Stabilizing High-Valence Copper(I) Sites with Cu-Ni Interfaces Enhances Electroreduction of CO2 to C2+ Products.

In this study, the copper-nickel (Cu-Ni) bimetallic electrocatalysts for electrochemical CO2 reduction reaction(CO2RR) are fabricated by taking the finely designed poly(ionic liquids) (PIL) containing abundant Salen and imidazolium chelating sites as the surficial layer, wherein Cu-Ni, PIL-Cu and PIL-Ni interaction can be readily regulated by different synthetic scheme. As a proof of concept, Cu@Salen-PIL@Ni(NO3)2 and Cu@Salen-PIL(Ni) hybrids differ significantly in the types and distribution of Ni species and Cu species at the surface, thereby delivering distinct Cu-Ni cooperation fashion for the CO2RR. Remarkably, Cu@Salen-PIL@Ni(NO3)2 provides a C2+ faradaic efficiency (FEC2+) of 80.9% with partial current density (jC 2+) of 262.9 mA cm-2 at -0.80 V (versus reversible hydrogen electrode, RHE) in 1 m KOH in a flow cell, while Cu@Salen-PIL(Ni) delivers the optimal FEC2+ of 63.8% at jC2+ of 146.7 mA cm-2 at -0.78 V. Mechanistic studies indicates that the presence of Cu-Ni interfaces in Cu@Salen-PIL@Ni(NO3)2 accounts for the preserve of high-valence Cu(I) species under CO2RR conditions. It results in a high activity of both CO2-to-CO conversion and C-C coupling while inhibition of the competitive HER.

Biogenic Solution Map Based on the Definition of the Metabolic Correlation Distance between 4-Dimensional Fingerprints.

Accurate discrimination and classification of unknown species are the basis to predict its characteristics or applications to make correct decisions. However, for biogenic solutions that are ubiquitous in nature and our daily lives, direct determination of their similarities and disparities by their molecular compositions remains a scientific challenge. Here, we explore a standard and visualizable ontology, termed "biogenic solution map", that organizes multifarious classes of biogenic solutions into a map of hierarchical structures. To build the map, a novel 4-dimensional (4D) fingerprinting method based on data-independent acquisition data sets of untargeted metabolomics is developed, enabling accurate characterization of complex biogenic solutions. A generic parameter of metabolic correlation distance, calculated based on averaged similarities between 4D fingerprints of sample groups, is able to define "species", "genus", and "family" of each solution in the map. With the help of the "biogenic solution map", species of unknown biogenic solutions can be explicitly defined. Simultaneously, intrinsic correlations and subtle variations among biogenic solutions in the map are accurately illustrated. Moreover, it is worth mentioning that samples of the same analyte but prepared by alternative protocols may have significantly different metabolic compositions and could be classified into different "genera".

Self-Healing, Adhesive, and Highly Stretchable Ionogel as a Strain Sensor for Extremely Large Deformation.

Fabricating a strain sensor that can detect large deformation over a curved object with a high sensitivity is crucial in wearable electronics, human/machine interfaces, and soft robotics. Herein, an ionogel nanocomposite is presented for this purpose. Tuning the composition of the ionogel nanocomposites allows the attainment of the best features, such as excellent self-healing (>95% healing efficiency), strong adhesion (347.3 N m-1 ), high stretchability (2000%), and more than ten times change in resistance under stretching. Furthermore, the ionogel nanocomposite-based sensor exhibits good reliability and excellent durability after 500 cycles, as well as a large gauge factor of 20 when it is stretched under a strain of 800-1400%. Moreover, the nanocomposite can self-heal under arduous conditions, such as a temperature as low as -20 °C and a temperature as high as 60 °C. All these merits are achieved mainly due to the integration of dynamic metal coordination bonds inside a loosely cross-linked network of ionogel nanocomposite doped with Fe3 O4 nanoparticles.

