Versatile photoelectrochemical biosensor based on AIS/ZnS QDs sensitized-WSe2 nanoflowers coupled with DNA nanostructure probe for"On-Off"assays of TNF-α and MTase.

Herein, a novel multifunctional photoelectrochemical (PEC) biosensor based on AgInS2 (AIS)/ZnS quantum dots (QDs) sensitized-WSe2 nanoflowers and DNA nanostructure signal probe was designed to achieve ultra-sensitive "On-Off" detection of human tumor necrosis factor α (TNF-α) and methylase Dam MTase (MTase). AIS/ZnS QDs as an excellent photosensitive material was found to match WSe2 in energy level for the first time, and the photocurrent signal after sensitization was 65 times that of WSe2 nanoflowers and 17.9 times that of AIS/ZnS QDs. Moreover, abundant AIS/ZnS QDs were loaded on the TiO2 nanoparticles with good conductivity by DNA to fabricate a multifunctional probe, which can not only amplify signal but also specifically recognize target. When target TNF-α was present, the AIS/ZnS QDs signal probe was attached to the WSe2 nanoflowers-modified electrode through binding to aptamer, and the amplified PEC signal was generated for "on" assay of TNF-α. Furthermore, Dam MTase as second target induced methylation of hairpin HDam, so it is cleaved by the endonuclease DpnI, resulting in the shedding of AIS/ZnS QDs signal probe for signal "off" detection of MTase. This work opened a new photosensitized probe and developed a promising PEC biosensor for dual-targets assay. By programming the DNA nanostructure, the biosensor can detect versatile targets in a simple and sensitive method, which has good practical application value in human serum.

Metal Salts of 4-Chloro-3,5-dinitropyrazole for Promising Eco-Friendly Primary Colors Pyrotechnics.

The construction and design of pyrotechnics with superior performance is not only a task of great significance but also a tremendous challenge. In this regard, we present the syntheses of novel green primary colors pyrotechnics (red, green, and blue light-generating pyrotechnics) by employing 4-chloro-3,5-dinitropyrazole (CDNP) as a multifunctional raw material. CDNP contains a flame enhancer, oxygen-rich functional group, and nitrogen heterocyclic combustibles, which contribute to the high performance of the pyrotechnics. The characteristic elements (strontium, barium, and copper) that impart color to the flame are combined with the CDNP to synthesize the primary colors pyrotechnics by an "all-in-one" strategy. The structures of three energetic metal salts (EMS-1, EMS-2, and EMS-3) are completely characterized, and their thermal stability, sensitivity, ignition performance, and color purity are systematically evaluated. All EMSs show excellent thermal stability and low mechanical sensitivities (>330 °C, >40 J, >360 N). Moreover, the EMSs demonstrate successful ignition and combustion under laser conditions and roasting test conditions, producing bright characteristic flames. Chromaticity analysis reveals that the three EMSs possess good color purities of 91, 80, and 70%, respectively. Consequently, the three integrated pyrotechnics exhibit exceptional combustion properties, highlighting their potential for use in various pyrotechnic applications.

Combining the advantages of 1,3,4-oxadiazole and tetrazole enables achieving high-energy insensitive materials.

Combining the advantages of energetic heterocycles to achieve high-energy insensitive explosives is a significant challenge. Herein, based on high-energy tetrazole rings and highly stable 1,3,4-oxadiazole rings, a series of novel nitrogen rich energetic compounds 5-9 were successfully constructed. The related compounds were fully characterized by EA, FT-IR, NMR, DSC, and MS, and compounds 6-9 were further confirmed by X-ray single crystal diffraction. Among them, the energetic ion salts 6-8 show high thermal stability (Tdec > 250 °C) and low mechanical sensitivity (IS > 40 J, FS > 360 N), as well as good energy properties (7552-8050 m s-1, 19.4-23.3 GPa). In particular, the azo compound 9 exhibits competent comprehensive performances (Tdec = 226.2 °C, D = 8502 m s-1, P = 28.9 GPa, IS = 32 J, FS = 320 N). These results suggest that the strategy of integrating tetrazole and 1,3,4-oxadiazole and employing an azo structure as a bridging unit are effective approaches to construct high-energy insensitive materials.

