Redox Reactions of Organic Molecules Using Rotating Magnetic Field and Metal Rods.

In recent years, redox reactions have harnessed light or mechanical energy to enable the formation of chemical bonds. We postulated a complementary approach that electromagnetic induction could promote the redox reaction of organic molecules using a rotating magnetic field and metal rods. Here, we report that electromotive force activates the redox-active trifluoromethylating reagents. This magnetoredox system can be applied to the trifluoromethylation of heteroarenes with high regioselectivity and hydrotrifluoromethylation of alkenes without the need for catalysts and organic additives.

Ultra-stretchable, adhesive, fatigue resistance, and anti-freezing conductive hydrogel based on gelatin/guar gum and liquid metal for dual-sensory flexible sensor and all-in-one supercapacitors.

Benefiting from the tissue-like mechanical properties, conductive hydrogels have emerged as a promising candidate for manufacturing wearable electronics. However, the high water content within hydrogels will inevitably freeze at subzero temperature, causing a degradation or loss of functionality, which severely prevent their practical application in wearable electronics. Herein, an anti-freezing hydrogel integrating high conductivity, superior stretchability, and robust adhesion was fabricated by dissolving choline chloride and gallium in gelatin/guar gum network using borax as the cross-linker. Based on the synergistic effect of dynamic borate ester bonds and hydrogen bonds, the hydrogel exhibited rapid self-healing property and excellent fatigue resistance. Profiting from these fascinating characteristics, the hydrogel was assembled as strain sensor to precisely detect various human activities with high strain sensitivity and fast response time. Meanwhile, the hydrogel was demonstrated high sensitivity and rapid response to temperature, which can be used as thermal sensor to monitor temperature. Moreover, the conductive hydrogel was encapsulated into supercapacitors with high areal capacitance and favorable cycle stability. Importantly, the flexible sensor and supercapacitors still maintain stable sensing performance and good electrochemical performance even at subzero temperature. Therefore, our work broaden hydrogels application in intelligent wearable devices and energy storage in extreme environments.

Electromagnetic Mill-Promoted Palladium-Catalyzed Heck-Type Cyclization/Decarboxylative Coupling of (Z)-1-Iodo-1,6-diene with Propiolic Acids.

Electromagnetic mill (EMM)-promoted solid-state cascade Heck-type cyclization/decarboxylative coupling of propiolic acid with (Z)-1-iodo-1,6-diene derivate was demonstrated. The reaction was realized via palladium catalysis, which is solvent-free and involves no additional heating. The collision between ferromagnetic rods could not only be a favor to the mixing between the solid substrates and the catalyst system, but also the thermogenic action could accelerate this transformation. More importantly, this EMM strategy realized multiple bond construction under mechanochemical conditions in one pot.

Enhanced metal-free photocatalyst performance by synergistic Coupling of internal magnetic field and piezoelectric field.

Graphitic carbon nitride (g-C3N4) is a promising metal-free photocatalyst; however, its high carrier recombination rate and insufficient redox capacity limit its degradation effect on antibiotics. In order to overcome these shortcomings, the photocatalytic activity is improved by regulating the spin polarization state, constructing the internal electric field, and applying the external piezoelectric field. In this paper, the chlorine-doped and nitrogen-deficient porous carbon nitride composite carbon quantum dots (Nv-Cl/UPCN@CQD) has been synthesized successfully. The doping position of chlorine and spin polarization properties are verified by DFT calculation. The key intermediates *O2- and *OOH for the synthesis of reactive oxygen species were detected by in-situ infrared testing, which promotes the production of •O2- and H2O2. The degradation rate constant of Nv-Cl/UPCN@CQD for removal of tetracycline is 8.45 times higher than that of g-C3N4. The active oxygen production and degradation efficiency of piezoelectric photocatalysis under the synergistic effect of intense stirring and vis-light irradiation are much higher than those of photocatalysis and piezoelectric catalysis, and the conversion of H2O2 to •OH is promoted by piezoelectric field. This paper provides a reliable way to improve the performance of piezoelectric photocatalysts by adjusting their energy band, electronic structure and piezoelectric force.

Multifunctional Conductive Double-Network Hydrogel Sensors for Multiscale Motion Detection and Temperature Monitoring.

