Visible-Light-Driven Method for the Selective Synthesis of Amides and N-Acylureas from Carboxylic Acids and Thioureas.

In this work, we developed a visible-light-driven method for the selective synthesis of amides and N-acylureas from carboxylic acids and thioureas. This protocol was featured as avoidance of additional oxidants and transition metal catalysts, simple manipulations, low cost, broad substrate scope, and good functional group tolerance. As only oxygen serves as the oxidation reagent, this method provides a promising synthesis candidate for the formation of N-aryl amides and N-acylureas, including late-stage functionalization of complex pharmaceutical molecules and biologically active molecules.

CoO supported NiFe layered double hydroxide sandwich-like nanosheets on hierarchical carbon framework for efficient electrocatalytic oxygen evolution.

Exploration of greatly efficient and steady non-noble oxygen evolution reaction (OER) electrocatalysts is of great significance in improving the overall efficiency of energy density systems such as regenerative fuel cells, water electrolyzes, and metal-air batteries. Herein, inspired by hierarchical 3D porous structures with open microchannels of natural wood, CoO@NiFe LDH sandwich-like nanosheets were anchored on the carbonized wood (CW) via electrodeposition and calcination strategies. The strong interactions between CoO nanosheets and NiFe LDH nanosheets endow CoO@NiFe LDH/CW electrocatalyst with high catalytic properties toward the OER comparable to CoO/CW and NiFe LDH/CW. The optimized CoO@NiFe LDH/CW electrocatalyst demonstrates good OER catalytic performance with an overpotential of 230 mV at 100 mA cm-2. This work presents an innovative approach to utilize renewable resources for constructing advanced free-standing catalysts.

Nanocellulose-based nanogenerators for sensor applications: A review.

With the rapid development of the Internet of Things, nanogenerator as a green energy collection technology has attracted great attention in various fields. Specifically, the natural renewable nanocellulose as a raw material can significantly improve the environmental friendliness of the nanocellulose-based nanogenerators, which also makes the nanocellulose based nanogenerators expected to further develop in areas such as wearable devices and sensor networks. This paper mainly reports the application of nanocellulose in nanogenerator, focusing on the sensor. The types, sources and preparation methods of nanocellulose are briefly introduced. At the same time, the special structure of nanocellulose highlights the advantages of nanocellulose in nanogenerators. Then, the application of nanocellulose-based nanogenerators in sensors is introduced. Finally, the future development prospects and shortcomings of this nanogenerator are discussed.

Preparation of nanocellulose and its applications in wound dressing: A review.

Nanocellulose, as a nanoscale polymer material, has garnered significant attention worldwide due to its numerous advantages including excellent biocompatibility, thermal stability, non-toxicity, large specific surface area, and good hydrophilicity. Various methods can be employed for the preparation of nanocellulose. Traditional approaches such as mechanical, chemical, and biological methods possess their own distinct characteristics and limitations. However, with the growing deterioration of our living environment, several green and environmentally friendly preparation techniques have emerged. These novel approaches adopt eco-friendly technologies or employ green reagents to achieve environmental sustainability. Simultaneously, there is a current research focus on optimizing traditional nanocellulose preparation methods while addressing their inherent drawbacks. The combination of mechanical and chemical methods compensates for the limitations associated with using either method alone. Nanocellulose is widely used in wound dressings owing to its exceptional properties, which can accelerate the wound healing process and reduce patient discomfort. In this paper, the principle, advantages and disadvantages of each preparation method of nanocellulose and the research findings in recent years are introduced Moreover, this review provides an overview of the utilization of nanocellulose in wound dressing applications. Finally, the prospective trends in its development alongside corresponding preparation techniques are discussed.

Chemo- and Regioselective Alkylation of Pyridine N-Oxides with Titanacyclopropanes.