A multifunctional electrochemiluminescence and photoelectrochemical biosensor based on a quantum dot ion-exchange reaction for two-channel detection of thrombin.

Herein, a multifunctional electrochemiluminescence (ECL) and photoelectrochemical (PEC) biosensor based on exchange of Ag+ with CdTe QDs was developed for dual-mode detection of thrombin. First, CdTe QDs assembled on an electrode displayed superior ECL and PEC signals. At the same time, C-rich hairpin (HP) DNA linked to silicon spheres loaded a large amount of Ag+, and the specific binding of thrombin to an aptamer led to the release of DNA P; then, DNA P interacted with HP DNA to produce numerous Ag+ ions by an enzyme-digestion amplification reaction. Ag+ underwent ion exchange with CdTe QDs to generate AgTe/CdTe QDs, resulting in much reversed PEC and changed ECL signals for dual-mode detection of thrombin. This work takes advantage of outstanding multi-signals of QDs coupled with convenient ion exchange to achieve multi-mode detection of the target, avoiding false positive or false negative signals generated in the traditional detection process, and thus can be used for the rapid detection of various biomolecules in actual samples.

A multi-fused heat-resistant energetic compound constructed by hydrogen bonds.

The design of heat-resistant energetic compounds generally employs symmetry, planarity, and multi-hydrogen bonds to obtain compounds with high density, good thermal stability, and low sensitivity. In this paper, a heat-resistant hydrazine-bridged compound, 6,6'-(hydrazine-1,2-diyl)bis(5-nitropyrimidine-2,4-diamine) (PHP), was designed and synthesized with the strategy of multi-fused conjugated structure constructed by hydrogen bonds. The compound featured high symmetry, high planarity, and strong conjugation with good thermal stability (364 °C). This strategy provides a basis for the design of heat-resistant energetic compounds.

Splicing oxygen-rich multidentate ligands and characteristic metals to construct flame colorants: abundant structures and attractive colors.

Tetranitroethane (TNE), an energetic compound with high-nitrogen (N%, 26.7%) and oxygen (O%, 60.9%) content, is deprotonated by alkali and alkaline earth metal bases to form the corresponding metal salts of TNE which are characterized by FT-IR spectroscopy, elemental analysis, and single crystal X-ray diffraction. All the prepared energetic metal salts show excellent thermal stabilities, and the decomposition temperatures of EP-3, EP-4, and EP-5 are higher than 250 °C, due to the numerous coordination bonds of the complexes. Furthermore, the energy of formation of the nitrogen-rich salts were calculated utilizing heat of combustion. The detonation performances were calculated with the EXPLO5 software, and the impact and friction sensitivities were determined. EP-7 shows excellent energy performance (P = 30.0 GPa, VD = 8436 m s-1). EP-3, EP-4, EP-5, and EP-8 are more sensitive to mechanical stimulation. These alkali and alkaline earth metal salts of TNE show good monochromaticity by atomic emission spectroscopy (visible light), and may be used as potential flame colorants in pyrotechnics.

Phase transition-induced initial decomposition of nitrogen-rich binary CN compound 2,2'-azobis(5-azidotetrazole) and its precursor 2-amino-5-azidotetrazole via tetrazole ring opening under external electric fields: a comparative DFT-D study.

A comparative DFT-D study was performed to investigate the external electric field-induced crystal structures, electronic features, Hirshfeld surfaces, vibrational properties and initial decomposition mechanisms of nitrogen-rich binary CN compound 2,2'-azobis(5-azidotetrazole) (C2N16) and its precursor 2-amino-5-azidotetrazole (CH2N8). The results show that there exist phase transitions at the critical points of 0.006 a.u. and 0.008 a.u. for CH2N8 and C2N16, respectively, which are embodied in various properties of these compounds and induce their initial decomposition of the tetrazole ring opening via the breaking of N-N single bonds. The analysis of band gaps and density of states suggests the external electric field-induced enhancing ability for electron transition from the occupied orbitals to empty ones and N-N bond breaking may be the initial decomposition pathway for them. The variations in Hirshfeld surfaces indicate the spatial change and adjustment of non-bonding interactions in the two crystals. The discussions on vibrational properties indicate that IR characteristic peaks of all vibrational modes in the two crystals show a gradual red shift toward a low frequency region. The external electric field-induced initial decomposition pathways of both crystals are tetrazole ring opening via the breaking of a N-N single bond. Our findings provide insights for a comprehensive understanding of external electric field-induced phase transition and initial decomposition mechanisms of nitrogen-rich binary CN energetic compounds.

