Coordination Compound Guided a Novel Composite Film with Zn2V2O7 Nanoflake and VO2@Zn2V2O7 Nanoparticle for Enhanced Thermochromism Smart Window.

Thermochromic vanadium dioxide (VO2) can intelligently modulate the transmittance of indoor solar radiation to reduce the energy consumption of air conditioning in buildings. Nevertheless, it remains a great challenge to simultaneously improve the luminous transmittance (Tlum) and solar modulation ability (ΔTsol) of VO2. In this study, a novel approach is employed utilizing a coordination compound to finely tune the growth of a VO2 based composite film, yielding a hierarchical film comprising Zn2V2O7 nanoflakes and VO2@Zn2V2O7 core-shell nanoparticles. Remarkably, the resulting composite films showcase exceptional optical performance, achieving a Tlum of up to 73.0% and ΔTsol of 15.7%. These outcomes are attributed to the antireflection properties inherent in the nanoflake structure and the localized surface plasmon resonance of well-dispersed VO2 nanoparticles. In addition, the Zn2V2O7-VO2 film demonstrates remarkable environmental durability, retaining 90% of its initial ΔTsol even after undergoing aging at 100 °C under 50% relative humidity for a substantial period of 30 days - a durability equivalent to ≈20 years under ambient conditions. This work not only achieves a harmonious balance between Tlum and ΔTsol but also introduces a promising avenue for the design of distinctive composite nanostructures.

Interfacial Reaction-Directed Green Synthesis of CeO2-MnO2 Catalysts for Imine Production through Oxidative Coupling of Alcohols and Amines.

Direct oxidative coupling of alcohols with amines over cheap but efficient catalysts is a promising choice for imine formation. In this study, porous CeO2-MnO2 binary oxides were prepared via an interfacial reaction between Ce2(SO4)3 and KMnO4 at room temperature without any additives. The as-prepared porous CeO2-MnO2 catalyst has a higher fraction of Ce3+, Mn3+, and Mn4+ and contains larger surface area and more oxygen vacancies. During the oxidative coupling reaction of alcohol with amine to imine, the as-obtained CeO2-MnO2 catalyst is motivated by the above encouraging characteristics and exhibits superior catalytic activity (98% conversion and 97% selectivity) and can also work effectively under a wide scope of temperatures and substrates. The in-depth in situ DRIFTS and density functional theory (DFT) results demonstrate that there is a strong interaction between CeO2 and MnO2 in the CeO2-MnO2 catalyst, exhibiting especially a positive synergistic effect in the direct coupling of alcohol and amine reaction.

Normal Reference Intervals of Neutrophil-To-Lymphocyte Ratio, Platelet-To-Lymphocyte Ratio, Lymphocyte-To-Monocyte Ratio, and Systemic Immune Inflammation Index in Healthy Adults: a Large Multi-Center Study from Western China.

BACKGROUND: Numerous studies have shown that the hematological components of the systemic inflammatory response, including the neutrophil-to-lymphocyte ratio (NLR), the platelet-to-lymphocyte ratio (PLR), the lymphocyte-to-monocyte ratio (LMR), and the systemic immune inflammation index (SII) are efficient prognostic indicators in patients with cancers. Most of the studies did not investigate the reference intervals (RIs) of these parameters in healthy controls. METHODS: A retrospective cohort study was performed on healthy ethnic Han population aged between 18 and 79 years of age by retrieving the data from a healthy routine examination center database and laboratory infor-mation system of four participating centers in western China. By following the Clinical and Laboratory Standards Institute (CLSI), RIs of each parameter was established and validated. RESULTS: The analysis included 5,969 healthy subjects. We found that the individual's gender can significantly influence PLR, LMR, and SII (all p < 0.05), but not NLR (p > 0.05). Surprisingly, we also found that with an increase in age, the PLR, LMR, and SII tend to decrease, while NLR remained stable. PLR, LMR, and SII values were significantly higher in the young adults (18 - 64 years) than in old adults (65 - 79 years) (p < 0.001). The RIs of NLR, PLR (adults), PLR (old adults), LMR and SII were 0.88 - 4.0, 49 - 198, 42 - 187, 2.63 - 9.9, 142 x 109/L - 804 x 109/L, respectively. CONCLUSIONS: Our study addresses possible variations and establishes consensus for the NLR, PLR, LMR, and SII RIs for healthy Han Chinese adults in western China. Further, established RIs can standardize clinical applications and promote the use of these indicators into the routine complete blood count report.