While titanacyclopropanes are used to react mainly with ester, amide, and cyano to undergo cyclopropanation, herein they react preferentially with pyridine N-oxide to accomplish C2-H alkylation beyond these functionalities with double regioselectivity. After being pyridylated at the less hindered C-Ti bond, the remaining C-Ti bond of titanacyclopropanes can be further functionalized by various electrophiles, allowing facile introduction of complex alkyls onto the C2 of pyridines. Its synthetic potential has been demonstrated by late-stage diversification of drugs.

High Rate Performance Supercapacitors Based on N, O Co-Doped Hierarchical Porous Carbon Foams Synthesized via Chemical Blowing and Dual Templates.

N, O Co-Doped porous carbon materials are promising electrode materials for supercapacitors. However, it is still a challenge to prepare high capacitance performance N, O Co-Doped porous carbon materials with balanced pore structure. In this work, a simple chemical blowing method was developed to produce hierarchal porous carbon materials with Zn(NO3)2·6H2O and Fe(NO3)3·9H2O as the foaming agents and precursors of dual templates. Soybean protein isolate served as a self-doping carbon source. The amount of Fe(NO3)3·9H2O influenced the microstructure, element content and capacitance performance of the obtained porous carbon materials. The optimized sample CZnFe-5 with the addition of 5% Fe(NO3)3·9H2O displayed the best capacitance performance. The specific capacitance reached 271 F g-1 at 0.2 A g-1 and retained 133 F g-1 at 100 A g-1. The CZnFe-5//CZnFe-5 symmetric supercapacitors delivered a maximum energy density of 16.83 Wh kg-1 and good stability with capacitance retention of 86.33% after 40,000 cycles tests at 50 A g-1. The symmetric supercapacitors exhibited potential applications in lighting LED bulbs with a voltage of 3 V. This work provides a new strategy for the synthesis of hierarchical porous carbon materials for supercapacitors from low-cost biomass products.

Platinum-palladium-on-reduced graphene oxide as bifunctional electrocatalysts for highly active and stable hydrogen evolution and methanol oxidation reaction.

In the context of the gradual depletion of global fossil fuel resources, it is increasingly necessary to explore new alternative energy. Hydrogen energy has attracted great interest from researchers because of its green and pollution-free characteristics. Moreover, the methanol oxidation reaction (MOR) can combine the hydrogen evolution reaction (HER), replacing the anode reaction (oxygen evolution reaction-OER) in overall water splitting and efficiently producing hydrogen. In this study, platinum-palladium nanoparticles on reduced graphene oxide (PtPd/rGO) were successfully synthesized as HER and MOR bifunctional electrocatalysts under alkaline conditions by the stepwise loading of Pt and Pd bimetallic nanoparticles on rGO using a simple liquid-phase reduction method. PtPd/rGO-2 with 0.99 wt% Pt and 2.86 wt% Pd in the HER has the lowest overpotential (87.16 mV at 100 mA cm-2), with the smallest Tafel slope (18.9 mV dec-1). The exceptional mass activity of PtPd/rGO-2 in the MOR reaches 10.75 A mg-1PtPd, which is 18.22 and 53.75 times greater than that of commercial Pt/C (Pt/C) and commercial Pd/C (Pd/C), respectively. PtPd/rGO-2 is 0.935 V lower in the coupling reaction of HER and MOR (MOR ∥ HER) compared to the overall water splitting (OER ∥ HER) without methanol (10 mA cm-2). This is probably because appropriate Pt and Pd loading exposes many more catalytic sites, and the synergistic interaction between Pt, Pd, and Pt-Pd enhances the catalytic performance. This strategy can be used for the synthesis of novel bifunctional electrocatalysts.

Small extrachromosomal circular DNA harboring targeted tumor suppressor gene mutations supports intratumor heterogeneity in mouse liver cancer induced by multiplexed CRISPR/Cas9.