Synthesis, Crystal Structure, and Characterization of Energetic Salts Based on 3,5-Diamino-4H-Pyrazol-4-One Oxime.

In order to broaden the study of energetic cations, a cation 3,5-diamino-4H-pyrazol-4-one oxime (DAPO) with good thermal stability was proposed, and its three salts were synthesized by a simple and efficient method. The structures of the three salts were verified by infrared spectroscopy, mass spectrometry, elemental analysis, and single crystal X-ray diffraction. The thermal stabilities of the three salts were verified by differential scanning calorimetry and thermos-gravimetric analysis. DAPO-based energetic salts are analysed using a variety of theoretical techniques, such as 2D fingerprint, Hirshfeld surface, and non-covalent interaction. Among them, the energy properties of perchlorate (DAPOP) and picrate (DAPOT) were determined by EXPLO5 program combined with the measured density and enthalpy of formation. These compounds have high density, acceptable detonation performance, good thermal stability, and satisfactory sensitivity. The intermolecular interactions of the four compounds were studied by Hirshfeld surface and non-covalent interactions, indicating that hydrogen bonds and π-π stacking interactions are the reasons for the extracellular properties of perchlorate (DAPOP) and picrate (DAPOT), indicating that DAPO is an optional nitrogen-rich cation for the design and synthesis of novel energetic materials with excellent properties.

Electrochemiluminescence resonance energy transfer biosensing platform between g-C3N4 nanosheet and Ru-SiO2@FA for dual-wavelength ratiometric detection of SARS-CoV-2 RdRp gene.

Rational detection of syndrome coronavirus 2 (SARS-CoV-2) is crucial to prevention, control, and treatment of disease. Herein, a dual-wavelength ratiometric electrochemiluminescence (ECL) biosensor based on resonance energy transfer (RET) between g-C3N4 nanosheets and Ru-SiO2@folic acid (FA) nanomaterials was designed to realize ultrasensitive detection of SARS-CoV-2 virus (RdRp gene). Firstly, the unique g-C3N4 nanosheets displayed very intense and stable ECL at 460 nm, then the triple helix DNA was stably and vertically bound to g-C3N4 on electrode by high binding affinity between ssDNA and g-C3N4. Meanwhile, trace amounts of target genes were converted to a large number of output by three-dimensional (3D) DNA walker multiple amplification, and the output bridged a multifunctional probe Ru-SiO2@FA to electrode. Ru-SiO2@FA not only showed high ECL at 620 nm, but also effectively quenched g-C3N4 ECL. As a result, ECL decreased at 460 nm and increased at 620 nm, which was used to design a rational ECL biosensor for detection of SARS gene. The results show that the biosensor has excellent detection sensitivity for RdRp gene with a dynamic detection range of 1 fM to 10 nM and a limit of detection (LOD) of 0.18 fM. The dual-wavelength ratio ECL biosensor has inestimable value and application prospects in the fields of biosensing and clinical diagnosis.

Access to Green Pyrotechnic Compositions via Constructing Coordination Polymers: A New Approach to the Application of 3,4-Dinitropyrazole.

Alkali and alkaline-earth metal salts with 3,4-dinitropyrazole (DNP) were synthesized by the reaction of DNP with stoichiometric amounts of the corresponding metal hydroxide-, oxide-, or carbonate-based highly pure salts, and products were fully characterized. Determination of single-crystal structures of all new complexes except for the lithium and strontium salts was performed by X-ray diffraction techniques. The cesium salt crystallized no water among them. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) manifested that these salts have satisfactory thermal stabilities with decomposition temperatures above 210 °C. They also showed that there exists strong bonding of crystallized water among lattices, which disappeared at temperatures equal to or above 115 °C except for salts MES-3, MES-4, and MES-9. In addition, the percentage of water contents was confirmed by using DSC and TGA methods. The constant-volume combustion heats of these metal salts containing DNP anions were measured using an oxygen bomb calorimeter due to their expectant interest in energetic materials, and their standard molar formation enthalpies were obtained. The investigated salts were found to be insensitive toward friction and impact. Findings of burning tests performed with experimental formulations using MES-1, MES-7, MES-8, and MES-9 certify that these four salts might be more promising candidates for application in green pyrotechnics.

