Rational Design of a Highly Sensitive Carboxylesterase Probe and Its Application in High-Throughput Screening for Uncovering Carboxylesterase Inhibitors.

Tracking carboxylesterases (CESs) through noninvasive and dynamic imaging is of great significance for diagnosing and treating CES-related metabolic diseases. Herein, three BODIPY-based fluorescent probes with a pyridine unit quaternarized via an acetoxybenzyl group were designed and synthesized to detect CESs based on the photoinduced electron transfer process. Notably, among these probes, BDPN2-CES exhibited a remarkable 182-fold fluorescence enhancement for CESs within 10 min. Moreover, BDPN2-CES successfully enabled real-time imaging of endogenous CES variations in living cells. Using BDPN2-CES, a visual high-throughput screening method for CES inhibitors was established, culminating in the discovery of an efficient inhibitor, WZU-13, sourced from a chemical library. These findings suggest that BDPN2-CES could provide a new avenue for diagnosing CES-related diseases, and WZU-13 emerges as a promising therapeutic candidate for CES-overexpression pathological processes.

Modulating band structure through introducing Cu0/CuxO composites for the improved visible light driven ammonia synthesis.

The photocatalytic performance of ceria-based materials can be tuned by adjusting the surface structures with decorating the transition-metal, which are considered as the important active sites. Herein, cuprous oxide-metallic copper composite-doped ceria nanorods were assembled through a simple hydrothermal reduction method. The photocatalytic ammonia synthesis rates exhibit an inverted "V-shaped" trend with increasing Cu0/CuxO mole ratio. The best ammonia production rate, approximately 900 or 521 µmol·gcal-1·h-1 under full-spectra or visible light, can be achieved when the Cu0/CuxO ratio is approximately 0.16, and this value is 8 times greater than that of the original sample. The absorption edge of the as-prepared samples shifted towards visible wavelengths, and they also had appropriate ammonia synthesis levels. This research provides a strategy for designing noble metal-free photocatalysts through introducing the metal/metallic oxide compositesto the catalysts.

Strategic design of an NIR probe for viscosity imaging in inflammatory and non-alcoholic steatohepatitis mice.

Two novel near-infrared (NIR) fluorescent probes Cy-Vis1 and Cy-Vis2 with large Stokes shifts (>100 nm) were constructed using a "symmetry collapse" strategy. Notably, Cy-Vis2 was significantly more sensitive to viscosity than Cy-Vis1 through an enhanced intramolecular interaction strategy. The fluorescence intensities of Cy-Vis1 and Cy-Vis2 exhibited increases, by 7.6- and 19.9-fold, respectively, across the viscosity range from 0.8 cp to 359.9 cp. Cy-Vis2 was successfully used to visualize viscosity abnormalities in lipopolysaccharide (LPS)-induced inflammatory and NASH model mice.

Two Stable Bifunctional Zinc Metal-Organic Frameworks with Luminescence Detection of Antibiotics and Proton Conduction.

Functionalized crystalline solids based on metal-organic frameworks (MOFs) enable efficient luminescence detection and high proton conductivity, making them crucial in the realms of environmental monitoring and clean energy. Here, two structurally and functionally distinct zinc-based MOFs, [Zn(TTDPa)(bodca)]·H2O (1) and [Zn(TTDPb)(bodca)]·H2O (2), were successfully designed and synthesized using 3,6-di(pyridin-4-yl)thieno[3,2-b]thiophene (TTDPa) and 2,5-di(pyridin-4-yl)thieno[3,2-b]thiophene (TTDPb) as ligands, in the presence of bicyclo[2.2.2]octane-1,4-dicarboxylic acid (H2bodca). Both 1 and 2 display a three-dimensional (3D) structure with 5-fold interpenetration, and notably, 2 forms a larger one-dimensional pore measuring 17.16 × 10.81 Å2 in size. Fluorescence experiments demonstrate that 1 and 2 can function as luminescent sensors for nitrofurantoin (NFT) and nitrofurazone (NFZ) with low detection limits, remarkable selectivity, and good recyclability. A comprehensive analysis was conducted to investigate the differing sensing effects of compounds 1 and 2 and to explore potential sensing mechanisms. Additionally, at 328 K and 98% relative humidity, 1 and 2 exhibit proton conductivity values of 2.13 × 10-3 and 4.91 × 10-3 S cm-1, respectively, making them suitable proton-conducting materials. Hence, the integration of luminescent sensing and proton conductivity in monophasic 3D Zn-MOFs holds significant potential for application in intelligent multitasking devices.

