Photofunctional Gold Nanocluster Composites for Bioapplications.

Gold nanoclusters (AuNCs), with customized structures and diverse optical properties, are promising optical materials. Constructing composite systems by the assembly and incorporation of AuNCs can utilize their optical properties to achieve diagnostic and therapeutic applications in the biological field. Therefore, the exploration of the assembly behaviors of AuNCs and the enhancement of their performance has attracted widespread interest. In this review, we introduce multiple interactions and assembly modes that are prevalent in nanocomposites and microcomposites based on AuNCs. Then, the functions of AuNC composites for bioapplications are demonstrated in detail. These composite systems have inherited and enhanced the inherent optical performances of the AuNCs to meet diverse requirements for biological sensing and optical treatments. Finally, we discuss the prospects of AuNC composites and highlight the challenges and opportunities in biomedical applications.

Soil N2 O emissions from specialty crop systems: A global estimation and meta-analysis.

Nitrous oxide (N2 O) exacerbates the greenhouse effect and thus global warming. Agricultural management practices, especially the use of nitrogen (N) fertilizers and irrigation, increase soil N2 O emissions. As a vital sector of global agriculture, specialty crop systems usually require intensive input and management. However, soil N2 O emissions from global specialty crop systems have not been comprehensively evaluated. Here, we synthesized 1137 observations from 114 published studies, conducted a meta-analysis to evaluate the effects of agricultural management and environmental factors on soil N2 O emissions, and estimated global soil N2 O emissions from specialty crop systems. The estimated global N2 O emission from specialty crop soils was 1.5 Tg N2 O-N year-1 , ranging from 0.5 to 4.5 Tg N2 O-N year-1 . Globally, soil N2 O emissions exponentially increased with N fertilizer rates. The effect size of N fertilizer on soil N2 O emissions generally increased with mean annual temperature, mean annual precipitation, and soil organic carbon concentration but decreased with soil pH. Global climate change will further intensify the effect of N fertilizer on soil N2 O emissions. Drip irrigation, fertigation, and reduced tillage can be used as essential strategies to reduce soil N2 O emissions and increase crop yields. Deficit irrigation and non-legume cover crop can reduce soil N2 O emissions but may also lower crop yields. Biochar may have a relatively limited effect on reducing soil N2 O emissions but be effective in increasing crop yields. Our study points toward effective management strategies that have substantial potential for reducing N2 O emissions from global agricultural soils.

Tunable Fluorescence, Morphology, and Antibacterial Behaviors of Conjugated Oligomers via Host-Guest Supramolecular Self-Assembly.

Host-guest supramolecular self-assembly has become one facile but efficient way to regulate the optical properties of conjugated oligomers and construct promising photofunctional materials. Herein, we design two linear conjugated oligomers terminated with two or four pyridinium moieties, which show different 1:1 'head-to-tail' binding patterns with cucurbit[8]uril (CB[8]) to form host-guest supramolecules. After being encapsulated in the hydrophobic cavity of the CB[8] host, the fluorescence emission of the conjugated oligomers undergoes significant changes, resulting in tunable fluorescence color with enhanced quantum yields. Triggered by the aggregation of supramolecules, the regular or rigid binding modes lead to the formation of cuboids and spheroids in nanoscale, respectively. Due to the macrocyclic-confinement effect, the light-driven reactive oxygen species (ROS) production of the host-guest complex is increased significantly, thereby improving the photodynamic antibacterial performance toward Staphylococcus aureus (S. aureus).

Coupling vibration analysis of heat exchanger tube bundles under different stiffness conditions.