BACKGROUND: Primary liver cancer has significant intratumor genetic heterogeneity (IGH), which drives cancer evolution and prevents effective cancer treatment. CRISPR/Cas9-induced mouse liver cancer models can be used to elucidate how IGH is developed. However, as CRISPR/Cas9 could induce chromothripsis and extrachromosomal DNA in cells in addition to targeted mutations, we wondered whether this effect contributes to the development of IGH in CRISPR/Cas9-induced mouse liver cancer. METHODS: CRISPR/Cas9-based targeted somatic multiplex-mutagenesis was used to target 34 tumor suppressor genes (TSGs) for induction of primary liver tumors in mice. Target site mutations in tumor cells were analyzed and compared between single-cell clones and their subclones, between different time points of cell proliferation, and between parental clones and single-cell clones derived from mouse subcutaneous allografts. Genomic instability and generation of extrachromosomal circular DNA (eccDNA) was explored as a potential mechanism underlying the oscillation of target site mutations in these liver tumor cells. RESULTS: After efficiently inducing autochthonous liver tumors in mice within 30-60 days, analyses of CRISPR/Cas9-induced tumors and single-cell clones derived from tumor nodules revealed multiplexed and heterogeneous mutations at target sites. Many target sites frequently displayed more than two types of allelic variations with varying frequencies in single-cell clones, indicating increased copy number of these target sites. The types and frequencies of targeted TSG mutations continued to change at some target sites between single-cell clones and their subclones. Even the proliferation of a subclone in cell culture and in mouse subcutaneous graft altered the types and frequencies of targeted TSG mutations in the absence of continuing CRISPR/Cas9 genome editing, indicating a new source outside primary chromosomes for the development of IGH in these liver tumors. Karyotyping of tumor cells revealed genomic instability in these cells manifested by high levels of micronuclei and chromosomal aberrations including chromosomal fragments and chromosomal breaks. Sequencing analysis further demonstrated the generation of eccDNA harboring targeted TSG mutations in these tumor cells. CONCLUSIONS: Small eccDNAs carrying TSG mutations may serve as an important source supporting intratumor heterogeneity and tumor evolution in mouse liver cancer induced by multiplexed CRISPR/Cas9.

Rhodamine-Anchored Polyacrylamide Hydrogel for Fluorescent Naked-Eye Sensing of Fe3.

A fluorescent and colorimetric poly (acrylamide)-based copolymer probe P(AAm-co-RBNCH) has been designed via free radical polymerization of a commercial acrylamide monomer with a rhodamine-functionalized monomer RBNCH. Metal ion selectivity of RBNCH was investigated by fluorescence and colorimetric spectrophotometry. Upon addition of Fe3+, a visual color change from colorless to red and a large fluorescence enhancement were observed for the ring-opening of the rhodamine spirolactam mechanism. The monomer gives a sensitive method for quantitatively detecting Fe3+ in the linear range of 100-200 µM, with a limit of detection as low as 27 nM and exhibiting high selectivity for Fe3+ over 12 other metal ions. The hydrogel sensor was characterized by FTIR, and the effects of RBNCH amount on gel content and swelling properties were explored. According to the recipe of 1.0 mol% RBNCH to the total monomers, the fabricated hydrogel sensor displayed a good swelling property and reversibility performance and has potential for application in the imaging of Fe3+ level in industrial wastewater.

Constructing High-Performance Ternary Device Using Analogous Polymer Donors.

Both ternary copolymerization and ternary blending are effective methods to fine-tune polymer structure and manipulate thin-film morphology to improve device performance. In this work, three D-A-A-A (D: donor, A: acceptor) terpolymer donors (FY1, FY2, and FY3) are synthesized by introducing BDD (1,3-bis(2-ethylhexyl)-5,7-di(thiophen-2-yl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione) units into the D-A alternating copolymer PM6 backbone. Owing to the promoted conjugated planarity and excellent absorption of BDD, the obtained terpolymers display an extended absorption range and enhanced π-π stacking orientation, which is a promising third component in ternary device. As a result, the optimal FY1:PM6:BTP-eC9-based ternary device afforded an impressive power conversion efficiency (PCE) as high as 18.52%, owing to the efficient charge transport, negligible energy loss, and suitable domain size. The result provides an efficient method to obtain high-performance polymer solar cells by using analogous polymer donors in ternary device.

