecular cross-linking to generate drug delivery systems, which is attributed predominantly to their satisfactory biocompatibility, bio-responsiveness, high stability, and low toxicity. Recently, immunotherapy has experienced unprecedented growth and has become the preferred strategy for cancer treatment, and mainly involves the mobilisation of the immune system and an enhanced anti-tumour immunity of the tumour microenvironment. Despite the inspiring success, immunotherapeutic strategies are limited due to the low response rates and immune-related adverse events. Like other nanomedicines, nanogels are comparably limited by lower focal enrichment rates upon introduction into the organism via injection. Because nanogels are three-dimensional cross-linked aqueous materials that exhibit similar properties to natural tissues and are structurally stable, they can comfortably cope with shear forces and serum proteins in the bloodstream, and the longer circulation life increases the chance of nanogel accumulation in the tumour, conferring deep tumour penetration. The large specific surface area can reduce or eliminate off-target effects by introducing stimuli-responsive functional groups, allowing multiple physical and chemical modifications for specific purposes to improve targeting to specific immune cell subpopulations or immune organs, increasing the bioavailability of the drug, and conferring a low immune-related adverse events on nanogel therapies. The slow release upon reaching the tumour site facilitates long-term awakening of the host's immune system, ultimately achieving enhanced therapeutic effects. As an effective candidate for cancer immunotherapy, nanogel-based immunotherapy has been widely used. In this review, we mainly summarize the recent advances of nanogel-based immunotherapy to deliver immunomodulatory small molecule drugs, antibodies, genes and cytokines, to target antigen presenting cells, form cancer vaccines, and enable chimeric antigen receptor (CAR)-T cell therapy. Future challenges as well as expected and feasible prospects for clinical treatment are also highlighted. [ABSTRACT FROM AUTHOR]

A novel metal-free nitrative bicyclization of 1,7-diynes with tBuONO in the presence of H2O is reported, producing three types of skeletally diverse tricyclic pyrroles, namely pyrrolo[3,4-c]quinolines, chromeno[3,4-c]pyrroles and benzo[e]isoindoles, with moderate to good yields by simply tuning the linkers of the 1,7-diynes. This domino protocol demonstrates remarkable compatibility regarding 1,7-diynes with different linkers, such as nitrogen and oxygen atoms and a hydroxymethyl group, and tBuONO plays dual roles as a nitro precursor as well as a nitrogen atom source. [ABSTRACT FROM AUTHOR]

Two new β-diketone-boron difluoride based near-infrared fluorescent probes 1 and 2 which exhibit polarity sensitivity have been designed and synthesized. Probes 1 and 2 are composed of a β-diketone-boron difluoride moiety as an acceptor unit, and a diethylamino group and a phenolic hydroxyl group as donor units. The long conjugate structures form a "donor–acceptor–donor" configuration, induce intramolecular charge transfer (ICT), and confer near-infrared fluorescence emission and excellent polarity sensitivity. The photophysical properties of these two probes were investigated in detail. Experimental data demonstrated that as the environmental polarity decreased, the fluorescence intensity of the probes increased obviously, accompanied by a blue-shift of the maximum emission wavelength. In addition, these two probes were photostable and solely sensitive to polarity without interference from viscosity, pH and common active species. Theoretical calculations indicated that probes 1 and 2 displayed lower energy gaps and faster non-radiative decay in polar solvents. Furthermore, probes 1 and 2 were utilized to quantitatively detect the polarity of a binary mixture through the satisfactory linear relationship between the fluorescence emission intensity ratios and the orientation polarizability of the mixed solvent. Additionally, probe 1 was successfully utilized to visualize the polarity distribution of live cells. Both of these probes are perfect candidates for studying polarity in vitro and even in live systems. [ABSTRACT FROM AUTHOR]

A dinuclear dysprosium cluster [Dy2(NO3)4(H2O)2(L)2]·2CH3CN was successfully prepared by employing HL (HL = 2,6-dimethoxyphenol) and Dy(NO3)3·6H2O in a mixture of CH3OH and CH3CN. The conversion of this Dy2 compound by reaction with additional deprotonated ligand generated a Dy9 cluster [Dy9(μ4-OH)2(μ3-OH)8(μ2-OCH3)4(NO3)8(H2O)8(L)4](OH)·2H2O with the well-known "diabolo" topology. Magnetic investigation revealed that both of the clusters exhibit typical SMM characteristics, and variable magnetic relaxation with the energy barrier changing from 217.87 K to 9.24 K along with the transition from a dinuclear dysprosium cluster to a nonanuclear one. Ab initio calculations further confirm the corresponding structure–activity relationships that originate the different magnetic behaviours. This design may afford a feasible strategy for modulating the magnetic relaxation dynamics of polynuclear systems. [ABSTRACT FROM AUTHOR]