Dual-Physical Cross-Linked Tough and Photoluminescent Hydrogels with Good Biocompatibility and Antibacterial Activity.

Development of novel photoluminescent hydrogels with toughness, biocompatibility, and antibiosis is important for the applications in biomedical field. Herein, novel tough photoluminescent lanthanide (Ln)-alginate/poly(vinyl alcohol) (PVA) hydrogels with the properties of biocompatibility and antibiosis have been facilely synthesized by introducing hydrogen bonds and coordination bonds into the interpenetrating networks of Na-alginate and PVA, via approaches of frozen-thawing and ion-exchanging. The resultant hydrogels exhibit high mechanical strength (0.6 MPa tensile strength, 5.0 tensile strain, 6.0 MPa compressive strength, and 900 kJ m-3 energy dissipation under 400% stretch), good photoluminescence as well as biocompatibility and antibacterial activity. The design strategy provides a new avenue for the fabrication of multifunctional photoluminescent hydrogels based on biocompatible polymers.

Fe3 O4 Anisotropic Nanostructures in Hydrogels: Efficient Catalysts for the Rapid Removal of Organic Dyes from Wastewater.

Fe3 O4 anisotropic nanostructures that exhibit excellent catalytic performance are rarely used to catalyze Fenton-like reactions because of the inevitable drawbacks resulting from traditional preparation methods. In this study, a facile, nontoxic, water-based approach is developed for directly regulating a series of anisotropic morphologies of Fe3 O4 nanostructures in a hydrogel matrix. In having the advantages of both the catalytic activity of Fe3 O4 and the adsorptive capacity of an anionic polymer network, the hybrid nanocomposites have the capability to effect the rapid removal of cationic dyes, such as methylene blue, from water samples. Perhaps more interestingly, hybrid nanocomposites loaded with Fe3 O4 nanorods exhibit the highest catalytic activity compared to those composed of nanoneedles and nanooctahedra, revealing the important role of nanostructure morphology. By means of scanning electrochemical microscopy, it is revealed that Fe3 O4 nanorods can efficiently catalyze H2 O2 decomposition and thus generate more free radicals ((.) OH, (.) HO2 ) for methylene blue degradation, which might account for their high catalytic activity.

Exceptionally tough and notch-insensitive magnetic hydrogels.

Most existing magnetic hydrogels are weak and brittle. The development of strong and tough magnetic hydrogels would extend their applications into uncultivated areas, such as in actuators for soft machines and guided catheters for magnetic navigation systems, which is still a big challenge. Here a facile and versatile approach to fabricating highly stretchable, exceptionally tough and notch-insensitive magnetic hydrogels, Fe(3)O(4)@Fe-alginate/polyacrylamide (PAAm), is developed, by dispersing alginate-coated Fe(3)O(4) nanoparticles into the interpenetrating polymer networks of alginate and PAAm, with hybrid physical and chemical crosslinks. A cantilever bending beam actuator as well as a proof-of-concept magnetically guided hydrogel catheter is demonstrated. The method proposed in this work can be integrated into other strong and tough magnetic hydrogels for the development of novel hydrogel nanocomposites with both desirable functionality and superior mechanical properties.

Tough photoluminescent hydrogels doped with lanthanide.

Photoluminescent hydrogels have emerged as novel soft materials with potential applications in many fields. Although many photoluminescent hydrogels have been fabricated, their scope of usage has been severely limited by their poor mechanical performance. Here, a facile strategy is reported for preparing lanthanide (Ln)-alginate/polyacrylamide (PAAm) hydrogels with both high toughness and photoluminescence, which has been achieved by doping Ln(3+) ions (Ln = Eu, Tb, Eu/Tb) into alginate/PAAm hydrogel networks, where Ln(3+) ions serve as both photoluminescent emitters and physical cross-linkers. The resulting hydrogels exhibit versatile advantages including excellent mechanical properties (∼ MPa strength, ≈ 20 tensile strains, ≈ 10(4) kJ m(-3) energy dissipation), good photoluminescent performance, tunable emission color, excellent processability, and cytocompatibility. The developed tough photoluminescent hydrogels hold great promises for expanding the usage scope of hydrogels.

