Search

Mechanical nonreciprocity, or the asymmetric transmission of mechanical quantities between two points in space, is crucial for developing systems that can guide, damp, and control mechanical energy. We report a uniform composite hydrogel that displays substantial mechanical nonreciprocity, owing to direction-dependent buckling of embedded nanofillers. This material exhibits an elastic modulus more than 60 times higher when sheared in one direction compared with the opposite direction. Consequently, it can transform symmetric vibrations into asymmetric ones that are applicable for mass transport and energy harvest. Furthermore, it exhibits an asymmetric deformation when subjected to local interactions, which can induce directional motion of various objects, including macroscopic objects and even small living creatures. This material could promote the development of nonreciprocal systems for practical applications such as energy conversion and biological manipulation.

Ultralong organic phosphorescence (UOP) has aroused enormous interest in recent years. UOP materials are mainly limited to crystals or rigid host-guest systems. Their poor processability and mechanical properties critically hamper practical applications. Here, we reported a series of ultralong phosphorescent foams with high mechanical strength. Phosphorescence lifetime of the foam can reach up to 485.8 ms at room temperature. Impressively, lightweight gelatin foam can bear a compressive pressure of 4.44 MPa. Moreover, phosphorescence emission of polymer foam can be tuned from blue to orange through varying the excitation wavelength. Experimental data and theoretical calculations revealed that ultralong phosphorescence was ascribed to the fixation of multiple hydrogen bonds to the clusters of carbonyl groups. These results will allow for expanding the scope of luminescent foams, providing an ideal platform for developing ultralong phosphorescent materials with high mechanical strength.

Heterogeneous analysis has great application prospects in the detection of post-translational modification (PTM) enzymes with the advantages of signal enhancement, less sample demand, and high sensitivity and selectivity. Nevertheless, once the substrate was fixed on a solid interface, the steric hindrance might limit the approaching of catalytic center to the substrate, thus reducing the efficiency of PTM. Herein, we suggested that the avidin-modified interface could be used to develop heterogeneous sensing platforms with biotin-labeled substrates as the probes, in which the enzymatic PTM was performed in solution and the heterogeneous assay was conducted on a solid surface. The sensing strategy integrates the advantages but overcomes the defects of both homogeneous and heterogeneous assays. Protein kinase A (PKA) and histone acetyltransferase (HAT) were determined as the examples by using sequence-specific peptide substrates. The signal changes were monitored by HRP-based colorimetric assay and antibody-amplified surface plasmon resonance (SPR). The methods were used for analysis of cell lysates and evaluation of inhibition efficiency with satisfactory results. The strategy can be used for the detection of a variety of biological enzymes and provide a new idea for the design of various heterogeneous biosensors. Thus, this work should be of great significance to the popularization and practical application of biosensors.

The sluggish nature of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) coupled with the high cost of related noble-metal catalysts stimulate the research of active non-noble met...

The in situ polymerization of monomers to form a second network within a preexisting network (first network) is a facile and effective strategy to fabricate semi-interpenetrating (semi-IPN) hydrogels with enhanced mechanical strength; while to comprehend the effects of the first polymer network on the polymerization process of the second network is still a challenging project. This paper introduces a simple method of employing dynamic rheological measurement loops to monitor the real time progress of the in situ polymerized acrylamide (AAm) in a chitosan (CS) solution towards the formation of a semi-IPN hydrogel. To identify the effects of the preexisting network on the polymerization gelation process, the concept “Effective Conversion Ratio (ECR)” is introduced to evaluate the first network effects on the requirement for the polymerized conversion ratio of the second network to form a critical gel. The rheological properties before gel point, at gel point, and at post-gel stage are discussed via the obtained real time data, respectively. The experimental results have proved the suitability of utilizing dynamic rheology to obtain the real time details of the semi-IPN gel fabrication process.

