Thermal characteristics of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate in contact with nitrocellulose/nitroglycerine under continuous heat flow

Dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) and nitrocellulose/nitroglycerine (NC/NG) possess good energy properties, which were widely used in propellants, explosives and pyrotechnics. They are easy to contact with each other during their application and storage. However, their thermal characteristics under continuous heat flow have not been reported yet. Therefore, it is of great practical significance to study the thermal properties of TKX-50/NC/NG (mixture of TKX-50 and NC/NG). In this paper, the thermal characteristics and pressure behaviors of TKX-50/NC/NG, TKX-50 and NC/NG were characterized by high pressure differential scanning calorimetry (HPDSC) and adiabatic scanning calorimetry (ASC). The results showed that TKX-50 and NC/NG can promote each other to decompose under continuous heat flow, especially the thermal decomposition which affected by gases generation and heat feedback was more violent in the confined space. The decomposition peak temperature of TKX-50/NC/NG shifted to low temperature when the heat loss was ignored and the removal of decomposition gas was suppressed. The possible decomposition mechanism of TKX-50/NC/NG was speculated. It was considered that the intermediate products of TKX-50 and NC/NG decomposition under thermal stimulation would react with each other, which promoted TKX-50/NC/NG decomposition in one step at lower temperature. Thus, TKX-50 has high reactivity and high potential risk after contact with NC/NG under continuous heat flow. TKX-50 is not suitable for application with NC/NG. This study provides a reference for the structural design of nitrogen rich explosives and further broadens the researchers’ understanding of the application of TKX-50.     

Enhanced photoactivity of CdS nanorods by MXene and ZnSnO3: Application in photoelectrochemical biosensor for the effect of environmental pollutants on DNA hydroxymethylation in wheat tissues

The photoactivity of CdS nanorods was greatly improved by amino functionalized accordion-like MXene and spherical ZnSnO₃. MXene possesses good electron transfer capability and ZnSnO₃ presents matched energy band with CdS, which deeply accelerate the electron transfer and prevent the recombination of photogenerated electron-hole pair, leading to a strong photoelectrochemical (PEC) response. Taking the merit of the improved photoactivity of CdS nanorods, a novel PEC biosensor was constructed for DNA hydromethylation detection based on immune recognition of target molecule, where 5-hydroxymethyl-2′-deoxycytidine triphosphate (5hmdCTP) was employed as detect target, CdS/MXene was used as photoactive material, and ZnSnO₃ was adopted as signal amplification unit. Under enzymatic covalent reaction of –CH₂OH of 5hmdCTP with –NH₂ of MXene, 5hmdCTP was specifically recognized and captured. Then, taking advantages of the covalent reaction between phosphate group of 5hmdCTP and ZnSnO₃, the signal amplification unit was captured. Under the optimum conditions, this PEC biosensor presents wide linear range of 0.008–100 nM and low detection limit of 4.21 pM (3σ). The applicability of the developed method was evaluated by investigating the effect of Cd²⁺ and perfluorohexane compound pollutant on 5-hydroxymethylcytosine content in the genomic DNA of the roots and leaves of wheat seedlings.     

One step nanoencapsulation of corrosion inhibitors for gradual release application

The direct application of corrosion inhibitors on metal surfaces is potentially dangerous for the environment and the restoration operators, thus new conservation strategies are mandatory. In this study, two copper corrosion inhibitors, 1H-benzotriazole (BTA) and 5-phenyl-1H-tetrazole (PT), are encapsulated in a silica nanocontainer, for future application in smart coatings, with the aim to reduce the amount of chemicals used in treatments, their dispersion in the environment and the direct exposure of the operators to these chemicals. In particular, composite silica nanocapsules, containing the corrosion inhibitors, are prepared via one-step synthesis, based on mini-emulsion polymerisation processes.The morphology, structure, and texture of these loaded silica nanocontainers are characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N₂ physisorption (BET/BJH). Micro-Raman spectroscopy (RS) is performed to characterise the composition. UV–visible spectroscopy and thermal analysis (TG/DSC) are performed for the loading and encapsulation efficiency (L%, EE%) study.Synthesised nanocapsules show a core-shell structure and, when loaded with the inhibitors, have size ranging from about 130 to 170 nm and a BET surface area of the order of 800 m²/g. The EE% is maximum in the case of BTA and decreases to ～52% in the case of PT.     