Electrodeposited Vanadium Dioxide Films with Unique Optical Property.

This study represents a facile but effective electrodeposition method to fabricate vanadium dioxide (VO2) thin films on fluorine doped tin oxide (FTO) glass at room temperature. The film microstructure (thickness, surface structure, particle size and composition) and relevant optical properties were investigated by several advanced techniques. The pertinent variables that can affect the thin film formation and structure, such as deposition potential, time and post-treatment annealing temperature were also studied. It was found that the film thickness could be tuned from 35 to 130 nm by adjusting the potential from -1.22 to -1.35 V, and consequently leading to optical transmittance decreasing from ∼60% to ∼38% in the wavelength of 500-1000 nm, further confirmed by computational simulations using three-dimension (3D) finite-difference time-domain method. The hysteresis loop of the generated VO2 film on FTO glass shows that the phase transition temperature from monoclinic to rutile is around 73 °C, a little higher than pure monoclinic VO2 (∼68 °C) in this study. This proposed electrodeposition method is possible to extend into obtaining metal oxide films with tuneable surface properties for thermochromic smart devices.

Superwettability Strategy: 1D Assembly of Binary Nanoparticles as Gas Sensors.

Binary 1D nanowires consisting of both SnO2 nanoparticles and Au nanorods are fabricated through a "substrate-particle solution template" assembling method, which shows highly enhanced gas sensitivity toward acetone under ambient conditions.

Seedless Synthesis of Monodispersed Gold Nanorods with Remarkably High Yield: Synergistic Effect of Template Modification and Growth Kinetics Regulation.

Gold nanorods (AuNRs) are versatile materials due to their broadly tunable optical properties associated with their anisotropic feature. Conventional seed-mediated synthesis is, however, not only limited by the operational complexity and over-sensitivity towards subtle changes of experimental conditions but also suffers from low yield (≈15 %). A facile seedless method is reported to overcome these challenges. Monodispersed AuNRs with high yield (≈100 %) and highly adjustable longitudinal surface plasmon resonance (LSPR) are reproducibly synthesized. The parameters that influence the AuNRs growth were thoroughly investigated in terms of growth kinetics and soft-template regulation, offering a better understanding of the template-based mechanism. The facile synthesis, broad tunability of LSRP, high reproducibility, high yield, and ease of scale-up make this method promising for the future mass production of monodispersed AuNRs for applications in catalysis, sensing, and biomedicine.

Direct Hydrothermal Synthesis of Carbonaceous Silver Nanocables for Electrocatalytic Applications.

This study demonstrates a facile but efficient hydrothermal method for the direct synthesis of both carbonaceous silver (Ag@C core-shell) nanocables and carbonaceous nanotubes under mild conditions (<180 °C). The carbonaceous tubes can be formed by removal of the silver cores via an etching process under temperature control (60-140 °C). The structure and composition are characterized using various advanced microscopic and spectroscopic techniques. The pertinent variables such as temperature, reaction time, and surfactants that can affect the formation and growth of the nanocables and nanotubes are investigated and optimized. It is found that cetyltrimethylammonium bromide plays multiple roles in the formation of Ag@C nanocables and carbonaceous nanotubes including: a shape controller for metallic Ag wires and Ag@C cables, a source of Br(-) ions to form insoluble AgBr and then Ag crystals, an etching agent of silver cores to form carbonaceous tubes, and an inducer to refill silver particles into the carbonaceous tubes to form core-shell structures. The formation mechanism of carbonaceous silver nanostructures depending upon temperature is also discussed. Finally, the electrocatalytic performance of the as-prepared Ag@C nanocables is assessed for the oxidation reduction reaction and found to be very active but much less costly than the commonly used platinum catalysts. The findings should be useful for designing and constructing carbonaceous-metal nanostructures with potential applications in conductive materials, catalysts, and biosensors.