Multicomponent hydroxides supported Cu/Cu2O nanoparticles for high efficient photocatalytic ammonia synthesis.

Environmentally friendly photocatalytic N2 fixation process has attracted considerable attention. Developing efficient photocatalysts with high electron-hole separation rates and gas adsorption capacities remains quite challenging. Herein, a facile fabrication strategy of Cu-Cu2O and multicomponent hydroxide S-scheme heterojunctions with carbon dot charge mediators is reported. The rational heterostructurebrings excellent N2 absorption ability and high photoinduced electron/hole separation efficiency, and the ammonia produced yield reach above 210 µmol·gcal-1·h-1 during the nitrogen photofixation process. More superoxide and hydroxyl radicals are generated simultaneously in the as-prepared samples under light illumination. This work offers a reasonable construction method to further develop suitable photocatalysts for ammonia synthesis.

CeO2-CDs clusters decorated Co(OH)2 nanosheets for improved photocatalytic ammonia synthesis.

The green synthesis process of photocatalytic ammonia production has received more and more attentions. Herein, a Z-scheme heterojunction with all-solid-state structures is constructed, in which carbon dots can act as electron transferring mediators. The photocatalytic measurement shows that the modified photocatalysts exhibit much higher activities, in which the ammonia production rates can reach above 232 µmol·gcal-1·h-1 under the light irradiation. The improved catalytic properties can be credited to the significantly increased number of photoinduced oxygen vacancies, the excellent visible-light adsorption abilities and photogenerated electron-hole separation efficiencies for the carbon dots bridged heterostructures. More hydroxyl and superoxide radicals can be simultaneously produced in the composites. This work provides reasonable guidance for applications in photocatalytic ammonia synthesis and a promising construction strategy of efficient Z-scheme photocatalysts.

Synthesis of 1-Aminoisoquinolines and Their Application in a Host-Guest Doped Strategy To Construct Ultralong Room-Temperature Phosphorescence Materials for Bioimaging.

Organic ultralong room-temperature phosphorescence (RTP) materials have attracted great attention for their wide applications in optoelectronic devices and bioimaging. However, the development of these materials remains a challenging task, partially due to the lack of rational molecular design strategies and unclear luminescence mechanisms. Herein, we present a method for facile access to structurally diverse substituted 1-aminoisoquinoline derivatives through a copper-catalyzed one-pot three-component coupling reaction that provides a promising approach to rapidly assemble a library of 1-aminoisoquinolines for exploring the regularity of the host-guest doped system. A series of host-guest RTP materials with wide-ranging lifetimes from 4.4 to 299.3 ms were constructed by doping various substituted isoquinolines derivatives into benzophenone (BP). Furthermore, 4 r/BP nanoparticles could be used for in-vivo imaging with a signal-to-noise ratio value as high as 32, revealing the potential of the isoquinoline framework for the construction of high-performance RTP materials.

Syntheses, structures, and magnetic properties of acetate-bridged lanthanide complexes based on a tripodal oxygen ligand.

Four homodinuclear lanthanide complexes, Dy2 (LOEt)2(OAc)4 (1), Tb2 (LOEt)2(OAc)4 (2), Ho2(LOEt)2(OAc)4 (3), and Gd2 (LOEt)2(OAc)4 (4), have been synthesized and characterized based on a tripodal oxygen ligand Na [(η5-C5H5)Co(P(O)(OC2H5)2)3] (NaLOEt). Structural analyses show that the acetate anions bridge two symmetry-related Ln3+ ions in the µ2:η1:η1 and µ2:η1:η2 coordination patterns, and each lanthanide (III) ion owns a twisted square antiprism (SAPR) conformation. Static magnetic measurements reveal the weak intramolecular ferromagnetic interaction between dysprosium (III) ions in 1 and antiferromagnetic Ln3+···Ln3+ couplings in the other three complexes. Through the analysis of the ligand-field effect and magnetic anisotropy axis orientation, the reasons for the lack of dynamic magnetic behavior in 1 were identified.

Rational Design of a Near-Infrared Ratiometric Probe with a Large Stokes Shift: Visualization of Polarity Abnormalities in Non-Alcoholic Fatty Liver Model Mice.

Tracking liver polarity with noninvasive and dynamic imaging techniques is helpful to better understand the non-alcoholic fatty liver (NAFL). Herein, a novel near-infrared (NIR) fluorescent probe Cy-Mp is constructed using a "symmetry collapse" strategy. The structure modification leads to the conversion of locally excited state fluorescence to charge transfer state fluorescence. Cy-Mp emits at near-infrared (NIR) wavelengths with high photostability as well as a large Stokes shift. Cy-Mp exhibits a ratiometric response to polarity, providing more accurate analysis of intracellular polarity via the built-in internal reference correction. Most importantly, the in vivo studies indicate that Cy-Mp can accumulate in the liver and the decreased polarity in the liver of mice with NAFL is verified by the ratiometric imaging, implying the great potential of Cy-Mp in the diagnosis of NAFL.