As typical soft materials, hydrogels have demonstrated great potential for the fabrication of flexible sensors due to their highly compatible elastic modulus with human skin, prominent flexibility, and biocompatible three-dimensional network structure. However, the practical application of wearable hydrogel sensors is significantly constrained because of weak adhesion, limited stretchability, and poor self-healing properties of traditional hydrogels. Herein, a multifunctional sodium hyaluronate (SH)/borax (B)/gelatin (G) double-cross-linked conductive hydrogel (SBG) was designed and constructed through a simple one-pot blending strategy with SH and gelatin as the gel matrix and borax as the dynamic cross-linker. The obtained SBG hydrogels exhibited a moderate tensile strength of 25.3 kPa at a large elongation of 760%, high interfacial toughness (106.5 kJ m-3), strong adhesion (28 kPa to paper), and satisfactory conductivity (224.5 mS/m). In particular, the dynamic cross-linking between SH, gelatin, and borax via borate ester bonds and hydrogen bonds between SH and gelatin chain endowed the SBG hydrogels with good fatigue resistance (>300 cycles), rapid self-healing performance (HE (healing efficiency) ∼97.03%), and excellent repeatable adhesion. The flexible wearable sensor assembled with SBG hydrogels demonstrated desirable strain sensing performance with a competitive gauge factor and exceptional stability, which enabled it to detect and distinguish various multiscale human motions and physiological signals. Furthermore, the flexible sensor is capable of precisely perceiving temperature variation with a high thermal sensitivity (1.685% °C-1). As a result, the wearable sensor displayed dual sensory performance for temperature and strain deformation. It is envisioned that the integration of strain sensors and thermal sensors provide a novel and convenient strategy for the next generation of multisensory wearable electronics and lay a solid foundation for their application in electronic skin and soft actuators.

Dual-Sensing, Stretchable, Fatigue-Resistant, Adhesive, and Conductive Hydrogels Used as Flexible Sensors for Human Motion Monitoring.

Hydrogel-based sensors serve as an ideal platform for developing personalized wearable electronics due to their high flexibility and conformability. However, the weak stretchability and inferior conductivity of hydrogels have severely restricted their large-scale application. Herein, a natural polymer-based conductive hydrogel integrated with favorable mechanical properties, good adhesive performance, and excellent fatigue resistance was fabricated via interpenetrating tannic acid (TA) into a chitosan (CS) cross-linked network in an acidic aqueous solution. The hydrogel was composed of a regular hierarchical porous structure, which was built by the hydrogen bonding between TA and CS. In addition, the hydrogels exhibited adjustable mechanical properties (maximum yield stress of 7000 Pa) and good stretchability (strain up to 320%). Benefiting from the abundant catechol groups of TA, the proposed hydrogels could repeatedly adhere to various material surfaces and could be easily peeled off without residue. Moreover, the hydrogel exhibited stable conductivity, high stretching sensitivity (gauge factor of 2.956), rapid response time (930 ms), and excellent durability (>300 cycles), which can be assembled as a strain sensor to attach to the human body for precise monitoring of human exercise behavior, distinguishing physiological signals, and recognizing speech. Furthermore, the prepared hydrogels also exhibited stable sensing performance to temperature. As a result, the hydrogels exhibited dual sensory performance for both temperature and strain deformation. It is anticipated that the incorporation of strain sensors and thermal sensors will provide theoretical guidance for developing multifunctional conductive hydrogels and pave a way for the versatile application of hydrogel-based flexible sensors in wearable devices and soft actuators.

A dual-signal output electrochemical immunosensor based on Au-MoS2/MOF catalytic cycle amplification strategy for neuron-specific enolase ultrasensitive detection.