A two-dimensional tube bundles fluid-structure coupling model was developed using the CFD approach, with a rigid body motion equation and the Newmark integral method. The numerical simulations were performed to determine the vibration coupling properties between various tube bundles of stiffness. Take the corner square tube bundles with a pitch ratio of 1.28 as the research object. The influence of adjacent tubes with different stiffness on the vibration of the central target tube was analyzed. The research results show that the vibration characteristic of tube bundles is affected by the flow field dominant frequency and the inherent frequency of tube bundles. The vibration of adjacent tube bundles significantly impacts the amplitude and frequency of the central target tube. The equal stiffness and large stiffness tubes upstream or downstream inhibit the vibration displacement of the target tube to some extent. The low-stiffness tubes upstream or downstream significantly enhanced the amplitude of the target tube. The findings can be used to provide a basis for reasonable design and vibration suppression of shell-and-tube heat exchangers.

Seedless wet synthesis of copper-twinned nanocrystals.

The wet synthesis of copper (Cu)-twinned nanostructures often requires the addition of noble metal seeds, as twinned Cu seeds are prone to oxidative etching, which inevitably introduces other metal species. In this study, a universal and seedless wet method is proposed for the synthesis of various Cu-twinned nanostructures, such as large Cu decahedrons (with sizes up to 300 nm), singly twinned Cu right bipyramids, and Cu nanorods. The amount of chloride ions (Cl-) and oleylamine and an optimal heating rate at the initial stage were proven to be crucial in this synthesis. Theoretical results revealed that the amount of Cl- could adjust the Gibbs free energy of Cu seeds by promoting the dissociation of oleylamine, which, in turn, determined the structure of thermodynamically favorable seeds based on the thermodynamic model. To the best of our knowledge, this is the first report on large Cu decahedrons and singly twinned Cu right bipyramids. Moreover, they both showed strong localized surface plasmon resonance in the near-infrared region. The photothermal conversion efficiency of large Cu decahedrons increased up to 52.9% upon 808 nm laser irradiation, which is the highest value ever reported for Cu nanocrystals.

Green Synthesis of Antimicrobial Peptide-Protected Silver Nanoclusters with Regulated Antibacterial Behavior.

The antibacterial system based on the silver element has been a very promising antibacterial material. However, the antibacterial activity of silver nanomaterials largely depends on their chemical composition and physical properties. Herein, we prepared ultrasmall silver nanoclusters by directly reducing silver ions with antimicrobial peptide in a green way. The positively charged peptide ligands drove the silver nanoclusters binding to bacteria by electrostatic attraction. Contrary to the large-sized silver nanomaterials, the ultrasmall silver nanoclusters were able to rapidly penetrate bacteria membranes via strong hydrophobic association, significantly promoting the generation of reactive oxygen species, and the subsequent high oxidative stress led to bacterial death. Moreover, the silver nanoclusters with antibacterial peptide ligand exhibited good stability, low cytotoxicity, and long-term antibacterial activity. Besides, synergistic enhancement of silver nanoclusters on antibacterial activity was observed. Therefore, the silver nanoclusters conjugated with the antimicrobial peptide can act as a synergistic antibacterial agent, in which their bio-interactions with bacteria have been regulated to achieve a rapid, long-lasting, and broad-spectrum antibacterial effect.

Restraining Interfacial Cu2+ by using Amorphous SnO2 as Sacrificial Protection Boosts CO2 Electroreduction.

The electrochemical carbon dioxide reduction reaction (CO2 RR) to formate is of great interest in the field of electrochemical energy. Cu-based material is an appealing electrocatalyst for the CO2 RR. However, retaining Cu2+ under the high cathodic potential of CO2 RR remains a great challenge, leading to low electrocatalytic selectivity, activity, and stability. Herein, inspired by corrosion science, a sacrificial protection strategy to stabilize interfacial crystalline CuO through embedding of active amorphous SnO2 (c-CuO/a-SnO2 ) is reported, which greatly boosts the electrocatalytic sensitivity, activity, and stability for CO2 RR to formate. The as-made hybrid catalyst can achieve superior high selectivity for CO2 RR to formate with a remarkable Faradaic efficiency (FE) of 96.7%, and a superhigh current density of over 1 A cm-2 that far outperforms industrial benchmarks (FE > 90%, current density > 300 mA cm-2 ). In situ X-ray absorption spectroscopy (XAS) and X-ray diffractionexperimental and theoretical calculation results reveal that the broadened s-orbital in interfacial a-SnO2 offers the lower orbital for extra electrons than Cu2+ , which can effectively retain nearby Cu2+ , and the high active interface significantly lowers the energy barrier of the limited step (* CO2 → * HCOO) and enhances the selectivity and activity for CO2 RR to formate.