柠檬酸处理对ZSM-5分子筛甲缩醛气相羰基化性能的影响

采用柠檬酸对晶种法制备的低硅铝比ZSM-5纳米晶聚集体进行改性处理,并将其应用于催化甲缩醛(DMM)气相羰基化合成甲氧基乙酸甲脂(MMAc)反应.结果表明,通过调控柠檬酸处理时间可以有效地改进所制备ZSM-5分子筛的催化羰基化性能.其中,使用0.2 mol/L柠檬酸在80℃下处理12 h后的ZSM-5分子筛可获得59.5%DMM转化率和59.3%的MMAc选择性,MMAc收率从16.9%提高到35.3%.通过SEM、 TEM、 ICP、 N_2-BET、 Py-FTIR、 NH_3-TPD等表征手段对分子筛进行详细表征分析,发现适当调控柠檬酸处理时间,可使得纳米晶聚集体ZSM-5分子筛酸强度降低,并暴露出更多的中强B酸位点,同时增大分子筛比表面积及孔道体积.酸性位点的增多促使DMM转化率提高,而酸强度的降低、比表面积及孔道体积的增加,有助于调控中间物种的反应路径及扩散程度,进而抑制部分副反应,提高目标产物MMAc的选择性.     

混合熔盐法低温合成Sm2Ti2S2O5及其光催化分解水产氢

以TiO2、TiS2及Sm2O3为前驱体,分别加入LiCl-KCl与LiCl-CsCl的最低共熔混合物作为熔盐,在较低温度下成功合成了Sm2Ti2S2O5(STSO)颗粒。通过对比不同温度下所制备产物的X射线衍射图,首次表明STSO的热力学结晶温度在520℃左右,远低于之前报道的650℃的最低合成温度。扫描电子显微镜照片显示,采用2种混合熔盐制备的STSO都呈片状形貌;同一合成温度下,采用LiCl-CsCl熔盐制备的STSO的厚度小于LiCl-KCl所得产物。采用出射光波长大于420 nm的氙灯作为光源,在含有Na2S-Na2SO3空穴牺牲剂的溶液中,所制备的STSO颗粒表现出最高35μmol·h-1的光催化分解水产氢活性以及20 h以上的产氢稳定性。     

The regulation of biothiol-responsive performance and bioimaging application of benzo[c][1,2,5]oxadiazole dyes

The different oxidation states of sulphur atom play a significant role on functional materials. In this work, a aryl-thioether and its sulphone substituted benzo[c][1,2,5]oxadiazole dyes were synthesized and utilized to determine thiol-containing amino acids. The result of selectivity experiments showed they detected the cysteine and homocysteine under physiological condition with negligible interference from other amino acids. In comparison to the thioether dye, the sulphone-based dye exhibited much faster response time for Cys and Hcy. However, the sulphone restricted its thiol-reactivity and bioimaging performance in living cells. By reducing the oxidation state of sulphur atom, we amazedly found that the sulfoxide-based dye still maintained high selectivity ultrafast response time for Cys/Hcy under physiological condition. It was worth mentioning that it also had high reactivity and good bioimaging performance that sulfone compounds did not have.     

The synergistic catalysis on Co nanoparticles and CoN_x sites of aniline-modified ZIF derived Co@NCs for oxidative esterification of HMF

An efficient sustainable and scalable strategy for the synthesis of porous cobalt/nitrogen co-doped carbons(Co@NCs) via pyrolysis of aniline-modified ZIFs,has been demonstrated.Aniline can coordinate and absorb on the surface of ZIF(ZIF-CoZn3-PhA),accelerate the precipitation of ZIFs,thus resulting in smaller ZIF particle size.Meanwhile,the aniline on the surface of ZIF-CoZn3-PhA promotes the formation of the protective carbon shell and smaller Co nanoparticles,and increases nitrogen content of the catalyst.Because of these prope rties of Co@NC-PhA-3,the oxidative esterification of 5-hydroxymethylfurfural can be carried out under ambient conditions.According to our experimental and computational results,a synergistic catalytic effect between CoN_x sites and Co nanoparticles has been established,in which both Co nanoparticles and CoN_x can activate O_2 while Co nanoparticles bind and oxidize HMF.Moreover,the formation and release of active oxygen species in CoN_x sites are reinfo rced by the electronic interaction between Co nanoparticles and CoN_x.     