Nanocellulose-based composite aerogels toward the environmental protection: Preparation, modification and applications.

Nanocellulose aerogel has the advantages of porosity, low density and high specific surface area, which can effectively realize the adsorption and treatment of wastewater waste gas. The methods of preparing nanocellulose mainly include mechanical, chemical and biological methods. Nanocellulose is formed into nanocellulose aerogel after gelation, solvent replacement and drying processes. Based on the advantages of easy modification of nanocellulose aerogels, nanocellulose aerogels can be functionalized with conductive fillers, reinforcing fillers and other materials to give nanocellulose aerogels in electrical, mechanical and other properties. Through functionalization, the properties of nanocellulose composite aerogel such as hydrophobicity and adsorption are improved, and the aerogel is endowed with the ability of electrical conductivity and electromagnetic shielding. Through functionalization, the applicability and general applicability of nanocellulose composite aerogel in the field of environmental protection are improved. In this paper, the preparation and functional modification methods of nanocellulose aerogels are reviewed, and the application prospects of nanocellulose composite aerogels in common environmental protection fields such as dye adsorption, heavy metal ion adsorption, gas adsorption, electromagnetic shielding, and oil-water separation are specifically reviewed, and new solutions are proposed.

A "turn-on" ESIPT fluorescence probe of 2-(aminocarbonyl)phenylboronic acid for the selective detection of Cu(ii).

Herein, we report a highly selective fluorescent probe for the detection of Cu(ii). The detection mechanism relies on the Cu(ii)-catalyzed oxidative hydroxylation of 2-(aminocarbonyl)phenylboronic acid into salicylamide, thus recovering the excited-state intramolecular proton transfer (ESIPT) effect and inducing more than 35-fold fluorescence enhancement. The simple structure and readily available fluorescent probe give a novel method for quantitatively detecting Cu(ii) in the linear range of 0-22 µM, with a limit of detection down to 68 nM, and exhibiting high selectivity for Cu(ii) over 16 other metal ions.

Terpolymerization strategy to achieve high-efficiency organic solar cells via construction of D1-A-D1-D2-type polymer donors.

Novel terpolymers were developed with ester group incorporation (BDT-2EST). DM1 with 5% BDT-2EST possesses suitable crystallinity and miscibility matching with Y6 acceptor to offer an excellent power conversation efficiency up to 17.21%. Moreover, the intertwined random features in DM1 offer robust photovoltaic performances with a broad molecular weight tolerance.

Source of Nanocellulose and Its Application in Nanocomposite Packaging Material: A Review.

Food packaging nowadays is not only essential to preserve food from being contaminated and damaged, but also to comply with science develop and technology advances. New functional packaging materials with degradable features will become a hot spot in the future. By far, plastic is the most common packaging material, but plastic waste has caused immeasurable damage to the environment. Cellulose known as a kind of material with large output, wide range sources, and biodegradable features has gotten more and more attention. Cellulose-based materials possess better degradability compared with traditional packaging materials. With such advantages above, cellulose was gradually introduced into packaging field. It is vital to make packaging materials achieve protection, storage, transportation, market, and other functions in the circulation process. In addition, it satisfied the practical value such as convenient sale and environmental protection, reduced cost and maximized sales profit. This review introduces the cellulose resource and its application in composite packaging materials, antibacterial active packaging materials, and intelligent packaging materials. Subsequently, sustainable packaging and its improvement for packaging applications were introduced. Finally, the future challenges and possible solution were provided for future development of cellulose-based composite packaging materials.

Incorporation of Al2O3, GO, and Al2O3@GO nanoparticles into water-borne epoxy coatings: abrasion and corrosion resistance.