Two-dimensional dysprosium(III) coordination polymer: Structure, single-molecule magnetic behavior, proton conduction, and luminescence.

A new dysprosium (III) coordination polymer [Dy(Hm-dobdc) (H2O)2]·H2O (Dy-CP), was hydrothermal synthesized based on 4,6-dioxido-1,3-benzenedicarboxylate (H4m-dobdc) ligand containing carboxyl and phenolic hydroxyl groups. The Dy(III) center adopts an octa-coordinated [DyO8] geometry, which can be described as a twisted square antiprism (D 4d symmetry). Neighboring Dy(III) ions are interconnected by deprotonated Hm-dobdc3- ligand to form the two-dimensional infinite layers, which are further linked to generate three-dimensional structure through abundant hydrogen bonds mediated primarily by coordinated and lattice H2O molecules. Magnetic studies demonstrates that Dy-CP shows the field-induced slow relaxation of magnetization and the energy barrier U eff/k B and relaxation time τ 0 are 35.3 K and 1.31 × 10-6 s, respectively. Following the vehicular mechanism, Dy-CP displays proton conductivity with σ equal to 7.77 × 10-8 S cm-1 at 353 K and 30%RH. Moreover, luminescence spectra reveal that H4m-dobdc can sensitize characteristic luminescence of Dy(III) ion. Herein, good magnetism, proton conduction, and luminescence are simultaneously achieved, and thus, Dy-CP is a potential multifunctional coordination polymer material.

Synthesis of Diverse γ-Lactams via Rh-Catalyzed C(sp2)-H Addition to Aliphatic Nitriles.

We herein report an unprecedented pathway to access γ-lactams using acetonitrile analogues as coupling partners without oxidants, ligands, and Lewis acids. The reaction undergoes Rh-catalyzed C(sp2)-H addition to carbon-bound nitriles with the aid of an amide traceless auxiliary followed by an annulation sequence, featuring a broad substrate scope, good functional group tolerance, and excellent chemo/stereoselectivity. Scale-up reactions and late-stage derivatizations highlight the potential synthetic utility of this methodology. A plausible mechanism is proposed based on mechanistic investigations.

Dysprosium(III) Metal-Organic Framework Demonstrating Ratiometric Luminescent Detection of pH, Magnetism, and Proton Conduction.

A multifunctional metal-organic framework, (Hdmbpy)[Dy(H2dobdc)2(H2O)]·3H2O (Dy-MOF, H4dobdc = 2,5-dihydroxyterephthalic acid, dmbpy = 4,4'-dimethyl-2,2'-bipyridine), was synthesized and structurally characterized. The metal center DyIII is connected by four carboxyl groups to form the [Dy2(CO2)4] binuclear nodes, which are further interconnected by eight separate H2dobdc2- ligands to form a three-dimensional (3D) framework including hydrophilic triangular channels and abundant hydrogen-bonding networks. Dy-MOF has good stability in aqueous solution as well as in harsh acidic or alkaline solutions (pH range: 2.0-12.0). Furthermore, the luminescence signal of Dy-MOF undergoes a visualized color change as the acidity of the solution alters, which is the typical behavior of pH ratiometric probe. At a 100% relative humidity, Dy-MOF exhibits a high proton conductivity σ (1.70 × 10-4 S cm-1 at 303 K; 1.20 × 10-3 S cm-1 at 343 K) based on the proton hopping mechanism, which can be classified as a superionic conductor with σ exceeding 10-4 S cm-1. Additionally, the ferromagnetic interaction and magnetic relaxation behavior are simultaneously achieved in Dy-MOF. Herein, the combination of luminescence sensing, magnetism, and proton conduction in a single-phase 3D MOF may offer great potential applications in smart multitasking devices.

Cu-Based Conductive MOF Grown in situ on Cu Foam as a Highly Selective and Stable Non-Enzymatic Glucose Sensor.