Self-healing gels based on constitutional dynamic chemistry and their potential applications.

As representative soft materials with widespread applications, gels with various functions have been developed. However, traditional gels are vulnerable to stress-induced formation of cracks. The propagation of these cracks may affect the integrity of network structures of gels, resulting in the loss of functionality and limiting the service life of the gels. To address this challenge, self-healing gels that can restore their functionalities and structures after damage have been developed as "smart" soft materials. In this paper, we present an overview of the current strategies for synthesizing self-healing gels based on the concept of constitutional dynamic chemistry, which involves molecular structures capable of establishing dynamic networks based upon physical interactions or chemical reactions. The characterization methods of self-healing gels and the key factors that affect self-healing properties are analyzed. We also illustrate the emerging applications of self-healing gels, with emphasis on their usage in industry (coatings, sealants) and biomedicine (tissue adhesives, agents for drug or cell delivery). We conclude with a perspective on challenges facing the field, along with prospects for future development.

cDNA cloning and localization of Sp3111 (also called Ms4a14) in the rat testis.

With tetraspanning topology, members of the membrane-spanning four-domain subfamily A (MS4A) may facilitate signaling or ion channel functions in many tissues. In this study, we report the cloning of a full-length cDNA from rat testis, designated Ms4a14 (Sp3111), which encodes the MS4A protein with 1139 amino acid residues. In situ hybridization and immunohistochemical analyses indicate that Ms4a14 is predominantly expressed from round spermatids to spermatozoa at specific stages in the rat testis at both the mRNA and protein level. Immunofluorescence analysis revealed that MS4A14 (SP3111) is located in the acrosome and the midpiece of the flagellum in mature sperm. Previously, we explored and reported the involvement of MS4A14 in reproductive functions, using antibody blockage during IVF and a transgenic RNA interference method in a mouse model. Our results suggested that MS4A14 is involved in fertilization and zygote division. As MS4A14 protein exists in mammals, such as humans, cows, dogs, and rodents, MS4A14 may play a ubiquitous role in mammalian reproduction.

Tough, self-healing and injectable dynamic nanocomposite hydrogel based on gelatin and sodium alginate.

Biomacromolecules based injectable and self-healing hydrogels possessing high mechanical properties have widespread potential in biomedical field. However, dynamic features are usually inversely proportional to toughness. It is challenging to simultaneously endow these properties to the dynamic hydrogels. Here, we fabricated an injectable nanocomposite hydrogel (CS-NPs@OSA-l-Gtn) stimultaneously possessing excellent autonomous self-healing performance and high mechanical strength by doping chitosan nanoparticles (CS-NPs) into dynamic polymer networks of oxidized sodium alginate (OSA) and gelatin (Gtn) in the presence of borax. The synergistic effect of the multiple reversible interactions combining dynamic covalent bonds (i.e., imine bond and borate ester bond) and noncovalent interactions (i.e., electrostatic interaction and hydrogen bond) provide effective energy dissipation to endure high fatigue resistance and cyclic loading. The dynamic hydrogel exhibited excellent mechanical properties like maximum 2.43 MPa compressive strength, 493.91 % fracture strain, and 89.54 kJ/m3 toughness. Moreover, the integrated hydrogel after injection and self-healing could withstand 150 successive compressive cycles. Besides, the bovine serum albumin embedded in CS-NPs could be sustainably released from the nanocomposite hydrogel for 12 days. This study proposes a novel strategy to synthesize an injectable and self-healing hydrogel combined with excellent mechanical properties for designing high-strength natural carriers with sustained protein delivery.

Mussel inspired sequential protein delivery based on self-healing injectable nanocomposite hydrogel.