In this work, a dual-signal output electrochemical immunosensor based on the Au-MoS2/MOF high-efficiency catalytic cycle amplification strategy for the sensitive detection of neuron-specific enolase (NSE). The mixed-valence structure MOF (Fe2+/Fe3+-MOF) exhibits high-speed charge mobility and excellent electrochemical performance. Notably, nanoflowers-like MoS2 (MoS2 NFs), as a co-catalyst, were introduced into Fe2+/Fe3+-MOF to successfully ensure the stable cycle of Fe2+/Fe3+ at the electrode interface. The constantly emerging of "fresh" active sites significantly amplified the current signal response. According to the electrochemical behavior, the catalytic cycle mechanism and electron transfer pathways between MoS2 and Fe2+/Fe3+-MOF were further discussed. The two output signals of a sample realized the self-calibration of the immunoassay results, which improved the reliability and sensitivity of the immunosensor. Under optimal conditions, the linear range was 1.00 pg/mL∼100 ng/mL, and the low detection limits were 0.37 pg/mL and 0.52 pg/mL. The results suggest that the as-proposed immunosensor will be promising in the biological analysis and early clinical diagnosis of cancer biomarkers.

Hofmeister Series: Insights of Ion Specificity from Amphiphilic Assembly and Interface Property.

Hofmeister series (HS), ion specific effect, or lyotropic sequence acts as a pivotal part in a number of biological and physicochemical phenomena, e.g., changing the solubility of hydrophobic solutes, the cloud points of polymers and nonionic surfactants, the activities of various enzymes, the action of ions on an ion-channel, and the surface tension of electrolyte solutions, etc. This review focused on how ion specificity influences the critical micelle concentration (CMC) and how the thermoresponsive behavior of surfactants, and the dynamic transition of the aggregate, controls the aggregate transition and gel formation and tunes the properties of air/water interfaces (Langmuir monolayer and interfacial free energy). Recent progress of the ion specific effect in bulk phase and at interfaces in amphiphilic systems and gels is summarized. Applications and a molecular level theoretical explanation of HS are discussed comprehensively. This review is aimed to supply a fresh and comprehensive understanding of Hofmiester phenomena in surfactants, polymers, colloids, and interface science and to provide a guideline to design the microstructures and templates for preparation of nanomaterials.

An organocatalytic method for constructing pyrroles via the cycloisomerisation of Z-1-iodo-4-N-methylbenzenesulfonyl-1,6-enynes.

A new cycloisomerisation of Z-1-iodo-4-N-methylbenzenesulfonyl-1,6-enynes to functionalized pyrroles was realized in the presence of an organomolecule (4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridine) and KOtBu. The transformations were performed efficiently to produce different kinds of functionalized pyrroles within 10 min. This is the first example of an organomolecule promoted methodology with vinyl iodides from a non-aromatic system to an aromatic system, which offers an excellent option toward establishing a new horizon for cross-coupling reactions of vinyl halides. Preliminary mechanistic studies were performed and a crude radical pathway was proposed.

A label-free immunosensor based on PtPd NCs@MoS2 nanoenzymes for hepatitis B surface antigen detection.

Nowadays, nanomaterials with enzymatic properties have aroused wide interest because of their special advantages, such as catalytic activity, simple preparation method and high stability. We introduced new nanoenzymes to a label-free electrochemical immunosensor for Hepatitis B surface antigen (HBs Ag) detection. In this study, PtPd nanocubes@MoS2 nanoenzymes (PtPd NCs@MoS2) were prepared by loading PtPd nanocubes (PtPd NCs) on molybdenum disulfide nano-sheet (MoS2) through in situ redox polymerization. The prepared nanoenzymes exhibited enhanced peroxidase-like activity than separate MoS2 and PtPd NCs. The catalytic process of PtPd NCs@MoS2 is in agreement with the Michaelis-Menten kinetic equation. PtPd NCs@MoS2 were used for sensitive detection of HBs Ag, which is ascribed to their superior peroxidase activity, good conductivity and high specific surface area and synergistic amplification for current signals. Compared with the detection limit of colorimetric method (3.3 pg/mL), the electrochemical method (10.2 fg/mL) shows a lower detection limit and a wider linear range from 32 fg/mL to 100 ng/mL, so it is more suitable for quantitative analysis of Hepatitis B. In summary, the prepared immunosensor provides a better opportunity for early diagnosis of Hepatitis B and also has further applications in biosensing and medical diagnostics.

Sandwich-type electrochemical immunosensor based on Au@Pt DNRs/NH2-MoSe2 NSs nanocomposite as signal amplifiers for the sensitive detection of alpha-fetoprotein.