Covalent netting restrains dissolution enabling stable high-loading and high-rate iron difluoride cathodes.

Metal fluoride conversion cathodes are promising for the production of cheap, sustainable, and high-energy lithium-ion batteries. Yet, such systems are plagued by active material dissolution that causes capacity fade and hinders commercialization. Here, a covalent netting strategy is proposed to overcome this hurdle. In a proof-of-concept design, polydopamine derived carbon-mediated covalent binding inhibited the dissolution, while the pyrolyzed bacterial cellulose netting structure furnished fast electronic and ionic transport pathways. We demonstrate high-capacity, high-rate and long-lasting stability attained at practical loading levels. Our investigations suggest that the covalent netting-enabled formation of a robust and efficient blocking layer, highly competent in suppressing the leaching, is key for a stable performance. The successful stabilization of metal difluorides in the absence of electrolyte engineering opens an avenue for their practical deployment in future higher-level but lower-cost batteries, and provides a solution to similar challenges encountered by other dissolving energy electrode materials.

Protein-Assisted Molybdenum Disulfide as Biomimetic Nanozyme for Antibacterial Application.

Molybdenum-based nanomaterials with variable oxidation states can be developed as nanozyme catalysts. In this work, we developed a one-pot method for the preparation of molybdenum disulfide assisted by protein. Protamine was used as a cationic template to link molybdate anions and form complexes. During hydrothermal synthesis, protamine can affect the nucleation process of molybdenum disulfide and inhibit their aggregation, which facilitates the fabrication of small-sized molybdenum disulfide nanoparticles. Moreover, the abundant amino/guanidyl groups of protamine could both physically adsorb and chemically bond to molybdenum disulfide and further modulate the crystal structures. The optimized size and crystalline structure enabled a higher exposure of active sites, which enhanced the peroxidase-like activity of molybdenum disulfide/protamine nanocomposites. Meanwhile, the antibacterial activity of protamine was retained in the molybdenum disulfide/protamine nanocomposites, which could synergize with the peroxidase-like activity of molybdenum disulfide to kill bacteria. Therefore, the molybdenum disulfide/protamine nanocomposites are good candidates for antibacterial agents with lower chances of antimicrobial resistance. This study establishes an easy way to design artificial nanozymes by compounding suitable components.

SEanalysis 2.0: a comprehensive super-enhancer regulatory network analysis tool for human and mouse.

Super-enhancers (SEs) play an essential regulatory role in various biological processes and diseases through their specific interaction with transcription factors (TFs). Here, we present the release of SEanalysis 2.0 (http://licpathway.net/SEanalysis), an updated version of the SEanalysis web server for the comprehensive analyses of transcriptional regulatory networks formed by SEs, pathways, TFs, and genes. The current version added mouse SEs and further expanded the scale of human SEs, documenting 1 167 518 human SEs from 1739 samples and 550 226 mouse SEs from 931 samples. The SE-related samples in SEanalysis 2.0 were more than five times that in version 1.0, which significantly improved the ability of original SE-related network analyses ('pathway downstream analysis', 'upstream regulatory analysis' and 'genomic region annotation') for understanding context-specific gene regulation. Furthermore, we designed two novel analysis models, 'TF regulatory analysis' and 'Sample comparative analysis' for supporting more comprehensive analyses of SE regulatory networks driven by TFs. Further, the risk SNPs were annotated to the SE regions to provide potential SE-related disease/trait information. Hence, we believe that SEanalysis 2.0 has significantly expanded the data and analytical capabilities of SEs, which helps researchers in an in-depth understanding of the regulatory mechanisms of SEs.