In vitro mimics recognized that the propensity of a negatively charged phospholipid, DPPS, monolayers to self-aggregate to three-dimensional (3D) giant folds under overcompression at an air–water interface. Time elapsing microscopical observations confirmed that such giant folds were able to float stably on the air–water interface for weeks or even longer. Ex situ atomic force microscopy (AFM) and transmission electronic microscopy (TEM) characterizations pointed out that such giant folds were composed of compactly stacked lipid layers. Phospholipase A2 (PLA2), a principal bactericide in human and animal tear secretion, was chosen to drive the in situ lipid giant folds disassembly on water and supported substrate surfaces, respectively. Our experimental results confirmed the layer-by-layer structures of the giant folds. It is noteworthy that the defect-rich areas of the giant lipid folds were eliminated quickly by PLA2 while defect-free lipid zones were left untouched, suggesting that PLA2 may serve as a ...

This work proposed a new sensing strategy for protease detection by converting a homogeneous assay into a surface-tethered electrochemical analysis. Streptavidin (SA), a tetramer protein, was used as the sensing unit based on the SA-biotin coupling chemistry. Caspase-3 was used as the model analyte, and a biotinylated peptide with a sequence of biotin-GDEVDGK-biotin was designed as the substrate. Specifically, the peptide substrate could induce an assembly of SA to form (SA-biotin-GDEVDGK-biotin)n aggregates through SA-biotin interactions, which was confirmed by atomic force microscopy (AFM). The peptide substrate-induced assembly of SA was facilely initiated on an electrode-liquid surface by modification of the electrode with SA. The in situ formation of (SA-biotin-GDEVDGK-biotin)n aggregates created an insulating layer, thus limiting the electron transfer of ferricyanide. Once the peptide substrate was cleaved into two shorter fragments (biotin-GDEVD and GK-biotin) by caspase-3, the resulting products would compete with biotin-GDEVDGK-biotin to bind SA proteins immobilized on the electrode surface and distributed in a solution, thus preventing the in situ formation of (SA-biotin-GDEVDGK-biotin)n assemblies. With the simple principle of the substrate-induced assembly of SA, a dual-signal amplification was achieved with improved sensitivity. Taking advantage of high sensitivity, simple principle, and easy operation, this method can be augmented to design various surface-tethered biosensors for practical applications.

We proposed a simple and sensitive strategy for the detection of microRNAs (miRNAs) by converting homogeneous assay into surface-tethered electrochemical analysis. Specifically, the biotinylated detection probes (biotin-DNA-biotin) can trigger the in-situ assembly of tetrameric streptavidin (SA) proteins on an electrode surface via the SA-biotin interactions. The (SA-biotin-DNA-biotin)n assemblies electrically insulated the electrode interface, thereby blocking the electron transfer of [Fe(CN)6]3-/4-. When the probe was hybridized with the target miRNA, it would be cleaved into small fragments (denoted as biotin-DNA) by duplex-specific nuclease (DSN). The released target miRNA can enter into the next hybridization-enzymolysis cycle, thus leading to the generation of considerable amounts of biotin-DNA fragments. The released biotin-DNA competed with the detection probe to bind SA, thus limiting the in-situ formation of (SA-biotin-DNA-biotin)n assemblies. The surface-tethered electrochemical analysis by the dual signal amplification of DSN and (SA-biotin-DNA-biotin)n assemblies has been used for the determination of miRNAs in cell lysate with a satisfactory result. The method showed a detection limit down to 10 aM. The "one-step" immobilization-free strategy can be used to design novel biosensors for the detection of other biomarkers.