Crystal plane-dependent gas-sensing properties of zinc oxide nanostructures: experimental and theoretical studies.

The sensitivity of a metal oxide gas sensor is strongly dependent on the nature of the crystal surface exposed to the gas species. In this study, two types of zinc oxide (ZnO) nanostructures: nanoplates and nanorods with exposed (0001) and (10̄10) crystal surfaces, respectively, were synthesized through facile solvothermal methods. The gas-sensing results show that sensitivity of the ZnO nanoplates toward ethanol is two times higher than that of the ZnO nanorods, at an optimum operating temperature of 300 °C. This could be attributed to the higher surface area and the exposed (0001) crystal surfaces. DFT (Density Functional Theory) simulations were carried out to study the adsorption of ethanol on the ZnO crystal planes such as (0001), (10̄10), and (11̄20) with adsorbed O(-) ions. The results reveal that the exposed (0001) planes of the ZnO nanoplates promote better ethanol adsorption by interacting with the surface oxygen p (O2p) orbitals and stretching the O-H bond to lower the adsorption energy, leading to the sensitivity enhancement of the nanoplates. These findings will be useful for the fabrication of metal oxide nanostructures with specifically exposed crystal surfaces for improved gas-sensing and/or catalytic performance.

Main group metal elements enhance electrochemical nitrogen reduction reaction of vanadium-based single atom catalysts through d-p orbital hybridization.

Developing active sites with flexibility and diversity is crucial for single atom catalysts (SACs) towards sustainable nitrogen fixation at ambient conditions. Herein, the effects of doping main group metal elements (MGM) on the stability, catalytic activity, and selectivity of vanadium-based SACs is systematically investigated based on density functional theory calculations. It is found that the catalytic activity of V site can be significantly enhanced by the synergistic effect between MGM and vanadium atoms. More importantly, a volcano curve between the catalytic activity and the adsorption free energy of NNH* can be established, in which V-Pb dimer embedded on N-coordinated graphene (VPb-NG) exhibits optimal NRR activity due to its location at the top of volcano. Further analysis of electronic structures reveals that the unoccupancy ratio (eg/t2g) of V site is dramatically increased by the strong d-p orbital hybridization between V and Pb atoms, subsequently, N2 is activated to a larger extent. These interesting findings may provide a new path for designing active sites in SACs with excellent performance.

Highly selective fluorescent probe for cysteine via a tandem reaction and its bioimaging application in HeLa cells.

Cysteine, as a vital endogenous small molecule mercaptan, plays a crucial role in various physiological processes. The high sensitivity and selectivity of fluorescent probes provide a method to monitor cysteine, which is helpful to understand the mechanism of cysteine in physiological processes more comprehensively. However, the detection of cysteine can be interfered by other small molecule biothiols. Therefore, the design of fluorescent probe based on the structural characteristics and reactivity of cysteine has become research focus currently. Given the biological compatibilities, biological targets, the metabolic pathway of 3-hydoxythalidomide, and its unique fluorescent properties, herein, we have designed a chemodosimeter, 2-(2,6-dioxopiperidin-3-yl)-1,3-dioxoisoindolin-4-yl acrylate, for the detection of cysteine based on a tandem reaction of thiol-ene click chemistry and aminolysis involving 3-hydroxythalidomide as a parent compound. Experimental data exhibited that the probe showed unique selectivity and sensitivity for cysteine over other amino acid and biothiols. In addition, the fluorescent intensity at 511 nm increased linearly as a function of cysteine concentration in the range of 0-6 × 10-7 M (regression factor, R2 = 0.999), with a limit of detection of 6.1 nM. The sensing mechanism was confirmed through 1H NMR titration and density functional theory calculations. Additionally, the probe was also successfully utilized for the detection of cysteine in sewage and for bioimaging in HeLa cells.

Surface hydrophobization of zeolite enables mass transfer matching in gas-liquid-solid three-phase hydrogenation under ambient pressure.