A non-enzymatic electrochemical sensor for glucose detection is executed by using a conductive metal-organic framework (MOF) Cu-MOF, which is built from the 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) ligand and copper acetate by hydrothermal reaction. The Cu-MOF demonstrates superior electrocatalytic activity for glucose oxidation under alkaline pH conditions. As an excellent non-enzymatic sensor, the Cu-MOF grown on Cu foam (Cu-MOF/CF) displays an ultra-low detection limit of 0.076 µM through a wide concentration range (0.001-0.95 mM) and a strong sensitivity of 30,030 mA µM-1 cm-2. Overall, the Cu-MOF/CF exhibits a low detection limit, high selectivity, excellent stability, fast response time, and good practical application feasibility for glucose detection and can promote the development of MOF materials in the field of electrochemical sensors.

Iron(II) Spin Crossover Coordination Polymers Derived From a Redox Active Equatorial Tetrathiafulvalene Schiff-Base Ligand.

Two polymorphic FeII coordination polymers [FeIIL (TPPE)0.5] 1) and [(FeII 3L3 (TPPE)1.5)] 2), were obtained from a redox-active tetrathiafulvalene (TTF) functionalized ligand [H2L = 2,2'-(((2-(4,5-bis-(methylthio)-1,3-dithiol-2-ylidene)benzo(d) (1,3) dithiole-5,6-diyl)bis-(azanediyl))bis-(meth anylylidene)) (2E,2E')-bis(3-oxobutanoate)] and a highly luminescent connector {TPPE = 1,1,2,2-tetrakis[4-(pyridine-4-yl)phenyl]-ethene}. Complex 1 has a layered structure where the TPPE uses its four diverging pyridines from the TPPE ligand are coordinated by the trans positions to the flat TTF Schiff-base ligand, and complex 2 has an unprecedented catenation of layers within two interpenetrated frameworks. These coordination polymers reserved the redox activity of the TTF unit. Complex 1 shows gradual spin transition behavior without hysteresis. And the fluorescence intensity of TPPE in 1 changes in tandem with the spin crossover (SCO) transition indicating a possible interplay between fluorescence and SCO behavior.

Identification and Functional Analysis of the Sex-Determiner Transformer-2 Homologue in the Freshwater Pearl Mussel, Hyriopsis cumingii.

Transformer-2 (Tra-2) is an upstream regulatory element of the sex regulation mechanism in insects and plays a critical role in sex formation. To understand the role of tra-2 in Hyriopsis cumingii, the full-length Hctra-2 (1867 bp) was obtained from the gonads, and sequence alignment with other species showed that HCTRA-2 protein had a highly conserved RRM domain. Phylogenetic analysis showed that the HCTRA-2 protein was a close relative to of the mollusks TRA-2 protein. The qRT-PCR of tissue-specific expression pattern showed that the Hctra-2 was abundant in gonads, and the expression in testes was higher than that in ovaries (p < 0.01). It suggests that Hctra-2 may play a potential regulatory role in gonadal development of H. cumingii. In the early gonadal development, the Hctra-2 expression was the highest on the third day after fertilization and increased slightly from 4 months to 5 months, which may be related to the embryonic sex determination and early gonadal development. In situ hybridization showed that Hctra-2 mRNA signals were present in both male and female gonads. After silencing Hctra-2 by RNAi, the expression levels of Hcfem-1b and Hcdmrt were changed. It is speculated that there may be a certain relationship between them, which plays an important role in the sex regulation of H. cumingii. Our research will help to deepen our understanding of the shellfish sex determination mechanisms.

Isospin Pomeranchuk effect in twisted bilayer graphene.

In condensed-matter systems, higher temperatures typically disfavour ordered phases, leading to an upper critical temperature for magnetism, superconductivity and other phenomena. An exception is the Pomeranchuk effect in 3He, in which the liquid ground state freezes upon increasing the temperature1, owing to the large entropy of the paramagnetic solid phase. Here we show that a similar mechanism describes the finite-temperature dynamics of spin and valley isospins in magic-angle twisted bilayer graphene2. Notably, a resistivity peak appears at high temperatures near a superlattice filling factor of -1, despite no signs of a commensurate correlated phase appearing in the low-temperature limit. Tilted-field magnetotransport and thermodynamic measurements of the in-plane magnetic moment show that the resistivity peak is connected to a finite-field magnetic phase transition3 at which the system develops finite isospin polarization. These data are suggestive of a Pomeranchuk-type mechanism, in which the entropy of disordered isospin moments in the ferromagnetic phase stabilizes the phase relative to an isospin-unpolarized Fermi liquid phase at higher temperatures. We find the entropy, in units of Boltzmann's constant, to be of the order of unity per unit cell area, with a measurable fraction that is suppressed by an in-plane magnetic field consistent with a contribution from disordered spins. In contrast to 3He, however, no discontinuities are observed in the thermodynamic quantities across this transition. Our findings imply a small isospin stiffness4,5, with implications for the nature of finite-temperature electron transport6-8, as well as for the mechanisms underlying isospin ordering and superconductivity9,10 in twisted bilayer graphene and related systems.