Nano-Al2O3 particles and graphene oxide (GO) nanosheets were modified by 3-aminopropyltriethoxysilane (KH550), and then dispersed in epoxy resin, and finally modified-Al2O3/epoxy, modified-GO/epoxy and modified-Al2O3@GO/epoxy composite coatings were prepared on steel sheets by the scraping stick method. The microstructure, phase identification, surface bonding and composition of the nanoparticles were characterized by SEM, XRD, FT-IR, and Raman spectroscopy, respectively. The hardness of the coating was assessed by the pencil hardness method. The abrasion resistance of the coating was tested by a sand washing machine. The corrosion resistance of the coating was assessed using salt spray, a long-period immersion test, potentiodynamic polarization curves and electrochemical impedance spectra. With the addition of a small amount of nanoparticles, the dispersion of nanoparticles in the epoxy resin was good. When the content of nano-Al2O3 particles was equal to 1.5 wt%, the particles in the epoxy exhibited the best dispersion and stability. However, the GO and Al2O3@GO nanofillers in the epoxy resin exhibited poor dispersion and stability. The hardness, abrasion and corrosion resistance of the composite coatings were improved with the addition of a small amount of nanoparticles, but the performance began to decline after exceeding a certain content range of the nanoparticles. A relatively good abrasion resistance for the coatings was obtained when the content of Al2O3, GO and Al2O3@GO after modification was 1.5 wt%, 0.2 wt% and 0.4 wt%, respectively. The corrosion resistance of the coatings doped with nano-Al2O3 particles was better than that of the coatings incorporating GO nanosheets and Al2O3@GO hybrids. The corrosion mechanism of the composite coatings in 3.5 wt% NaCl solution was addressed and studied.

DNA nicks induce mutational signatures associated with BRCA1 deficiency.

Analysis of human cancer genome sequences has revealed specific mutational signatures associated with BRCA1-deficient tumors, but the underlying mechanisms remain poorly understood. Here, we show that one-ended DNA double strand breaks (DSBs) converted from CRISPR/Cas9-induced nicks by DNA replication, not two-ended DSBs, cause more characteristic chromosomal aberrations and micronuclei in Brca1-deficient cells than in wild-type cells. BRCA1 is required for efficient homologous recombination of these nick-converted DSBs and suppresses bias towards long tract gene conversion and tandem duplication (TD) mediated by two-round strand invasion in a replication strand asymmetry. However, aberrant repair of these nick-converted one-ended DSBs, not that of two-ended DSBs in Brca1-deficient cells, generates mutational signatures such as small indels with microhomology (MH) at the junctions, translocations and small MH-mediated TDs, resembling those in BRCA1-deficient tumors. These results suggest a major contribution of DNA nicks to mutational signatures associated with BRCA1 deficiency in cancer and the underlying mechanisms.

Facile Electrodeposition of NiCo2O4 Nanosheets on Porous Carbonized Wood for Wood-Derived Asymmetric Supercapacitors.

Multichannel-porous carbon derived from wood can serve as a conductive substrate for fast charge transfer and ion diffusion, supporting the high-theory capacitance of pseudocapacitive materials. Herein, NiCo2O4 nanosheets, which are hierarchically porous, anchored on the surface of carbonized wood via electrodeposition for free-binder high-performance supercapacitor electrode materials, were proposed. Benefiting from the effectively alleviated NiCo2O4 nanosheets accumulation and sufficient active surface area for redox reaction, a N-doped wood-derived porous carbon-NiCo2O4 nanosheet hybrid material (NCNS-NCW) electrode exhibited a specific electric capacity of 1730 F g-1 at 1 A g-1 in 1 mol L-1 KOH and splendid electrochemical firmness with 80% capacitance retention after cycles. Furthermore, an all-wood-based asymmetric supercapacitor based on NCNS-NCW//NCW was assembled and a high energy density of 56.1 Wh kg-1 at a watt density of 349 W kg-1 was achieved. Due to the great electrochemical performance of NCNS-NCW, we expect it to be used as an electrode material with great promise for energy storage equipment.