Energetic bimetallic complexes as catalysts affect the thermal decomposition of ammonium perchlorate.

Two bimetallic complexes of 4-hydroxy-3,5-dinitropyrazole, [K2Mn(DNPO)2(H2O)4]n·2H2O (BMEP-1) and [K2Zn(DNPO)2(H2O)6]n (BMEP-2), were synthesized and characterized by IR spectroscopy and elemental analysis. The crystal structures of BMEP-1 and BMEP-2 were determined by single-crystal X-ray diffraction. It is noteworthy that these complexes presented different metal-organic frameworks. The thermal behaviors of BMEP-1 and BMEP-2 were investigated by differential scanning calorimetry and thermogravimetric analysis measurements. These bimetallic complexes exhibited high thermal stability (348.0 °C and 331.0 °C) due to their large coordination bonds and three-dimensional interconnected structure. The catalytic performances of BMEP-1 and BMEP-2 on the thermal decomposition of ammonium perchlorate were investigated by TGA-DSC, TGA-FTIR, and non-isothermal kinetic analyses. The results showed that BMEP-1 and BMEP-2 exhibited excellent catalytic performance in the thermal decomposition of ammonium perchlorate. Notably, there was only a single exothermic peak at 302.6 °C and 318.6 °C, and the activation energy values of ammonium perchlorate decreased to 123.88 kJ mol-1 and 128.43 kJ mol-1, respectively. TGA-FTIR results showed that BMEP-1 and BMEP-2, as effective components of catalysis, will promote the production of H2O, N2O, NO2, and HCl in advance, during the thermal decomposition of ammonium perchlorate. BMEP-1 and BMEP-2 are expected to be two candidate additives for the catalytic decomposition of ammonium perchlorate in composite solid propellants.

Phase transition induced by an external electric field as a buffer to facilitate the initial decomposition of a series of catenated nitrogen energetic systems: a first-principles study.

The effect of an external electric field on the crystal and electronic structures, Hirshfeld surfaces, hydrogen-bonding network, mechanical properties, vibrational properties and initial decomposition mechanisms of a series of chain-catenated Nx (x = 4, 8, 10) energetic crystals was investigated via a first-principles study. The results indicate that the response behaviors to the external electric field show a great dependence on the nitrogen chain length and the intensity of the external electric field. The critical points of the phase transition were found and are embodied in various properties of all the compounds. Analysis of the electronic structures shows the increasing ability of the electron transition, thereby leading to possible subsequent decomposition reactions. The studies on Hirshfeld surfaces and the hydrogen-bonding network suggest that the external electric field can modify and tune the spatial distribution of the hydrogen-bonding network, thereby affecting the physicochemical properties. Our comprehensive analysis based on the mechanical properties, vibrational features and initial decomposition mechanism reveals that the external electric field can weaken the trigger bonds, reduce the thermal stability, and initiate decomposition. Our findings provide insights into the comprehensive understanding of the effects of an external electric field on energetic materials, especially for polynitrogen chain-catenated and even all-nitrogen compounds.

Construction of Coplanar Bicyclic Backbones for 1,2,4-Triazole-1,2,4-Oxadiazole-Derived Energetic Materials.