Rare-Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox-Switchable Single-Molecule Magnets.

Using the redox-active tetrathiafulvalene tetrabenzoate (TTFTB4- ) as the linker, a series of stable and porous rare-earth metal-organic frameworks (RE-MOFs), [RE9 (µ3 -OH)13 (µ3 -O)(H2 O)9 (TTFTB)3 ] (1-RE, where RE=Y, Sm, Gd, Tb, Dy, Ho, and Er) were constructed. The RE9 (µ3 -OH)13 (µ3 -O) (H2 O)9 ](CO2 )12 clusters within 1-RE act as segregated single-molecule magnets (SMMs) displaying slow relaxation. Interestingly, upon oxidation by I2 , the S=0 TTFTB4- linkers of 1-RE were converted into S= 1 / 2 TTFTB.3- radical linkers which introduced exchange-coupling between SMMs and modulated the relaxation. Furthermore, the SMM property can be restored by reduction in N,N-dimethylformamide. These results highlight the advantage of MOFs in the construction of redox-switchable SMMs.

Magnetic Relaxation Dynamics of a Binuclear Diluted Er(III)/Y(III) Compound Influenced by Lattice Solvent.

It is crucial to investigate the slow relaxation mechanisms of binuclear ErIII -based single-molecule magnets (SMMs) and explore strategies for optimizing their magnetic properties. Herein, a doped compound, [Y1.75 Er0.25 (thd)4 Pc] ⋅ 2C6 H6 (YEr ⋅ 2C6 H6 , Hthd=2,2,6,6-tetramethylheptanedione, H2 Pc=phthalocyanine), was synthesized by doping the paramagnetic erbium(III) compound Er2 ⋅ 2C6 H6 in the diamagnetic yttrium(III) matrix Y2 ⋅ 2C6 H6 . The doping effect was studied using SQUID magnetization measurements. The results suggest that magnetic-site dilution improves the magnetic property from a fast relaxation of the pure ErIII compound to a typical SMM relaxation process of the doped sample. In this binuclear system, the dominant single-ion relaxation is entangled with the neighboring ErIII ion through the intramolecular ErIII ⋅⋅⋅ErIII interaction, which plays an important role in suppressing the quantum tunneling of the magnetization (QTM) process. Furthermore, the influence of lattice solvents on single-ion relaxation was studied. By releasing the benzene molecules, compound YEr ⋅ 2C6 H6 can be successfully transformed to a desolvated sample YEr accompanied by structural alteration and improved SMM performance.

ZnO nanoparticles: recent advances in ecotoxicity and risk assessment.

The widespread application of zinc oxide nanoparticles (nano-ZnO) has received increasing attention because of their potential risks to human health and the environment. This review summarizes the relationship between the toxic effects and physicochemical properties of nano-ZnO and the underlying toxicity mechanisms of nano-ZnO. This study presents the possible human health hazards posed by nano-ZnO exposure and the biotoxicity to bacteria, algae, higher plants, aquatic animals, terrestrial invertebrates and vertebrates in vitro and in vivo. The advances in research on the ecotoxicity of nano-ZnO and the potential risks to human health are discussed. Finally, the current research deficiencies in this area are identified, and recommendations for future research are proposed.

High selective detection of mercury (II) ions by thioether side groups on metal-organic frameworks.

Mercury ions can significantly affect the organism and environment even at a very low concentration. Thus, great efforts have been devoted to developing high sensitive electrochemical sensors, especially the one that not only detect the mercury ions but also effective sensitive to thymine-Hg2+-thymine in aqueous solution. Metal-organic-frameworks (MOFs) possess hollow nature and are easy for grafting functional groups, however, there is still no attempts for working as electrochemical sensors in detecting mercury ions. Herein, we report a novel type sensor of Zr(IV)-based MOFs with specifically attached thioether side groups allowing mercury ions to be easily adsorbed and detected. The Zr(IV)-involved MOFs show strong binding to mercury ions compared with the bare MOFs, as confirmed by both experiment measurements and theoretical calculations. The as-prepared senor is sensitive ranging from 0.01 nM to 3 µM with detection limitation of 7.3 fM, which is better than most of T-Hg2+-T- and enzyme-based sensors reported so far. The high sensitivity could be due to the straightforward adsorption pathway and the biomolecule exclusion nature of the Zr(IV)-involved MOFs sensor. We anticipate that our findings could pave the way for MOFs-based sensor exploration towards its commercial applications.