Attaining high hydrogenation performance under mild conditions, especially at ambient pressure, remains a considerable challenge due to the difficulty in achieving efficient mass transfer at the gas-liquid-solid three-phase interface. Here, we present a zeolite nanoreactor with joint gas-solid-liquid interfaces for boosting H2 gas and substrates to involve reactions. Specifically, the Pt active sites are encapsulated within zeolite crystals, followed by modifying the external zeolite surface with organosilanes. The silane sheath with aerophilic/hydrophobic properties can promote the diffusion of H2 and the mass transfer of reactant/product molecules. In aqueous solutions, the gaseous H2 molecules can rapidly diffuse into the zeolite channels, thereby augmenting H2 concentration surround Pt sites. Simultaneously, the silane sheath with lipophilicity nature promotes the enrichment of the aldehydes/ketones on the catalyst and facilitates the hydrophilia products of alcohol rediffusion back to the aqueous phase. By modifying the wettability of the catalyst, the hydrogenation of aldehydes/ketones can be operated in water at ambient H2 pressure, resulting in a noteworthy turnover frequency up to 92.3 h-1 and a 4.3-fold increase in reaction rate compared to the unmodified catalyst.

Bimetallic Ag-Au nanowires: synthesis, growth mechanism, and catalytic properties.

Silver-gold (Ag-Au) bimetallic nanowires were controllably synthesized by a newly developed wet-chemical method at room temperature. The Ag nanowires and Au nanoparticles were sequentially formed by reduction with vanadium oxide (V2O3) nanoparticles so as to form Ag-Au bimetal, in which the Ag nanowires show a diameter of ~20 nm and length up to 10 µm. A few unique features were noted in our new approach: it was rapid (within a few minutes), controllable in shape and size, reproducible, and there was no need for any surface modifiers. The formation and growth mechanisms of these Ag-Au bimetallic nanostructures driven by lattice match and a unique reducing agent (V2O3) have been proposed in this study. Moreover, the application of such bimetallic nanoparticles for catalytic reduction of 4-nitrophenol to 4-aminophenol was performed, and they exhibit catalytic properties superior to those of the Ag nanowires, Au nanoparticles, and Ag-Pd bimetallic nanostructures prepared under the reported conditions. These Ag-Au bimetallic nanoparticles have potential to be highly efficient catalysts for the reduction of 4-nitrophenol. This study may lead to new path for the generation of other bimetallic nanostructures with excellent catalytic efficiency.

Feasibility of nanofluid-based optical filters.

In this article we report recent modeling and design work indicating that mixtures of nanoparticles in liquids can be used as an alternative to conventional optical filters. The major motivation for creating liquid optical filters is that they can be pumped in and out of a system to meet transient needs in an application. To demonstrate the versatility of this new class of filters, we present the design of nanofluids for use as long-pass, short-pass, and bandpass optical filters using a simple Monte Carlo optimization procedure. With relatively simple mixtures, we achieve filters with <15% mean-squared deviation in transmittance from conventional filters. We also discuss the current commercial feasibility of nanofluid-based optical filters by including an estimation of today's off-the-shelf cost of the materials. While the limited availability of quality commercial nanoparticles makes it hard to compete with conventional filters, new synthesis methods and economies of scale could enable nanofluid-based optical filters in the near future. As such, this study lays the groundwork for creating a new class of selective optical filters for a wide range of applications, namely communications, electronics, optical sensors, lighting, photography, medicine, and many more.

Plasmonic "pump-probe" method to study semi-transparent nanofluids.

Nanofluids have been increasingly used in a wide range of thermal applications. Although these applications can benefit greatly from investigating the behavior of nanoparticles under different heating scenarios, there is a lack of experiments that can achieve this. To overcome this challenge, an optical "pump-probe"-type experiment is suggested in this paper. In experiments of this type, a set of "pumping" nanoparticles are specifically selected to absorb laser radiation. These particles represent a flexible tool for volumetric heating. A second set of "probing" nanoparticles can be tailored to scatter a separate optical probing signal. This work presents a selection procedure for nanoparticles of both types. The selection procedure is then demonstrated for a specific example where the pump and probe wavelengths are of 980 and 532 nm, respectively. Gold nanorods with diameters of 10 and a length of 58 nm are selected as the "most suitable" absorbing particles, while silver nanospheres with a diameter of 110 nm are selected as the "most suitable" scattering particles. These particles are synthesized and shown to experimentally match the desired optical properties. Overall, this paper proposes and demonstrates an approach by which it is possible to design and fabricate particles for a wide range of optical studies in semi-transparent nanofluids.