Butylated hydroxytoluene (BHT), one of the most widely used synthetic phenolic antioxidants, is a popular food additive. Previous studies have reported the possible health hazards of BHT. However, BHT effects on female reproduction, especially on endometrial decidualization, are still unknown. During early pregnancy, decidualization plays important roles for embryo implantation and pregnancy establishment. This study aimed to explore the effects of BHT on endometrial decidualization in pregnant mice. The pregnant mice received BHT via intraperitoneal injection at doses of 0, 200, and 400 mg/kg/day from day 1 (D1) of pregnancy until sacrifice. Under BHT exposure, maternal body weight was significantly decreased during early pregnancy. Compared with the control group, the number of implantation sites and uterine weight were significantly reduced in the BHT groups. The uterine lumen failed to close after BHT exposure, and the decidual morphology of endometrial stromal cells was inhibited by BHT. Furthermore, BHT significantly decreased the expression of endometrial decidual markers including COX2, HOXA10, and MMP9. Notably, the levels of serum estrogen (E2) and progesterone (P4) and expression levels of uterus estrogen receptor α (ERα) and progesterone receptor (PR) during early pregnancy were significantly upregulated following BHT exposure. In conclusion, these results demonstrated that gestational BHT exposure could inhibit decidualization of mouse endometrium during early pregnancy. The disorders of reproductive hormones and changes of hormone receptor signals could be responsible for the impaired decidualization. This study provided new evidence for the deleterious effects of BHT on female reproduction and revealed the potential reproductive toxicity of synthetic phenolic antioxidants.

Atomically dispersed metal catalysts have demonstrated superb electrocatalytic activity because of optimal atom efficiency. However, a rational design of low-cost, high-performance single atom catalysts remains a great challenge due to the elusive chemical reactions of the formation of metal active sites. In this work, biomass hydrogel is prepared as a template for mass production of three-dimensional carbon aerogel-supported single metal atom catalysts. By tailoring the structure of the hydrogel templates, the obtained carbon aerogels exhibit an increase of microporous defects which capture and stabilize isolated metal atoms and minimize aggregation during pyrolysis. Extended X-ray absorption fine structure, Mossbauer spectroscopy, and nitrogen adsorption–desorption isotherm measurements indicate that single metal centers of FeN4 are formed and embedded within the hierarchical porous carbon frameworks. The obtained composites exhibit outstanding catalytic activity towards oxygen reduction in alkaline media, with a high onset potential of +1.05 V and half-wave potential of +0.88 V, as well as excellent durability. Remarkably, when the carbon aerogels are used as the cathode catalyst in an aluminum–air battery, the battery achieves an ultrahigh open-circuit voltage of 1.81 V, large power density of 181.1 mW cm−2 and stable discharge voltage of 1.70 V at 20 mA cm−2, markedly better than those with commercial Pt/C as the cathode catalyst.

This paper demonstrates a rational protocol for the synthesis of ultrasmall bimetallic alloy nanoparticles (FeCo, FeNi, and NiCo

The accurate analysis of circulating tumor cells (CTCs) holds great promise in early diagnosis and prognosis of cancers. However, the extremely low abundance of CTCs in peripheral blood samples limits the practical utility of the traditional methods for CTCs detection. Thus, novel and powerful strategies have been proposed for sensitive detection of CTCs. In particular, nanomaterials with exceptional physical and chemical properties have been used to fabricate cytosensors for amplifying the signal and enhancing the sensitivity. In this review, we summarize the recent development of nanomaterials-based optical and electrochemical analytical techniques for CTCs detection, including fluorescence, colorimetry, surface-enhanced Raman scattering, chemiluminescence, electrochemistry, electrochemiluminescence, photoelectrochemistry and so on.

It is a great challenge to finely tune the morphology of iron oxides for energy storage. In this work, we introduced a facile hydrothermal method to obtain single crystalline hematite (α-Fe2O3) nano-coffee beans (NCBs) with the assistance of acetic acid. Interestingly, α-Fe2O3 nanostructures with this special morphology were formed under the effect of Ostwald ripening and oriented etching of H+ ions along [001] direction, which could be proved by the scanning electron microscope /transmission electron microscope and X-ray diffraction. After calcination at high temperature, the as-prepared α-Fe2O3 NCBs were used as potential anode materials, showing a very high reversible capacity of 810 mA h g−1 (0.2 C), excellent cycling stability, and high-rate performance for lithium storage. Hence, in virtue of the good performances, the structural design of nanomaterials would be promoted in the fabrication of electrode materials for lithium-ion batteries.