A sandwich-type electrochemical immunosensor was fabricated for the quantitation of alpha fetoprotein (AFP). To this end, the Au@Pt dendritic nanorods loaded with amino functionalized molybdenum selenide nanosheets (Au@Pt 41 DNRs/NH2-MoSe2 NSs) with enhanced peroxidase-like properties were selected as the secondary antibody label (Ab2) to achieve signal amplification. The as-obtained Au@Pt DNRs/NH2-MoSe2 NSs exhibited better catalytic activity toward hydrogen peroxide reduction and offered rich anchors for bioconjugation. Meanwhile, gold nanoparticles anchored on an amino functionalized graphene (Au NPs/NH2-GS) composite with admirable conductivity and biocompatibility was used as the matrix material to improve sensitivity. Under optimal conditions, amperometric current responses had a good linear relationship with the logarithm values of AFP concentration in the range 10 fg mL-1 to 200 ng mL-1 with a detection limit of 3.3 fg mL-1 (S/N = 3). Additionally, the immunosensor had excellent reproducibility, selectivity, and stability, which indicated superior performance for AFP detection compared with previous reports. The satisfactory results of human serum samples analysis showed that the designed immunosensor has potential applicability for the sensitive detection of other tumor markers.

Stretchable self-healing hydrogels capable of heavy metal ion scavenging.

Self-healing hydrogels were prepared by simply mixing phytic acid (PA) and chitosan (CS) in water. Determined by scanning electron microscopy (SEM), the hydrogels were found to be a three-dimensional (3D) porous network structure. The formation of the network structure was considered to be mainly driven by electrostatic interactions and hydrogen bonding, cooperating with the subtle balance of multiple noncovalent interactions. The rheological data indicated that the hydrogels presented excellent mechanical properties with an elastic modulus of 20 000 Pa and a yield stress exceeding 7000 Pa. The dynamic dissociation and recombination of hydrogen bonding and electrostatic interaction in fractured regions of the gels initiated the self-healable property of PA/CS hydrogels. Since PA had high coordination ability to metal ions, PA/CS hydrogels were shown to exhibit excellent capability for capturing heavy metal ions, for example, Pb2+ and Cd2+. The PA/CS hydrogels provided a simple, green, and high efficiency strategic approach to scavenging heavy-metal ions from industrial sewage.

Ultrasensitive sandwich-type immunosensor for cardiac troponin I based on enhanced electrocatalytic reduction of H2O2 using ß-cyclodextrins functionalized 3D porous graphene-supported Pd@Au nanocubes.

In this study, Pd@Au nanocubes supported ß-cyclodextrins functionalized three-dimensional porous graphene (CDs-3D-PG-Pd@Au NCs) was synthesized using a facile method. ß-cyclodextrins (CDs) were beneficial in improving the dispersibility of three-dimensional porous graphene (3D-PG) and displayed good capture capability towards secondary antibodies (Ab2). Moreover, large amounts of Pd@Au NCs could load on the CDs-3D-PG, which effectively improved the electrochemical signals. The obtained CDs-3D-PG-Pd@Au NCs composite was utilized as signal amplification labels. Furthermore, Au nanoparticles (AuNPs) and thionine (Th) decorated on amino-functionalized microporous carbon spheres (AuNPs-FMCS-Th) as sensor platforms, which not only effectively immobilized primary antibodies (Ab1) by interacting with Au-NH2, but also accelerated the electron transfer process on the electrode surface using the mediated effect of Th, resulted in further amplification of the signal response. The morphology and composition of the as-prepared nanomaterials were characterized using scanning electron microscopy (SEM), UV-vis spectroscopy, Raman spectroscopy and transmission electron microscopy (TEM). Cyclic voltammetry (CV) and amperometric i-t methods were used to investigate the electrocatalytic reduction of H2O2 by CDs-3D-PG-Pd@Au NCs using electron mediation of Th. Under optimal conditions, the proposed immunosensor exhibited high selectivity, acceptable stability and good reproducibility for the detection of cardiac troponin I (cTnI) with a low detection limit of 33.3 fg mL-1. Importantly, satisfactory results were obtained for analysing real serum samples, indicating that the designed method could provide an effective strategy in clinical research.

Sandwich-type electrochemical immunosensor based on Au@Ag supported on functionalized phenolic resin microporous carbon spheres for ultrasensitive analysis of α-fetoprotein.