Polysaccharide based self-healing and injectable hydrogels with reversible characteristics have widespread potential in protein drug delivery. However, it is a challenge to design the dynamic hydrogel for sequential release of protein drugs. Herein, we developed a novel mussel inspired sequential protein delivery dynamic polysaccharide hydrogel. The nanocomposite hydrogel can be fabricated through doping polydopamine nanoparticles (PDA NPs) into reversible covalent bond (imine bonds) crosslinked polymer networks of oxidized hyaluronic acid (OHA) and carboxymethyl chitosan (CEC), named PDA NPs@OHA-l-CEC. Besides multiple capabilities (i.e., injection, self-healing, and biodegradability), the nanocomposite hydrogel can achieve sustained and sequential protein delivery of vascular endothelial growth factor (VEGF) and bovine serum albumin (BSA). PDA NPs doped in hydrogel matrix serve dual roles, acting as secondary protein release structures and form dynamic non-covalent interactions (i.e., hydrogen bonds) with polysaccharides. Moreover, by adjusting the oxidation degree of OHA, the hydrogels with different crosslinking density could control overall protein release rate. Analysis of different release kinetic models revealed that Fickian diffusion drove rapid VEGF release, while the slower BSA release followed a Super Case II transport mechanism. The novel biocompatible system achieved sequential release of protein drugs has potentials in multi-stage synergistic drug deliver based on dynamic hydrogel.

Recent Advances in Biopolymer-Based Hydrogel Electrolytes for Flexible Supercapacitors.

Growing concern regarding the impact of fossil fuels has led to demands for the development of green and renewable materials for advanced electrochemical energy storage devices. Biopolymers with unique hierarchical structures and physicochemical properties, serving as an appealing platform for the advancement of sustainable energy, have found widespread application in the gel electrolytes of supercapacitors. In this Review, we outline the structure and characteristics of various biopolymers, discuss the proposed mechanisms and assess the evaluation metrics of gel electrolytes in supercapacitor devices, and further analyze the roles of biopolymer materials in this context. The state-of-the-art electrochemical performance of biopolymer-based hydrogel electrolytes for supercapacitors and their multiple functionalities are summarized, while underscoring the current technical challenges and potential solutions. This Review is intended to offer a thorough overview of recent developments in biopolymer-based hydrogel electrolytes, highlighting research concerning green and sustainable energy storage devices and potential avenues for further development.

Dextran-based self-healing hydrogels formed by reversible diels-alder reaction under physiological conditions.

A dextran-based self-healing hydrogel is prepared by reversible Diels-Alder reaction under physiological conditions. Cytocompatible fulvene-modified dextran as main polymer chains and dichloromaleic-acid-modified poly(ethylene glycol) as cross-linkers are used. Both macro- and microscopic observation as well as the rheological recovery test confirm the self-healing property of the dextran-l-poly(ethylene glycol) hydrogels ("l" means "linked-by"). In addition, scanning electrochemical microscopy is used to qualitatively and quantitatively in situ track the self-healing process of the hydrogel for the first time. It is found that the longitudinal depth of scratch on hydrogel surface almost completely healed at 37 °C after 7 h. This work represents a facile approach for fabrication of polysaccharide self-healing hydrogel, which can be potentially used in several biomedical fields.

Tough, durable and saline-tolerant CNT@Gel-nacre nanocomposite for interfacial solar steam generation.