Enhanced conversion of α-cellulose to 5-HMF in aqueous biphasic system catalyzed by FeCl_3-CuCl_2

This study was to investigate the optimal additions of the cellulose decomposition reaction to obtain the most yield of 5-HMF and other furan derivatives in various biphasic systems with FeCl_3-CuCl_2 mixed catalysts,and explore its depolymerization kinetics.A series of controllable reactions have been performed under mild environmentally friendly atmosphere.The experiment results showed that49.13 wt% of 5-HMF was the maximum production along with 2.98 wt% other furan derivatives catalyzed by mixed Lewis acid FeCl_3-CuCl_2 under the two phases which included high concentration NaCl aqueous phase and n-butanol organic phase at 190℃ for 45 min.The conclusion suggested that two-phase systems benefited the yield of 5-HMF,furan derivatives via extracting the target products from reaction phase to organic phase to avoid rehydration of 5-HMF.The kinetic calculation revealed the conversion with mixed catalysts had lower reaction apparent activation energy(21.65 kJ/mol,190-230℃) and the reaction rate was faster than that with acid-based catalysts.Based on experiment exploration,the probable mechanism of cellulose decomposition with FeCl_3-CuCl_2 was proposed.     

Comparative study of Co3O4-ZSM-5 catalysts synthesized by different hydrothermal methods for the catalytic oxidation of dichloromethane

In this work, various Co₃O₄-ZSM-5 catalysts were prepared by the microwave hydrothermal method (MH-Co₃O₄@ZSM-5), dynamic hydrothermal method (DH-Co₃O₄@ZSM-5), and conventional hydrothermal method (CH-Co₃O₄/ZSM-5). Their catalytic oxidation of dichloromethane (DCM) was analyzed. Detailed characterizations such as X-ray diffractometer (XRD), scanning microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET), H₂ temperature-programmed reduction (H₂-TPR), temperature-programmed desorption of O₂ (O₂-TPD), temperature-programmed desorption of NH₃ (NH₃-TPD), diffuse reflectance infrared Fourier-transform spectra with NH₃ molecules (NH₃-DRIFT), and temperature-programmed surface reaction (TPSR) were performed. Results showed that with the assistance of microwave, MH-Co₃O₄@ZSM-5 formed a uniform core-shell structure, while the other two samples did not. MH-Co₃O₄@ZSM-5 possessed rich surface adsorbed oxygen species, higher ratio of Co³⁺/Co²⁺, strong acidity, high reducibility, and oxygen mobility among the three Co₃O₄-ZSM-5 catalysts, which was beneficial for the improvement of DCM oxidation. In the oxidation of dichloromethane, MH-Co₃O₄@ZSM-5 presented the best activity and mineralization, which was consistent with the characterizations results. Meanwhile, according to the TPSR test, HCl or Cl₂ removal from the catalyst surface was also promoted in MH-Co₃O₄@ZSM-5 by their abundant Brønsted acid sites and the promotion of Deacon reaction by Co₃O₄ or the synergistic effect of Co₃O₄ and ZSM-5. According to the results of in situ DRIFT studies, a possible reaction pathway of DCM oxidation was proposed over the MH-Co₃O₄@ZSM-5 catalysts.     

CO2 and photo-controlled reversible conversion of supramolecular assemblies based on water soluble pillar[5]arene and coumarin-containing guest

In this communication,a new supramolecualr amphiphile was successfully constructed based on water soluble pillar[5]arene and a unique guest which contain a CO₂ responsive tertiary amine unit and a UV responsive coumarin group.When guest molecule 1 dispersed in water,it self-assembled into sheet-like structures.Upon bubbling CO₂,1 transformed into 1 H due to the tertiary amine unit was protonated,accompany the nano-sheets transformed into vesicles.Further irradiation of 1 H with 365 nm light for 3 h,the coumarin group reacted with each other to form bola-type amphiphie 2 H.In this case,vesicles collapsed and re-assembled into nano-tubes.However,when addition of WPS into the solution of 1 H,the vesicles transformed into micelles,this is due to the formation of supramolecular amphiphile WP5&1 H.Upon irradiation of WP5&1 H with 365 nm light for 3 h,nano-ribbons observed instead of micelles in the solution.Notably,nanotubes from 2 H could also transform into nano-ribbons after adding WPS.The selfassembly process and the resultant assemblies were characterized by TEM,SEM,DLS,SAXS and NMR technologies.Due to both CO₂ and light are "green" for living organisms,we anticipated our system can offer the possibilities in "on demand" drug absorption and release.