Si-based nanostructure composites have been intensively investigated as anode materials for next-generation lithium-ion batteries because of their ultra-high-energy storage capacity. However, it is still a great challenge to fabricate a perfect structure satisfying all the requirements of good electrical conductivity, robust matrix for buffering large volume expansion, and intact linkage of Si particles upon long-term cycling. Here, we report a novel design of Si-based multicomponent three-dimensional (3D) networks in which the Si core is capped with phytic acid shell layers through a facile high-energy ball-milling method. By mixing the functional Si with graphene oxide and functionalized carbon nanotube, we successfully obtained a homogeneous and conductive rigid silicon-based gel through complexation. Interestingly, this Si-based gel with a fancy 3D cross-linking structure could be writable and printable. In particular, this Si-based gel composite delivers a moderate specific capacity of 2711 mA h g–1 ...

This work reports on a simple and sensitive electrochemical strategy for the detection of telomerase extracted from HeLa cells. It was based on the signal amplification of in-situ performed streptavidin-biotin-DNA-biotin (SA-biotin-DNA-biotin) networks. Specifically, the DNA primer immobilized on a gold electrode was elongated by telomerase. After the hybridization of biotin-DNA-biotin to the extended primer, the in-situ formation of SA-biotin-DNA-biotin networks was initiated on the electrode surface within 10 min through the SA-biotin interactions. The resulting networks created an insulating layer, thus hampering the electron transfer and causing the significant increase in the electrochemical impedance. Telomerase extracted from 2 HeLa cells can be readily measured. The method showed a linear relationship in the range of 50 ∼ 5000 cells/mL. The signal-amplified strategy can be applied to develop novel sensing platforms for the detection of different biomarkers.

A novel hollow-structured CuO derived from chitosan-coated Cu/Cu2O composite hollow spheres was mass produced via a supramolecular hydrogel templating method and homogeneously co-doped with C and N. Evaluation of the as-produced co-doped CuO hollow spheres as anode materials for Li ion batteries showed that they had superior electrochemical properties.

It is a challenge to prepare organic electrodes for sodium-ion batteries with long cycle life and high capacity. The highly reactive radical intermediates generated during the sodiation/desodiation process could be a critical issue because of undesired side reactions. Here we present durable electrodes with a stabilized α-C radical intermediate. Through the resonance effect as well as steric effects, the excessive reactivity of the unpaired electron is successfully suppressed, thus developing an electrode with stable cycling for over 2,000 cycles with 96.8% capacity retention. In addition, the α-radical demonstrates reversible transformation between three states: C=C; α-C·radical; and α-C− anion. Such transformation provides additional Na+ storage equal to more than 0.83 Na+ insertion per α-C radical for the electrodes. The strategy of intermediate radical stabilization could be enlightening in the design of organic electrodes with enhanced cycling life and energy storage capability., Reactive radical intermediates can be a problem leading to fast degradation of organic electrodes in sodium-ion batteries. Here, the authors show a stabilized α-C radical displaying reversible transformations between C=C, α-C radical and α-C anionic states to facilitate long cycling and improved capacity.

Nanomaterials composed of electroactive elements have increasingly being used as the signal labels of electrochemical biosensors. In this work, we proposed a novel strategy for the preparation of signal labels used for electrochemical biosensors. The method is based on the signal amplification of self-assembled nanomaterials of small molecules and the in situ dissolution of nanostrutures into electroactive elements on electrode surface. Ferrocenoyl phenylalanine (Fc-F) nanoparticles (FcFNPs) were prepared and used as the example of signal labels. The FcFNPs captured by sensor electrode were in situ disassembled into tens or hundreds of monomers by methnol. After evaporation of methnol, the released Fc-F monomers were concentrated on electrode surface to produce a strong electrochemical signal. With prostate specific antigen and cancer cells as the model analytes, the target concentration as low as 1 pg/mL or 10 cells can be readily measured. This work should be valuable for designing of novel nanolabels and development of sensitive sensing platforms.