Stimuli-Induced Subconformation Transformation of the PSI-LHCI Protein at Single-Molecule Resolution.

Photosynthesis is a very important process for the current biosphere which can maintain such a subtle and stable circulatory ecosystem on earth through the transformation of energy and substance. Even though been widely studied in various aspects, the physiological activities, such as intrinsic structural vibration and self-regulation process to stress of photosynthetic proteins, are still not in-depth resolved in real-time. Herein, utilizing silicon nanowire biosensors with ultrasensitive temporal and spatial resolution, real-time responses of a single photosystem I-light harvesting complex I (PSI-LHCI) supercomplex of Pisum sativum to various conditions, including gradient variations in temperature, illumination, and electric field, are recorded. Under different temperatures, there is a bi-state switch process associated with the intrinsic thermal vibration behavior. When the variations of illumination and the bias voltage are applied, two additional shoulder states, probably derived from the self-conformational adjustment, are observed. Based on real-time monitoring of the dynamic processes of the PSI-LHCI supercomplex under various conditions, it is successively testified to promising nanotechnology for protein profiling and biological functional integration in photosynthesis studies.

Labile carbon and soil texture control nitrogen transformation in deep vadose zone.

Understanding transient nitrogen (N) storage and transformation in the deep vadose zone is critical for controlling groundwater contamination by nitrate. The occurrence of organic and inorganic forms of carbon (C) and nitrogen and their importance in the deep vadose zone is not well characterized due to difficulty in sampling and the limited number of studies. We sampled and characterized these pools beneath 27 croplands with different vadose zone thicknesses (6-45 m). We measured nitrate and ammonium in different depths for the 27 sites to evaluate inorganic N storage. We measured total Kjeldahl nitrogen (TKN), hot-water extractable organic carbon (EOC), soil organic carbon (SOC), and δ13C for two sites to understand the potential role of organic N and C pools in N transformations. Inorganic N stocks in the vadose zone were 21.7-1043.6 g m-2 across 27 sites; the thicker vadose zone significantly stored more inorganic N (p < 0.05). We observed significant reservoirs of TKN and SOC at depths, likely representing paleosols that may provide organic C and N to subsurface microbes. The occurrence of deep C and N needs to be addressed in future research on terrestrial C and N storage potential. The increase of ammonium and EOC and δ13C value in the proximity of these horizons is consistent with N mineralization. An increase of nitrate, concurrent with the sandy soil texture and the water-filled pore space (WFPS) of 78 %, suggests that deep vadose zone nitrification may be supported in vadose zones with organic-rich layers such as paleosol. A profile showing the decrease of nitrate concentrations, concurrent with the clay soil texture and the WFPS of 91 %, also suggests denitrification may be an important process. Our study shows that microbial N transformation may be possible even in deep vadose zone with co-occurrence of C and N sources and controlled by labile C availability and soil texture.

Single-exonuclease nanocircuits reveal the RNA degradation dynamics of PNPase and demonstrate potential for RNA sequencing.

The degradation process of RNA is decisive in guaranteeing high-fidelity translation of genetic information in living organisms. However, visualizing the single-base degradation process in real time and deciphering the degradation mechanism at the single-enzyme level remain formidable challenges. Here, we present a reliable in-situ single-PNPase-molecule dynamic electrical detector based on silicon nanowire field-effect transistors with ultra-high temporal resolution. These devices are capable of realizing real-time and label-free monitoring of RNA analog degradation with single-base resolution, including RNA analog binding, single-nucleotide hydrolysis, and single-base movement. We discover a binding event of the enzyme (near the active site) with the nucleoside, offering a further understanding of the RNA degradation mechanism. Relying on systematic analyses of independent reads, approximately 80% accuracy in RNA nucleoside sequencing is achieved in a single testing process. This proof-of-concept sets up a Complementary Metal Oxide Semiconductor (CMOS)-compatible playground for the development of high-throughput detection technologies toward mechanistic exploration and single-molecule sequencing.