7-Hydroxycoumarin is a privileged structure for anti-inflammatory drug development. In this study, several new 3-acetyl-7-hydroxycoumarin derivatives were designed, synthesized and tested as anti-inflammatory agents. Interestingly, Mannich bases and Betti bases were separately obtained under acidic or neutral conditions. The regioselectivity of aminomethylation was studied based on the atomic electron density distribution by analysing the Voronoi deformation density (VDD) atomic charges, which reasonably explained the experimental outcome. Detection of nitric oxide (NO) and tumour necrosis factor alpha (TNF-α) release revealed that Mannich bases displayed stronger anti-inflammatory activity than the corresponding Betti bases. [ABSTRACT FROM AUTHOR]

In this work, an electroanalytical platform for nereistoxin (NRT)-related insecticide detection is proposed on the basis of NRT induced DNA conformational switching and exonuclease III (Exo III) assisted target recycling. NRT-related insecticides were first hydrolyzed and converted into NRT with two thiol groups (–SH). Then, a cytosine–Ag+–cytosine (C–Ag+–C) mismatched base pair was adopted to induce a blunt-ended hairpin configuration of HP DNA. In the presence of converted NRT, it could take up Ag+ from HP DNA to change its conformation from a hairpin to single-stranded structure (HP ssDNA). Thereafter, the obtained HP ssDNA was further hybridized with an H1 hairpin probe on the electrode surface to trigger the Exo III cleavage process, releasing HP ssDNA for recycling leaving the G-quadruplex fragment of H1, which was used for hemin/G-quadruplex complex formation. The reversible redox reaction of Fe(III)/Fe(II) of hemin gave a remarkable electrochemical response for quantitative determination of the NRT-related insecticides. As an analytical model, a low detection limit of 3.9 ng L−1 and a wide linear range of 0.01–1500 μg L−1 with excellent selectivity were achieved for cartap detection. The proposed method also displayed great applicability for cartap detection in agricultural products. [ABSTRACT FROM AUTHOR]

Tb3+/Eu3+@Ni-BTC (H3BTC = 1,3,5-benzenetricarboxylic acid) composites were prepared by soaking the Ni-BTC parent framework in Tb3+ and Eu3+ ethanol solutions. Various factors were optimized, with the ratio of Tb3+ : Eu3+at 6 : 4, the soaking time being 30 h, and the MOF dosage being 100 μg. The sensitivity tests of DPA detection by the optimized Tb3+0.6/Eu3+0.4@Ni-BTC indicated a linear relationship of I545/I613 = 1.24098·CDPA + 3.80396 where CDPA = 2–20 μmol L−1, and the limit of detection was calculated as 14.7 nM. Tb3+0.6/Eu3+0.4@Ni-BTC exhibited high selectivity without interference from seven interferents. The detection mechanism is inferred as that DPA sensitizes Tb3+ and transfers energy to Eu3+, however it blocks the energy transfer from HBTC2− to Eu3+. Tb3+0.6/Eu3+0.4@Ni-BTC can be regarded as a potential candidate for a quantitative ratiometric fluorescence sensor for DPA detection with high sensitivity and selectivity. [ABSTRACT FROM AUTHOR]

Ag NPs are encapsulated into ZIF-71 via a deposition–reduction method. The resulting products are tested as adjustable molecular sieves for hydrogen and acetone. The gas sensing performances show that the response to acetone is reduced and that to hydrogen increased, demonstrating an engineered selectivity. A novel design of molecular sieving MOF materials for gas separation in gas-sensing selectivity is thus provided. [ABSTRACT FROM AUTHOR]

Three metal–organic frameworks have been synthesized by using N-containing ligands and meso-tetra(4-carboxyphenyl)porphyrin, which all exhibit distinct selective adsorption capacities toward various organic dyes, illustrating the most important influence of the structural tuning. [ABSTRACT FROM AUTHOR]