Recent Advances in Light-Conversion Phosphors for Plant Growth and Strategies for the Modulation of Photoluminescence Properties.

The advent of greenhouses greatly promoted the development of modern agriculture, which freed plants from regional and seasonal constraints. In plant growth, light plays a key role in plant photosynthesis. The photosynthesis of plants can selectively absorb light, and different light wavelengths result in different plant growth reactions. Currently, light-conversion films and plant-growth LEDs have become two effective ways to improve the efficiency of plant photosynthesis, among which phosphors are the most critical materials. This review begins with a brief introduction of the effects of light on plant growth and the various techniques for promoting plant growth. Next, we review the up-to-date development of phosphors for plant growth and discussed the luminescence centers commonly used in blue, red and far-red phosphors, as well as their photophysical properties. Then, we summarize the advantages of red and blue composite phosphors and their designing strategies. Finally, we describe several strategies for regulating the spectral position of phosphors, broadening the emission spectrum, and improving quantum efficiency and thermal stability. This review may offer a good reference for researchers improving phosphors to become more suitable for plant growth.

Cellulose phosphonate/polyethyleneimine nano-porous composite remove toxic Pb(II) and Cu(II) from water in a short time.

Current cellulose-based adsorbents suffer from the drawbacks of low adsorption capacity or slow adsorption rate for heavy metal ions. It is imperative to prepare new cellulose-based materials to improve the adsorption ability. In this work, we aim to introduce phosphonate groups to improve the adsorption ability of cellulose and select polyethyleneimine (PEI) for synergistic adsorption. A novel cellulose phosphonate/polyethyleneimine composite (MCCP-PEI) is prepared via the Mannich reaction. The structure and composition of MCCP-PEI are characterized by various advanced microscopy and spectroscopy techniques, and the results show that MCCP-PEI possesses abundant nano-porous structure, strong chelating sites, and excellent hydrophilicity. Besides, the adsorption behavior of MCCP-PEI for heavy metals has been systematically investigated. The results show that the adsorbent can quickly remove toxic Cu(II) and Pb(II) from water within 15 min and 20 min, respectively. The saturated adsorption capacity for Cu(II) and Pb(II) is 250.0 and 534.7 mg·g-1, respectively. X-ray photoelectron spectroscopy analysis combined with Density Functional Theory calculations reveal that the adsorption mechanism is chemical complexation and electrostatic attraction, and the phosphonate group plays a key role in the adsorption process.

Controllable synthesis of magic cube-like Ce-MOF-derived Pt/CeO2 catalysts for formaldehyde oxidation.

Controllable synthesis of MOFs with desired structures is of great significance to deepen the understanding of the crystal nucleation-growth mechanism and deliver unique structural features to their derived metal oxides with target catalytic applications. In this study, NH2-Ce-BDC with morphology similar to a second-order magic cube (mc) is facile synthesized via H+ mediation in nucleation and growth stages. The pertinent variables that can greatly influence the formation of magic cube-like structures (MCS) were investigated, in which the concentric diffusion field was found to be one of the key factors. Upon calcination, the derived CeO2 inherits unique gullies and grooves located on the pristine MOFs surface, which is quite useful for atomic layer deposition (ALD) of platinum (Pt) nanoparticles because of strong interaction with MOF-derived CeO2 (mc-CeO2). XPS, H2-TPR, Raman, and in situ DRIFTS characterization results show that there is a stronger interaction between Pt and mc-CeO2 in mc-Pt/CeO2 compared with c-Pt/CeO2 that is derived from the well-developed cubic Ce-MOFs. Furthermore, Pt2+ ions, hydroxyl oxygen, and oxygen defects in mc-Pt/CeO2 account highly for exemplary catalytic activity toward HCHO oxidation.

Synergistic Effect of Au-PdO Modified Cu-Doped K2W4O13 Nanowires for Dual Selectivity High Performance Gas Sensing.