Controllable Gold Nanocluster-Emulsion Interface for Direct Cell Penetration and Photothermal Killing.

In the view of their ability to be uptaken by cells, colloidal particles can exert diverse physiological effects and are promising vehicles for the intracellular delivery of biologically active substances. Given that the modulation of biomaterial interfaces greatly facilitates the prediction and control of the corresponding cellular responses, the interfacial behavior of hydrophobic dye-modified gold (Au) nanoclusters (Au NCs) is rationally designed to develop Au NC-containing emulsions and control their biointerfacial interactions with cell membranes. The observed biological performance is indicative of a physical penetration mechanism. The amphiphilic Au NCs decrease the interfacial energy of two immiscible liquids and hinder droplet coalescence to facilitate the formation of emulsions thermodynamically stabilized by dipole-dipole and hydrophobic interactions. Moreover, the amphiphilic Au NCs are localized on the emulsion droplet surface and form segregated interfacial microdomains that adapt to the membrane structure and facilitate the traverse of the emulsions across the cell membrane via direct penetration. Fast penetration coupled with excellent photophysical performance endows the emulsions with multifluorescence tracing and efficient photothermal killing capabilities. The successful change of the interaction mode between NCs and biological objects and the provision of a universal formulation to modulate biointerfacial interactions are expected to inspire new bioapplications.

Covalent Organic Frameworks as Efficient Photoinitiators and Cross-Linkers To Fabricate Highly Stretchable Hydrogels.

In this work, two kinds of imine-type covalent organic framework (COF) nanoparticles are demonstrated as efficient photocatalytic initiators to trigger the free-radical polymerization of acrylamide (AM) to prepare polyacrylamide (PAM) hydrogels under visible light irradiation, without any assistance from the co-initiator. Simultaneously, the COF nanoparticles bearing vinyl side groups (COF-V) promote covalent cross-linking of the polymer chains, which significantly reinforces the mechanical properties of the nanocomposite hydrogel. The obtained PAM/COF-V hydrogel is highly stretchable with an extraordinary elongation up to 3300% strain. On the other hand, the COF nanoparticles modified with methoxy moieties (COF-OMe) endow the resulting PAM/COF-OMe hydrogel with a promising fluorescence feature. In addition, this strategy provides a visible-light-regulated photocatalytic polymerization approach with a simplified recipe to fabricate COF-based nanocomposite hydrogels or resins with diverse functions.

Chloride-ion-directed synthesis of plate-like Cu2O mesocrystals for effective nitrogen fixation.

Cuprous oxide (Cu2O) mesocrystals, which are composed of numerous nanocrystals with a common crystallographic orientation, are supposed to possess superior photocatalytic abilities than the normal constructions, but very few of them have been reported to date. In this work, plate-like Cu2O mesocrystals were successfully fabricated via a facile one-pot wet chemical strategy. Unlike the commonly used polymers or small molecules, chloride ions (Cl-) were employed as structure-directing agents and played the main role in the Cu2O mesocrystal formation. The formation mechanism was interpreted as follows: the presence of Cl- inhibited the formation of CuO and Cu by forming the intermediate product CuCl, which was further hydrolyzed to Cu2O nanocrystals. Cl- tended to adsorb on the (111) facets of the formed Cu2O nanocrystals and stabilize them. Then the Cu2O nanocrystals were aligned side by side through the unabsorbed side faces, leading to mutual nanocrystals orientation and crystallographic lock-in, facilitating the formation of plate-like Cu2O mesocrystals. The polymer, polyacrylamide (PAM), also promoted the mesocrystals formation by serving as a stabilizer and fixed the crystallographic orientation of the Cu2O nanocrystals during their orderly stacking process. The plate-like Cu2O mesocrystals showed a long decay time and pronounced performance toward the visible-light-driven photocatalytic reduction of N2 into NH3. This research may stimulate in-depth investigations into the exploration of new synthetic methods for the design and construction of novel mesocrystals.