Signal amplification is crucial for obtaining low detection limits in electrochemical immunosensor. In this work, we developed a novel signal amplification strategy using Au@Ag nanoparticles loaded by polydopamine functionalized phenolic resin microporous carbon spheres (Au@Ag/PDA-PR-MCS). Phenolic resin microporous carbon spheres (PR-MCS) possesses uniform size and a large surface area (1656.8 m2 g-1). Polydopamine (PDA) functionalized phenolic resin microporous carbon spheres (PDA-PR-MCS) retains the advantages of PR-MCS and possesses strong adsorption ability. With the unique structure of PDA-PR-MCS, it not only improves the loading capacity and dispersity of Au@Ag nanoparticles (Au@Ag NPs), but also enhances the stability for the combination of the Au@Ag NPs by chemical absorption between Au@Ag NPs and -NH2 of PDA. The Au@Ag/PDA-PR-MCS exhibits extraordinary electrocatalytic activity towards reduction of hydrogen peroxide (H2O2) to make the electrochemical response more sensitive. Furthermore, Au NPs with good biocompatibility and excellent conductivity were electrodeposited on the surface of electrode, which was used as a sensing platform to immobilize primary antibody (Ab1) and accelerate the electron transfer on the electrode interface. Herein, the designed immunosensor provided a broad linear range from 20 fg/mL to 100 ng/mL for alpha fetoprotein (AFP) detection and a low detection limit of 6.7 fg/mL (signal-to-noise ratio of 3) under optimal experimental conditions. Moreover, the excellent performance in detection of human serum samples indicated that the proposed immunosensor will provide promising applications in clinical monitoring of AFP.

Peroxidase mimetic activity of Fe3O4 nanoparticle prepared based on magnetic hydrogels for hydrogen peroxide and glucose detection.

Stimuli-response magnetic hydrogels were prepared in the mixtures of magnetic surfactants, (CnTAFB(C), n=12, 14, 16), and chiral amphiphiles, sodium cholate (SC). The gelation behavior of CnTAFB(C)/SC were studied in detail. The results proved that the hydrophobicity of surfactants and the hydration radius (Rh) of anions played a vital role in the gelation process. The microstructure of the hydrogels were determined to be three-dimensional network of fibrous aggregates. The formation of the hydrogel fibrils was considered to be mainly driven by a delicate balance of multiple non-covalent interactions including hydrophobic interaction, electrostatic interaction, hydrogen bonding, van der Waals force, and the steric effect of SC molecule. Rheological measurements demonstrated that the hydrogels are high mechanical strength materials (the yield stress exceeding 2000Pa). The mechanical strength of the hydrogels is dependent on the fiber density, which can be regulated by changing the proportion of the two compounds, the total concentration and the chain length of the surfactants. The magnetic hydrogels of C12TAFB/SC mixtures served as the precursors for preparing cubic Fe3O4 nanoparticles with the diameter of 7.2nm. The as-prepared Fe3O4 nanoparticles exhibit excellent ferromagnetic characteristic and high peroxidase-like activity and can be used as biosensor for hydrogen peroxide (H2O2) and glucose detection. We developed a convenient and green method for preparing Fe3O4 nanoparticles, which can be used as a promising candidate biosensor for glucose detection.

A novel label-free electrochemical immunosensor based on functionalized nitrogen-doped graphene quantum dots for carcinoembryonic antigen detection.

A novel and ultrasensitive label-free electrochemical immunosensor was fabricated for quantitative detection of carcino-embryonic antigen (CEA). The nitrogen-doped graphene quantum dots (N-GQDs) supported PtPd bimetallic nanoparticles (PtPd/N-GQDs) were synthesized by a simple and green hydrothermal procedure. Subsequently, PtPd/N-GQDs functionalized Au nanoparticles (PtPd/N-GQDs@Au) were prepared successfully via a self-assembly approach. Because of the synergetic effect present in PtPd/N-GQDs@Au, this novel nanocomposites has shown excellent electrocatalytic activity towards hydrogen peroxide (H2O2) reduction. Featuring good biocompatibility, excellent conductivity and large surface area, PtPd/N-GQDs@Au was applied as transducing materials to efficiently conjugate capture antibodies and amplify electrochemical signal. Under the optimal conditions, the proposed immunosensor was used for the detection of CEA with wide dynamic range in the range from 5 fg/mL to 50ng/mL with a low detection limit of 2fg/mL (S/N=3). Furthermore, this label-free immunosensor possesses high sensitivity, special selectivity and long-term stability, which shows promising application in bioassay analysis.