Self-assembling natural drug hydrogels formed without structural modification and able to act as carriers are of interest for biomedical applications. A lack of knowledge about natural drug gels limits there current application. Here, we report on rhein, a herbal natural product, which is directly self-assembled into hydrogels through noncovalent interactions. This hydrogel shows excellent stability, sustained release and reversible stimuli-responses. The hydrogel consists of a three-dimensional nanofiber network that prevents premature degradation. Moreover, it easily enters cells and binds to toll-like receptor 4. This enables rhein hydrogels to significantly dephosphorylate IκBα, inhibiting the nuclear translocation of p65 at the NFκB signalling pathway in lipopolysaccharide-induced BV2 microglia. Subsequently, rhein hydrogels alleviate neuroinflammation with a long-lasting effect and little cytotoxicity compared to the equivalent free-drug in vitro. This study highlights a direct self-assembly hydrogel from natural small molecule as a promising neuroinflammatory therapy., There is interest in the development of drug-based hydrogels for responsive sustained drug release. Here, the authors report on the self-assembly of natural small molecule, rhein, into hydrogels and the application of the hydrogels as stable controlled release agents for neuro-inflammatory therapy

Layered stacking and highly porous N, P co-doped Mo

Self-assembling natural drug hydrogels formed without structural modification and able to act as carriers are of interest for biomedical applications. A lack of knowledge about natural drug gels limits there current application. Here, we report on rhein, a herbal natural product, which is directly self-assembled into hydrogels through noncovalent interactions. This hydrogel shows excellent stability, sustained release and reversible stimuli-responses. The hydrogel consists of a three-dimensional nanofiber network that prevents premature degradation. Moreover, it easily enters cells and binds to toll-like receptor 4. This enables rhein hydrogels to significantly dephosphorylate IκBα, inhibiting the nuclear translocation of p65 at the NFκB signalling pathway in lipopolysaccharide-induced BV2 microglia. Subsequently, rhein hydrogels alleviate neuroinflammation with a long-lasting effect and little cytotoxicity compared to the equivalent free-drug in vitro. This study highlights a direct self-assembly hydrogel from natural small molecule as a promising neuroinflammatory therapy.

Novel three-dimensional (3D) concentration-gradient Ni-Co hydroxide nanostructures (3DCGNC) have been directly grown on nickel foam by a facile stepwise electrochemical deposition method and intensively investigated as binder- and conductor-free electrode for supercapacitors. Based on a three-electrode electrochemical characterization technique, the obtained 3DCGNC electrodes demonstrated a high specific capacitance of 1,760 F·g−1 and a remarkable rate capability whereby more than 62.5% capacitance was retained when the current density was raised from 1 to 100 A·g−1. More importantly, asymmetric supercapacitors were assembled by using the obtained 3DCGNC as the cathode and Ketjenblack as a conventional activated carbon anode. The fabricated asymmetric supercapacitors exhibited very promising electrochemical performances with an excellent combination of high energy density of 103.0 Wh·kg−1 at a power density of 3.0 kW·kg−1, and excellent rate capability—energy densities of about 70.4 and 26.0 Wh·kg−1 were achieved when the average power densities were increased to 26.2 and 133.4 kW·kg−1, respectively. Moreover, an extremely stable cycling life with only 2.7% capacitance loss after 20,000 cycles at a current density of 5 A·g−1 was achieved, which compares very well with the traditional doublelayer supercapacitors.