Bioproduction processes relying on natural photosynthesis have low solar energy-to-specific product conversion efficiency. A possible solution is the development of hybrid photosynthesis systems where sunlight is harvested by more efficient inorganic devices, which then generate energy used by microbial catalysts for the production of valuable chemicals from carbon dioxide. Microbial processes employing organic carbon molecules as a source of energy could also benefit from being coupled with inorganic photocatalysts to drive their metabolism toward a higher production yield. Here, the photocatalyst graphitic carbon nitride (g-C3N4) was employed to improve polyhydroxybutyrate (PHB) production from fructose by Ralstonia eutropha H16. PHB is a bioplastic generated by R. eutropha for energy and carbon storage purposes. Its synthesis requires reducing power in the form of NADPH. In this hybrid photosynthesis strategy, g-C3N4 harvested light energy and generated reducing power, which were then consumed by R. eutropha for the conversion of acetyl-CoA into PHB. Coupling illuminated R. eutropha with g-C3N4 augmented PHB production by 1.2 times in the absence of a sacrificial electron donor and by 1.4 times when triethanolamine was supplied. The formation of large aggregates composed of cells and photocatalyst particles was observed with SEM, indicating that direct physical contact between g-C3N4 and R. eutropha is required for the effective transfer of reducing power. The significantly increased ratio of intracellular NADPH/NADP+ further demonstrated the positive impact of g-C3N4 on R. eutropha energy metabolism. This proof-of-concept study illustrates that inorganic photocatalysts can augment the productivity of white biotechnologies aiming at converting organic carbon substrates into useful chemicals. [ABSTRACT FROM AUTHOR]

A novel fluorescent triazine-based covalent organic polymer (COP-1) sensor for HCl and NH3 gases has been designed and synthesized. Both the COP-1 powders that were dispersed in solvents and the COP-1 film that was formed on the surface of quartz sheets exhibited stable fluorescence and a sensitive HCl/NH3 response. Immersion in HCl-bubbled solvents weakens and red-shifts the fluorescence emission of the COP-1 powders, owing to a protonation-induced charge transfer (CT). Subsequent injection of NH3 into the solvents recovers the fluorescence via deprotonation. Interestingly, the microporous COP-1 film also shows a similar fluorescence response to HCl/NH3 gas, with high sensitivity and good reversibility, which suggests that it could serve as a solid-state optical probe for continuous and quantitative detection of HCl and NH3 gases. The formation of the red-shifting hydrogen bonds is found to be the origin of the response. [ABSTRACT FROM AUTHOR]

Selective valorization of lignin to achieve high value and commodity chemicals is attracting increasing attention. In this work, an efficient and reusable metal-based ionic liquid (MBIL) was developed for the selective tailoring of p-coumaric acid ester (pCA), a typical p-hydroxyphenyl (H) unit, into methyl p-hydroxycinnamate (MPC). Under optimized conditions and in the presence of catalyst [Bmim][FeCl4], a volatile aromatic product of 10.5 wt% was obtained, of which, 70.5% separated as pure MPC with an isolated yield of 71.1 mg g−1. FT-IR, 13C NMR, ANO and 2D HSQC demonstrated that the H unit was preferentially tailored from lignin, of which, 86.0 wt% of the H structure unit is cut off from lignin, with 70.6% being selectively converted to MPC. Further investigation demonstrated that MBIL prefers to tailor ester bonds compared to ether bonds using model compounds, and the superior catalytic ester bond cleavage performance exhibited by [Bmim][FeCl4] can be ascribed to the relatively narrow energy gap between the lignin ester bond and [FeCl4]− anion and to the comparatively low absolute binding energy between the cation and anion through DFT calculations. [ABSTRACT FROM AUTHOR]

Fluorescent unimolecular micelles (FUMs) with multicolor emission acting as fluorescent nanoagents for optical fluorescence imaging have, for the first time, been reported. The FUMs show good water-solubility, ultra-small size, and enhanced biocompatibility, which endow the FUMs with versatile applications including organelle labeling, multicolor markers and high tumor accumulation, revealing that our design can serve as a rational strategy for the development of UM-based fluorescent nanoagents for bioprocess monitoring. [ABSTRACT FROM AUTHOR]

By utilizing the pre-designed bi-functional ligand 4-{bis(4-benzoic)amino}-4H-1,2,4-triazole (H2L), five new transition-metal-based coordination polymers, namely, {[Zn(L)]·H2O·DMA}n (1), {[Zn2(L)2]·DMF}n (2),{[Mn(L)]·DMF}n (3), {[Cd(L)]·DMA}n (4) and [Cu3(OH)2(L)2]n (5) have been constructed and structurally characterized. In 1, the tetrahedral zinc ion was incorporated in the final structure. However, complexes 2, 3 and 4 bear 1D Zn-, Mn- and Cd-chains composed of metal ions, triazole and carboxyl groups, respectively. Differently, 1D [Cu4(μ3-OH)2] chains had been stabilized in the 3D structure of 5. In addition, the luminescence or magnetic properties of 1–5 had been correspondingly investigated with the consideration of their crystal structure. The whole research results manifest that utilizing a bi-functional ligand containing carboxyl and triazole groups is an efficient building method in constructing functional CPs. [ABSTRACT FROM AUTHOR]