Palladium-Catalyzed 6-Endo Selective Alkyl-Heck Reactions: Access to 5-Phenyl-1,2,3,6-tetrahydropyridine Derivatives.

A new type of palladium-catalyzed 6-endo-selective alkyl-Heck reaction of unactivated alkyl iodides has been described. This strategy provides efficient access to a variety of 5-phenyl-1,2,3,6-tetrahydropyridine derivatives, which are important structural motifs for bioactive molecules. This process displays a broad substrate scope with excellent 6-endo selectivity. Mechanistic investigations reveal that this alkyl-Heck reaction performs via a hybrid palladium-radical process.

Edge-nitrogenated graphene nanoplatelets as high-efficiency counter electrodes for dye-sensitized solar cells.

Edge-nitrogenated graphene nanoplatelets (ENGNPs) are prepared by a simple and eco-friendly mechanochemical pin-grinding process using flake graphite as the precursor in the presence of nitrogen and investigated as the counter electrodes of dye-sensitized solar cells (DSCs). SEM images and nitrogen adsorption analysis indicate an effective and spontaneous delamination of the pristine graphite into small graphene nanoplatelets by a mechanochemical pin-grinding process. The mechanochemical cracking of the graphitic C-C bond generates activated carbon sites that react directly with nitrogen at the broken edges. The resultant ENGNPs are deposited on a fluorine-doped tin oxide (FTO) substrate by spray coating, and their electrocatalytic activities are investigated systemically in the I(-)/I3(-) redox electrolyte. Electrochemical measurements show that the ENGNP electrode possesses excellent electrocatalytic activity for the redox reaction of I(-)/I3(-) as evidenced by the low charge-transfer resistance at the interface of the electrode and electrolyte. Under 100 mW cm(-2) illumination, the DSC with the optimized ENGNP counter electrode achieves a conversion efficiency of 7.69%, which is comparable to that of the device with Pt counter electrode.

Aluminium electrodeposition in chloroaluminate ionic liquid.

An efficient microwave enhanced synthesis of ambient temperature chloroaluminate ionic liquid ([EMIM]Br) that preceeds reaction of 1-methylimidazolium with bromoethane in a closed vessel, was described in our work. The reaction time was drastically reduced as compared to the conventional methods. The electrochemical techniques of impedance spectroscopy, cyclic voltammetry and chronoamperometry were used to investigate the mechanism of Al electrodeposition from 2:1 (molar ratio) AlCl3/[EMIM]Br ionic liquid at room temperature. Results indicated that Al electrode- position from this ionic liqud was a quasi-reversible process, and the kinetic complications during the reaction was probably attributed to the electron transfer or mass transport cooperative controlled processes, instantaneous nucleation with diffusion-controlled growth was also investigated. Electrodepositon experiment was conducted using constant current density of 40 mA·cm(-2) for 20 minutes at room temperature and the qualitative analysis of the deposits were performed using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and energy dispersive spectroscope (EDS). The deposits obtained on copper cathode were dense and compact and most Al crystal shows granular structure spherical with high purity.

Microwave assisted esterification of acidified oil from waste cooking oil by CERP/PES catalytic membrane for biodiesel production.

The traditional heating and microwave assisted method for biodiesel production using cation ion-exchange resin particles (CERP)/PES catalytic membrane were comparatively studied to achieve economic and effective method for utilization of free fatty acids (FFAs) from waste cooking oil (WCO). The optimal esterification conditions of the two methods were investigated and the experimental results showed that microwave irradiation exhibited a remarkable enhanced effect for esterification compared with that of traditional heating method. The FFAs conversion of microwave assisted esterification reached 97.4% under the optimal conditions of reaction temperature 60°C, methanol/acidified oil mass ratio 2.0:1, catalytic membrane (annealed at 120°C) loading 3g, microwave power 360W and reaction time 90min. The study results showed that it is a fast, easy and green way to produce biodiesel applying microwave irradiation.