A sandwich strategy for highly sensitive DNA analysis has been proposed by measuring the hindered diffusion flux of Fe(CN) 6 3− caused by DNA hybridization in nanopores of a porous anodic alumina (PAA) membrane. The flux of Fe(CN) 6 3− passing through the PAA nanopores is recorded using an electrochemical detector made with Au film sputtered on one face of PAA membrane. To achieve target DNA analysis, the PAA membranes are functionalized with capture DNA and followed by the hybridization event that gives rise to the pore blocking due to the synergetic effect of steric and electrostatic repulsion in the confined nanopores. Both of these two effects can be amplified by using 12-nm Au nanoparticle tags labeled with single strand DNA to perform a sandwich assay, which further amplified detection signals evidenced from the decreased flux of Fe(CN) 6 3− . Based on this strategy, the proposed DNA biosensor gives a detection limit of 1 pM. This thin piece of membrane sensor, coupled with the simple electrochemical system, fast response and high sensitivity, show potentials to be successfully used for bioanalysis.

This manuscript introduces a one-pot fabrication procedure for the preparation of supramolecular hybrid hydrogels from low-cost commercially available natural products through a "green" strategy. In particular, the hybrid hydrogels, which are developed with Fmoc-Glu-OMe, silver nanoparticles and chitosan, exhibit outstanding antibacterial properties and can be regarded as excellent mouldable wound healing biomaterials.

In this paper we present a new paradigm for designing hydrogelators that exhibit sharp phase transitions in response to a series of disparate stimuli, including oxidation-reduction reactions (redox), guest-host interactions, and pH changes. We have serendipitously discovered that ferrocenoyl phenylalanine (Fc-F) monomers aggregate in water via a rapid self-assembly mechanism to form stable, multistimuli hydrogels. In comparison to other known mono- and multiresponsive gelators, Fc-F is unique because of its small size, economy of gel-forming components, and exceptionally simple molecular structure. Density functional theory (DFT) ab initio calculations suggest gel formation initially involves an antiparallel, noncovalent dimerization step wherein the ferrocenoyl moiety of one axe-like monomer conjoins with the phenyl group of the second monomer via a π-π stacking interaction to form brick-like dimers. This stacking creates a cavity in which the carboxylic acid groups of each monomer mutually interact via hydrogen bond formation, which affords additional stability to the dimer. On the basis of structural analysis via optical and electrical measurements and additional DFT calculations, we propose a possible stepwise hierachical assembly mechanism for fibril formation. Insights into the self-assembly pathway of Fc-F should prove useful for understanding gelation processes of more complex systems. We expect that Fc-F will serve as a helpful archetypical template for others to use when designing new, stimuli specific hydrogelation agents.

Aggregates of amyloid beta (Aβ) peptides are believed to be responsible for the neuropathology of Alzheimer’s disease. In this work, ferrocene (Fc) is attached to the aggregating core of the Aβ peptides, KLVFFAE. Inhibition of Fc-KLVFFAE aggregation by curcumin, a natural compound, was monitored by HPLC-electrochemical detection (HPLC-EC). The Fc oxidation current is dependent on the incubation condition and curcumin can retain Fc-KLVFFAE in its monomeric form. We demonstrate that tagging Fc to KLVFFAE affords a cost-effective and electroactive mimicry of Aβ(142) and HPLC-EC is suitable for sensitive, reproducible, and facile screening of drugs for inhibiting the aggregation of Aβ peptides.

A biopolymer-chitosan based Supramolecular Hydrogel type solid state Electrolyte (SHE) is prepared via a simple and fast cross-linking between chitosan and Li+/Ag+. The obtained SHE itself shows high thermal stability and excellent flexible and mouldable properties. When integrated in an asymmetric supercapacitor with MnO2 as the positive electrode and active carbon as the negative electrode, it can survive more than 10000 cycles with the areal capacity of 10 mF cm−2 at the 1.8 mA cm−2 current density.