Solar-driven interfacial evaporation materials based on nanocomposite hydrogels have emerged for seawater desalination. Nevertheless, the issue of mechanical degradation derived from the swelling behavior of hydrogel is often seriously underestimated, which strongly hinders the practical application for long-term solar vapor generation, especially in high-salinity brine. Herein, a novel CNT@Gel-nacre with enhanced capillary pumping design has been proposed and fabricated for tough and durable solar-driven evaporator through uniformly doping carbon nanotubes (CNTs) into the tough gel-nacre. Particularly, the salting out process gives rise to volume shrinkage and phase separation of polymer chains, endowing the nanocomposite hydrogel with significantly enhanced mechanical properties while simultaneously rendering more compact microchannels for water transportation, boosting the capillary pumping. Based on this unique design, the gel-nacre nanocomposite exhibits outstanding mechanical performances (13.41 MPa strength, 55.60 MJ m-3 toughness), especially mechanical durability in high salinity brine for long-term service. Furthermore, excellent water evaporation rate of 1.31 kg m-2h-1 and conversion efficiency of 93.5% in 3.5 wt% sodium chloride solution, as well as stable cycling without salt accumulation can be achieved. This work demonstrates an effective strategy for achieving solar-driven evaporator with superior mechanical properties and durability even in brine environment, showing huge potentials in long-term seawater desalination.

Hyaluronic acid and chitosan-based injectable and self-healing hydrogel with inherent antibacterial and antioxidant bioactivities.

Injectable dressings offering intrinsic antibacterial activity and antioxidation are required, because persistent bacterial infection and oxidative damage are common issues associated with chronic non-healing wounds. Herein, a versatile QCS-l-TA-l-OHA hydrogel is fabricated using ubiquitous nature derived biological macromolecules, quaternized chitosan (QCS), tannic acid (TA) and oxidant hyaluronic acid (OHA), driving by multiple dynamic interactions under physiological conditions. The hydrogel can serve as multiple functional wound dress with injectable and self-healing capabilities coupling with attractive antibacterial activity and antioxidation. The biocompatible and self-biodegradable hydrogel augments free radical scavenging capacity, antibacterial, angiogenesis, mature granulation tissue and collagen disposition, enabling fast wound healing of rat skin full-thickness incision model. This study highlights a wound dressing platform of hyaluronic acid and chitosan based injectable and self-healing hydrogel with inherent antibacterial and antioxidant bioactivities, thereby avoiding the use of antibiotics or antioxidant agents.

Covalent Organic Frameworks Boost the Silver-Electrocatalyzed Reduction of CO2: The Electronic and Confinement Effect.

The electrocatalytic reduction of CO2 to CO with high efficiency is one of the most promising approaches for CO2 conversion due to its considerable economic feasibility and broad application prospects. In this study, three Ag@COF-R (R = -H, -OCH3, -OH) hybrids were facilely fabricated by impregnating silver acetate (AgOAc) into respective covalent organic frameworks (COFs) prepared in advance. They differ significantly in the crystallinity, porosity, distribution, size, and electronic configuration of AgOAc species, which thereby influences both the activity and the selectivity of electrolytic CO2-to-CO transformation. Impressively, Ag@COF-OCH3 provided a high FECO of 93.0% with a high jCO of 213.9 mA cm-2 at -0.87 V (vs reversible hydrogen electrode, RHE) in 1 M KOH using a flow cell. In addition, it exhibited long-term durability at 100 mA cm-2 for 30 h.

Dynamic and self-biodegradable polysaccharide hydrogel stores embryonic stem cell construct under ambient condition.

The proper microenvironment is critical for the storage and transportation of embryonic stem cells (ESCs). To mimic a dynamic 3D microenvironment as it exists in vivo and consider "off-the-shelf" availability reaching the destination, we proposed an alternative approach that allows for facile storage and transportation of stem cells in the form of ESCs-dynamic hydrogel construct (CDHC) under ambient conditions. To form CDHC, mouse embryonic stem cells (mESCs) were in-situ encapsulated within a polysaccharide-based dynamic and self-biodegradable hydrogel. After storing CDHC in a sterile and hermetic environment for 3 days and then transferring to a sealed vessel with fresh medium for another 3 days, the large and compact colonies retained a 90% survival rate and pluripotency. Furthermore, after transporting and arriving at the destination, the encapsulated stem cell could be automatically released from the self-biodegradable hydrogel. After continuous cultivation of 15 generations of retrieved cells, automatically released from the CDHC, the mESCs underwent 3D encapsulation, storage, transportation, release, and continuous long-term subculture; resumed colony forming capacity and pluripotency were revealed by stem cell markers both in protein and mRNA levels. We believe that the dynamic and self-biodegradable hydrogel provides a simple, cost-effective, and valuable tool for storing and transporting "ready-to-use" CDHC under ambient conditions, facilitating "off-the-shelf" availability and widespread applications.