Wood-Derived High-Mass-Loading MnO2 Composite Carbon Electrode Enabling High Energy Density and High-Rate Supercapacitor.

The simple design of a high-energy-density device with high-mass-loading electrode has attracted much attention but is challenging. Manganese oxide (MnO2 ) with its low cost and excellent electrochemical performance shows high potential for practical application in this regard. Hence, the high-mass-loading of the MnO2 electrode with wood-derived carbon (WC) as the current collector is reported through a convenient hydrothermal reaction for high-energy-density devices. Benefiting from the high-mass-loading of the MnO2 electrode (WC@MnO2 -20, ≈14.1 mg cm-2 ) and abundant active sites on the surface of the WC hierarchically porous structure, the WC@MnO2 -20 electrode shows remarkable high-rate performance of areal/specific capacitance ≈1.56 F cm-2 /45 F g-1 , compared to the WC electrode even at the high density of 20 mA cm-2 . Furthermore, the obtained symmetric supercapacitor exhibits high areal/specific capacitances of 3.62 F cm-2 and 87 F g-1 at 1.0 mA cm-2 and high energy densities of 0.502 mWh cm-2 /12.2 Wh kg-1 with capacitance retention of 75.2% after 10 000 long-term cycles at 20 mA cm-2 . This result sheds light on a feasible design strategy for high-energy-density supercapacitors with the appropriate mass loading of active materials and low-tortuosity structural design while also encouraging further investigation into electrochemical storage.

Anisotropic cellulose nanofibril composite sponges for electromagnetic interference shielding with low reflection loss.

With the development of the electronic industry bringing convenience to people, a series of caused electromagnetic pollution problems (e.g., electromagnetic interference (EMI)) have recently also become urgent tasks. In this work, an anisotropic composite sponge consisting of cellulose nanofibrils (CNFs) and chemical co-precipitated silver nanowire (AgNW)@Fe3O4 composites was successfully prepared. Due to the introduction of anisotropic structures and the synergistic effect among CNFs, AgNWs, and Fe3O4, this composite sponge exhibited low density (16.76 mg/cm3), good saturation magnetization (4.21 emu/g) and electrical conductivity (0.02 S/cm), and anisotropic EMI shielding ability. By adjusting the proportion (1:0.3) between AgNWs and Fe3O4 and their loading (0.15 vol%) inside the sponge, the reflection loss of the sponge with the improved interface impedance mismatch was only 2.3 dB, accounting for 7.2% of the total loss. It is expected to become a promising EMI shielding material, especially for effectively alleviating the secondary reflection EM pollution.

Liquid Transport and Real-Time Dye Purification via Lotus Petiole-Inspired Long-Range-Ordered Anisotropic Cellulose Nanofibril Aerogels.

Nowadays, large-scale oriented functional porous materials have been sought after by researchers. However, regulation of the long-range uniform and oriented structures of the material remains a challenge. Herein, ultralong anisotropic cellulose nanofibril (CNF) aerogels with uniformly ordered structures of pore walls inspired by lotus petioles were constructed by applying external speeds to counterbalance the growth driving forces of ice crystals. Based on the growth law of ice crystals, the ice crystals grew at a stable rate when the applied external speed was 0.04 mm/s, ensuring the consistent orientation of the large-scale CNF aerogel. The aerogel exhibited a rapid long-range directional transport ability to different liquid solvents, delivering ethanol up to 40 mm from bottom to top within 50 s. Moreover, by introducing rectorites with good cation-exchange properties, the resulting long-range composite possessed an enhanced adsorption capacity for methylene blue. Furthermore, aerogel successfully achieved real-time dye purification at a long distance, such as fast dye adsorption or selective adsorption. This flexible and straightforward strategy of fabricating ultralong oriented CNF aerogel materials is expected to promote the development of functional aerogels in directional liquid transport and sewage treatment.