In Situ Synthesis of Gold Nanoclusters in Covalent Organic Frameworks with Enhanced Photodynamic Properties and Antibacterial Performance.

In this work, ultrasmall gold nanoclusters (AuNCs) have been in situ synthesized in nanopores of covalent organic framework (COF) nanoparticles, which exhibited enhanced fluorescence, improved photosensitizing capabilities, and promising antibacterial performance. A small organic molecule, 1-vinylimidazole (Vim), was diffused into the nanopores of imine-based COFs and served as a reducing agent and capping ligand for the in situ synthesis of ultrasmall AuNCs. The as-obtained AuNCs were homogeneously distributed throughout the COF nanoparticles whose fluorescence intensity was enhanced remarkably. Due to the efficient electron transfer between AuNCs and COFs and increased separation of photogenerated electron-hole pairs, the light-triggered reactive oxygen species (ROS) production of COFs was prominently enhanced by AuNCs. Moreover, the obtained nanocomposites exhibited an efficient photodynamic killing behavior on Escherichia coli under visible light exposure. Thus, we provide a facile strategy to prepare COF/AuNC nanocomposites for ROS-related applications.

Layer-by-layer stacked vanadium nitride nanocrystals/N-doped carbon hybrid nanosheets toward high-performance aqueous zinc-ion batteries.

Aqueous zinc ion batteries (AZIBs) hold great potential in large scale, low-cost energy storage. Unfortunately, their development is limited by the poor performing cathode materials due to their unstable structures and low capacities. Hence, we develop novel layer-by-layer stacked vanadium nitride nanocrystals/N-doped carbon hybrid nanosheets (VN/NC) as cathode materials by in situ thermal conversion of pyrolyzing pentyl viologen intercalated V2O5. The combination of a leaf-like morphology, the nano structure of vanadium nitride crystals and the conductive porous nitrogen-doped carbon nanosheets endow the VN/NC cathode with excellent electrochemical performance in AZIBs. Thus, it delivers a high discharge specific capacity of 566 mA h g-1 at a current density of 0.2 A g-1 and a superior rate capability. Most importantly, it exhibits a remarkable cyclic stability with capacity retention of 131 mA h g-1 (85% of the initial capacity) after 1000 cycles at a current density of 10 A g-1. The design of the unique VN/NC hybrid nano sheets offers a pathway towards developing high performance electrode materials for energy storage.

Conjugated Molecule-Assisted Supramolecular Hydrogel with Enhanced Antibacterial and Antibiofouling Properties.

The hydrogel using natural and synthetic polymers to create a cross-linking network has drawn attention in diverse bioapplications. However, inhibition of bacterial infection is still a challenge for hydrogel's wide application. In this work, we reported a supramolecular hydrogel with a good antibacterial property built from conjugated molecules. The water-soluble molecular 4,7-bis[9,9-di(2-carboxy-ethyl)-fluoren-2-yl]-2,1,3-benzothiadiazole (OFBTCOOH) physically linked with monomers via hydrophobic interaction. The free-radical polymerized poly(N-acryloyl glycinamide) was hydrogen-bond cross-linked by dual amides in the side chains to form a hydrogel. An adjustable micro-network was obtained by increasing OFBTCOOH with evidence of enhanced intermolecular interaction. The successfully integrated OFBTCOOH could be excited upon light irradiation. The energy of triplet-state excitons of OFBTCOOH transferred to the ground-state oxygen to produce singlet oxygen, which endowed the hydrogel with the antibacterial property. Meanwhile, the superhydrophilic surface of the hydrogel can bind water molecules to form a stable hydration layer, which acted as barriers to resist protein and bacterial adsorption and achieve the anti-biofouling goal. The ease in introducing conjugated polyelectrolytes may provide a formulation to functionalize hydrogels via various physical interactions.