Novel phosphorescent hydrogels based on an Ir(III) metal complex.

Novel phosphorescent hydrogels have been explored by immobilizing an Ir(III) metal complex into the matrices of hydrogels. FTIR spectra demonstrate that the Ir(III) -PNaAMPS hydrogel is achieved by irreversible incorporation of positively charged [Ir(ppy)(2)(dmbpy)]Cl (ppy = 2-phenylpyrine, dmbpy = 4,4'-dimethyl-2,2'-bipyridine) into negatively charged poly(2-acrylamido-2-methylpropane sulfonic acid sodium) (PNaAMPS) hydrogel via electrostatic interaction. The photoluminescent spectra indicate that the Ir(III)-PNaAMPS hydrogel exhibits stable phosphorescence. In vitro cultivation of human retinal pigment epithelial cells demonstrates the cytocompatibility of the Ir(III)-PNaAMPS hydrogel. This work herein represents a facile pathway for fabrication of phosphorescent hydrogels.

Neural Stem Cell-Laden Self-Healing Polysaccharide Hydrogel Transplantation Promotes Neurogenesis and Functional Recovery after Cerebral Ischemia in Rats.

Exploring a strategy to effectively repair cerebral ischemic injury is a critical requirement for neuroregeneration. Herein, we transplanted a neural stem cell (NSC)-laden self-healing and injectable hydrogel into the brains of ischemic rats and evaluated its therapeutic effects. We observed an improvement in neurological functions in rats transplanted with the NSC-laden hydrogel. This strategy is sufficiently efficient to support neuroregeneration evidenced by NSC proliferation, differentiation, and athletic movement recovery of rats. This therapeutic effect relates to the inhibition of the astrocyte reaction and the increased expression of vascular endothelial growth factor. This work provides a novel approach to repair cerebral ischemic injury.

Improving the Reliability and Accuracy of Ammonia Quantification in Electro- and Photochemical Synthesis.

The reliable and accurate quantification of ammonia in electrochemical and photochemical experiments has been a technical challenge owing to the extremely low concentration of generated ammonia, interference from trace amounts of cations and organic compounds, and ammonia contamination from various sources. As a result, overestimation and significant errors may happen in many research works. Herein, accuracy and precision of ion chromatography (IC) are evaluated at different pH; excellent performance with a low detection limit (<2 µg L-1 ) under acidic and neutral conditions is found, whereas the linearity is unsatisfactory in the low NH4 + concentration range (0-100 µg L-1 ) under alkaline conditions. High concentrations of Li+ and Na+ are difficult to separate from NH4 + in conventional IC, but this can be solved by employing a high-exchange-capacity column or gradient elution. The interference effects of 14 common transition metal cations and 6 common organic compounds on the quantification of ammonium with low-level concentration (500 µg L-1 ) using IC are systematically investigated, and the results demonstrate good robustness. The overestimation caused by ammonia contamination from reagent water, surroundings, and even the analytical grade of inorganic and organic reagents are confirmed and the results indicate the necessity to prepare and test fresh electrolyte solutions before each experiment, owing to the high sensitivity of acidic and neutral solutions to ammonia contamination from the surroundings. The ammonization of a Nafion membrane during experiments and the underestimation in quantification are also discussed. Finally, a reliable level of synthesized ammonia is identified and some recommendations are presented to improve the reliability and accuracy of ammonia quantification.