Both 3-hydroxy-2-butanone and triethylamine are highly toxic and harmful to human health, and their chronic inhalation can cause respiratory diseases, eye lesions, dermatitis, headache, dizziness, drowsiness, and even fatality. Developing sensors for detecting such toxic gases with low power consumption, high response with superselectivity, and stability is crucial for healthcare and environmental monitoring. This study presents a typical gas sensor fabricated based on AuPdO modified Cu-doped K2W4O13 nanowires, which can selectively detect 3-hydroxy-2-butanone and triethylamine at 120 and 200 °C, respectively. The sensor displays excellent sensing performance at reduced operating temperature, high selectivity, fast response/recovery, and stability, which can be attributed to a synergistic effect of Cu dopants and AuPdO nanoparticles on the K2W4O13 host. The enhanced sensing response and selectivity could be attributed to the oxygen vacancies/defects, bandgap excitation, the electronic sensitization, the reversible redox reaction of PdO and Cu, the cocatalytic activity of AuPdO, and Schottky barrier contacts at the interface of tungsten oxide and Au. The significant variations in the activation capacities of Cu-doped K2W4O13, Pd/PdO, and Au nanoparticles toward 3H-2B and TEA, and the diffusion depth of the two gases in the coated sensing layer may cause dual selectivity. The designed gas sensor materials can serve as a sensitive target for detecting toxic biomarkers and hold broad application prospects in food and environmental safety inspection.

Multistimuli-Responsive Squaraine Dyad Exhibiting Concentration-Controlled Vapochromic Luminescence.

Stimuli-responsive organic materials with controllable luminescence are of enormous importance because of their potential applications in sensing, data security, and display devices. In this study, a multistimuli-responsive squaraine dyad (SQ-d) composed of two rigid squaraine moieties and a flexible ethylene linker was rationally designed and synthesized. SQ-d exhibits polymorphic luminescence, which can be reversibly switched by various external stimuli, including solvent vapor exposure, heat, and shear force. Unexpectedly, the weakly luminescent phase (O1) of SQ-d exhibits concentration-controlled vapochromic behavior. Film O1 can convert to a highly green-emissive phase (G1) under a low concentration of CHCl3 vapor and convert to a highly yellow-emissive phase (Y) under a high concentration of CHCl3 vapor; these originate from two distinct crystallization-induced emission enhancement processes. To the best of our knowledge, this is the first investigation of the effect of vapor concentration on the phase transitions of organic vapochromic luminophores. By analyzing the single-crystal structures and photophysical properties of SQ-d, we concluded that the green and yellow emissions probably originated from a zigzag stacking mode and an H-type π-π stacking mode, respectively. Finally, two prototypes based on SQ-d for applications in information encryption and vapor sensing were successfully demonstrated.

Temperature-triggered fluorocopolymer aggregate coating switching from antibacterial to antifouling and superhydrophobic hemostasis.

The multifunction antibacterial hemostatic materials can reduce blood loss, infection and wound complications, which probably decrease morbidity and health care costs. However, the contradictory relationship between antibacterial ability and biocompatibility, and the unnecessary blood loss restricts the practical application of hydrophilic cationic antibacterial hemostatic materials. Herein, a multifunctional temperature-triggered antibacterial hemostatic fluorocopolymer aggregate coating was developed. After self-assembly and quaternization process, the quaternized poly(N,N-dimethylaminoethylmethacrylate)-b-poly(1H,1H,2H,2H-heptadecafluorodecyl acrylate) block copolymers (PDMA-b-PFOEMA) aggregate coating consisting of fluoropolymer and quaternary ammonium salt were built. The synergistic effect on fluorinated block with low surface energy and quaternary ammonium salt block with bactericide activity severs the way of initial bacterial attachment and proliferation, while the migration of fluorinated block greatly promotes the biocompatibility and anti-adhesion performance in response to the switch from room temperature to physiological temperature. Furthermore, the fluorocopolymer aggregate coating with hydrophobic properties possessed the property of rapid coagulation, low blood loss, minor secondary bleeding and least bacteria infiltration. The multifunctional temperature-triggered fluorocopolymer aggregate coating with antifouling, antibacterial and hemostatic properties may have a great potential in the biomedical application.