We have developed mitochondria-targeted self-assembled nanoparticles (NPs) based on amphiphilic triphenylphosphine–quercetin (TPP–Que) conjugates, which were further modified by poly(ethylene glycol) via a pH-responsive coordination bond to form TQ-PEG NPs. And it is revealed that the TQ-PEG NPs were more effective therapeutic agents compared with Que in vitro and in vivo. [ABSTRACT FROM AUTHOR]

Uniform nanoshells of manganese oxides have been successfully prepared by controlling their growth kinetics in solution. The prepared manganese oxides show promising electrochemical performance when used as an anode material in lithium ion batteries. [ABSTRACT FROM AUTHOR]

Two trigeminal star-like platinum complexes were synthesized to induce the formation of human telomere G-quadruplex (hTel G4) with extremely high selectivity and affinity. The induced hTel G4 activates strong telomeric DNA damage response (TDDR), resulting in telomere dysfunction and cell senescence. [ABSTRACT FROM AUTHOR]

Solvothermal reactions of tetrakis(4-pyridyloxymethyl)methane (TPOM) and 4,4′-oxybisbenzoic acid (H2oba) with different metal ions under different synthesis temperatures produced three new coordination polymers (CPs), namely, {[Co2(TPOM)(oba)2(H2O)2]}n (1), {[Zn2(TPOM)(oba)2]}n (2) and {[Cd2(TPOM)(oba)2(H2O)2]}n (3). 1 and 3 present similar topological structures which can be analyzed in two different ways. 2 exhibits a rare porous structure assembled by the tetra-pyridinate ligand TPOM. The luminescence properties of 2 and 3 as well as those of the corresponding samples immersed in different solvents have been investigated, and they suggested a potential application in luminescence sensing. In addition, the dye and iodine adsorption properties of an activated sample of 2 were also investigated. All of the results indicate that the proper selection of metal ions and auxiliary ligands plays an important role in constructing porous coordination polymers. [ABSTRACT FROM AUTHOR]

Two distinct template mediated coordination polymers, [Co3(ina)4(N3)2(CH3OH)2] with tri-nuclear nodes (1) and [Co8(OH)(ina)8(N3)8·X] with dual tetra-nuclear cobalt nodes (2), have been synthesized under hydrothermal conditions by utilizing the template agent of pentaerythritol. 1 shows a 2D layer comprised of linear tri-nuclear CoII clusters, in which the central cobalt ion is inter-linked with two terminal ones via mixed bridges as syn–syn carboxylates and end-on azide ions. In contrast, compound 2 exhibits a three-dimensional framework based on two kinds of six-connected tetra-nuclear cobalt clusters: square-planar node and cuboidal node. Both 1 and 2 might exhibit spin-canted magnetism. In addition, the activated sample of 2 exhibits the sorption ability of H2 and CO2 molecules. [ABSTRACT FROM AUTHOR]

Solvothermal reactions of two ligands with different geometries, derived from cyclotriphosphazene, hexakis(4-carboxylato-phenoxy)cyclotriphosphazene (H6L1) and hexakis(3-carboxylato-phenoxy)cyclotriphosphazene (H6L2) with Eu(NO3)3·6H2O in H2O/DMF under similar synthesis conditions produced three new compounds, namely, {[Eu2(L1)(H2O)4]·(H2O)4·(DMA)2}n (1), {[Eu2(L1)(H2O)8]·(H2O)2·DMA}n (2), and {[Eu2(L2)(H2O)3(DMF)]·(H2O)2·(DMA)}n (3). Compounds 1 and 2 display a 2D layer crystal structure with a distinct topological network incorporating the extended hexa-carboxylate ligand L1; in contrast, 3 has a 1D crystal structure with the highly distorted hexa-carboxylate ligand L2. In these three compounds, the ligands L1 and L2 are fully deprotonated, whose six extended carboxyl arms connect six different/same metallic nodes to generate metal–organic frameworks. The luminescence properties of three compounds have been studied at room temperature in relative detail. [ABSTRACT FROM AUTHOR]