Combining different nitrogen-rich heterocycles into a molecule can fine-tune its energetic performance and physical properties as well as its safety for use in energetic materials. Here, 1,2,4-oxadiazole was incorporated into 1,2,4-triazole to construct new energetic backbones. 3-(5-Amino-1H-1,2,4-triazol-3-yl)-1,2,4-oxadiazol-5-amine (5) was designed and synthesized. Nitramino-functionalized N-(5-(5-amino-1,2,4-oxadiazol-3-yl)-3H-1,2,4-triazol-3-yl)nitramide (6) and N-(5-(5-(nitramino)-1,2,4-oxadiazol-3-yl)-3H-1,2,4-triazol-3-yl)nitramide (7) were also obtained, and two series of corresponding nitrogen-rich salts were prepared, leading to the creation of new energetic compounds. All derivatives were fully characterized, and five of them were further confirmed by X-ray diffraction. The theoretical calculations, energetic performance, safety, and the main decomposition gaseous products of 1,2,4-triazole-1,2,4-oxadiazole-derived energetic materials were studied. Compound 7 and its dihydroxylammonium salt (7 c) exhibited prominent detonation performance comparable to that of RDX while possessing satisfying thermal stabilities and mechanical sensitivities.

Diverse Synaptic Plasticity Induced by the Interplay of Ionic Polarization and Doping at Salt-Doped Electrolyte/Semiconducting Polymer Interface.

Pt/Ca2+-polyethylene oxide/polymer poly[3-hexylthiophene-2,5-diyl]/Pt devices were fabricated, and their pulse responses were studied. The discharging peak, represented by the postsynaptic current (PSC), first increases and then decreases with increasing input number in a pulse train. The weight of the PSC decreased for low-frequency stimulations but increased for high-frequency stimulations. However, the peak of the negative differential resistance during the charging process varied following the opposite trend. These behaviors suggested the ability for transferring the signal bidirectionally, confirming the equivalence between the ionic kinetics of our device and the transmitter kinetics of one kind of synapse. A facilitation (F)-depression (D) interplay model corresponding to the ionic polarization and doping interplay at the electrolyte/semiconducting polymer interface was adopted to successfully mimic the weight modification of the PSC. The simulation results showed that the observed synaptic plasticity was caused by the great disparity between the recovery time constants of F and D (τ F and τ D ). Moreover, such an interplay could inspire the features of responses to post-tetanic stimulations. Our study suggested a means to realize synaptic computation.

Home-based tele-supervising rehabilitation for brain infarction patients (HTRBIP): study protocol for a randomized controlled trial.

BACKGROUND: With high morbidity, mortality and disability rate, brain infarction brings a huge economic and health burden to the whole society in China. Although some previous studies suggested that telerehabilitation may facilitate rehabilitation for stroke survivors at home, the evidence is insufficient for clinical application; additionally, as yet no trial evaluates efficacy of telerehabilitation for brain infarction patients. Therefore, more high quality trials are needed to provide practice evidence for this novel rehabilitation strategy. METHODS/DESIGN: Based on recruitment criteria, this assessor blinded, paralleled randomized controlled trial will recruit 210 brain infarction patients. After being randomly allocated into two groups, participants will receive home-based tele-supervising rehabilitation or conventional rehabilitation. Outcome measurement will be conducted at the end of intervention and 90-day follow-up. Among which, Barthel index assessment will be considered as primary outcome measurement, secondary outcome measurements include NIHSS score, mRS score, 3-oz water swallow test and surface electromyography. Adverse events will also be recorded during the whole process of the trial for safety assessment. DISCUSSION: The HTRBIP trial will evaluate efficacy and safety of home-based tele-supervising rehabilitation for brain infarction patients. It is expected to provide new evidence for telerehabilitation application. TRIAL REGISTRATION: Registration date: 17 September 2014; REGISTRATION NUMBER: ChiCTR-TRC-14005233.

Controlling Ion Conductance and Channels to Achieve Synaptic-like Frequency Selectivity.

Enhancing ion conductance and controlling transport pathway in organic electrolyte could be used to modulate ionic kinetics to handle signals. In a Pt/Poly(3-hexylthiophene-2,5-diyl)/Polyethylene+LiCF3SO3/Pt hetero-junction, the electrolyte layer handled at high temperature showed nano-fiber microstructures accompanied with greatly improved salt solubility. Ions with high mobility were confined in the nano-fibrous channels leading to the semiconducting polymer layer, which is favorable for modulating dynamic doping at the semiconducting polymer/electrolyte interface by pulse frequency. Such a device realized synaptic-like frequency selectivity, i.e., depression at low frequency stimulation but potentiation at high-frequency stimulation.