Highly Stable Univalent Copper of a Cu@Al/SBA-15 Nanocomposite Catalyzes the Synthesis of Fluorescent Aminobenzotriazoles Derivatives

With the development of green chemistry, it is still a challenge to maintain the unstable valence state of the metal in heterogeneous catalysts and realize new catalytic synthesis methods. In this paper, it is reported that an univalent copper nanocomposite (Cu@Al/SBA-15) can efficiently catalyze the formation of novel amino-containing benzotriazoles with great fluorescence properties in a new synthetic strategy. Subsequently, its application is further verified by an acylation reaction to produce a series of novel benzotriazoles derivatives with high yield. It is worth noting that the Cu@Al/SBA-15 nanocomposites not only enable the reaction completed with high yield in a short time, but can also be recycled many times without a significant reduction in activity, and the leaching of copper and aluminum species in reaction system is negligible. Finally, the detailed and feasible reaction mechanism is also provided.     

新型暂堵酸化用自降解暂堵剂的制备及现场应用

针对传统暂堵酸化用暂堵剂颗粒耐酸性差、降解性差和除堵工艺复杂等问题，本研究通过水溶液自由基聚合法制备了一种新型的自降解暂堵剂CQZDJ。考察了单体加量、交联剂加量、引发剂加量对CQZDJ凝胶强度和降解性的影响；通过FT-IR、TGA、SEM对其结构进行表征；并对其降解机理进行了探讨；最后在长8区块的环平81-8实验井进行了现场实践。结果表明：CQZDJ凝胶强度及降解时间与单体加量、交联剂加量、引发剂加量成正比关系，且降解时间可控；降解性实验表明CQZDJ在(1%~10%)HCl溶液、水、（2%~10%）NaCl溶液中均可在4 d内完全降解，具备良好的降解性能，对地层伤害小；SEM照片显示CQZDJ的降解过程是从初始三维网状结构逐渐崩解为层状结构，最终降解为无规则线性小分子链的过程；暂堵后现场流压上升6.3 MPa，日产油由3.87 t/d增产至5.22 t/d，实现了储层的有效改造，增产效果显著。      

Combination of a modified quick,easy, cheap,efficient, rugged,and safe extraction method with a deep eutectic solvent based microwave‐assisted dispersive liquid–liquid microextraction: Application in extraction and preconcentration of multiclass pesticide residues in tomato samples

In this study, a new two–step extraction procedure based on the combination of a modified quick, easy, cheap, effective, rugged, and safe extraction method with a deep eutectic solvent based microwave‐assisted dispersive liquid–liquid microextraction has been developed for the extraction of multiclass pesticides in tomato samples before their analysis by gas chromatography with flame ionization detection. In this method, initially, an aliquot of tomato is crushed and diluted with deionized water. The mixture is then passed through a filter paper and its residue and aqueous phase are separated. Afterwards, acetonitrile as an extraction/disperser solvent is passed through the filter paper containing the refuse. The analytes remained in the refuse are extracted into the acetonitrile and then the obtained extract is mixed with a deep eutectic solvent. The obtained mixture is injected into the tomato juice and placed in a microwave oven for 15 s. Consequently, a cloudy state is formed and the extractant containing the analytes are sedimented at the bottom of the tube after centrifugation. Finally, 1 μL of the sedimented phase is removed and injected into the separation system. Under the optimum conditions, limits of detection and quantification were in the ranges of 0.42–0.74 and 1.4–2.5 ng/g, respectively.     

Cyclohexane‐1,3‐dione as a derivatizing agent for the analysis of aldehydes by micelar electrokinetic chromatography with diode array detection

Aldehydes are important compounds in a large number of samples, especially food and beverages. In this work, for the first time, cyclohexane‐1,3‐dione (CHD) was used as a derivatizing reagent aiming aldehyde (formaldehyde, acetaldehyde, propionaldehyde, and valeraldehyde) analysis by MEKC‐DAD. The optimized separation of the derivates was performed using a voltage program (+20 kV, 0–15 min.; +23 kV, 15–17 min.) at a temperature of 26°C, and using as the running buffer a mixture containing 100 mmol/L of sodium dodecyl sulfate and 29 mmol/L of sodium tetraborate at pH 9.2, with maximum absorbance at 260 nm. CHD was compared with two other derivatizing agents: 3‐methyl‐2‐benzothiazolinone hydrazone and phenylhydrazine‐4‐sulfonic acid. The CHD‐aldehyde derivatives were also characterized by LC‐MS. The calibration curves for all aldehydes had r² above 0.999 and LODs ranged from 0.01 to 0.7 mg/L. The optimized methodology was applied in sugar cane brandy (cachaça) samples successfully. CHD showed to be an alternative derivatization reagent due to its stability, aqueous solubility, high selectivity and sensitivity, reduced impurities, and simple preparation steps.     

Zinc(II)-poly(urea-formaldehyde) supported on magnetic nanoparticles: A hybrid nanocatalyst for green synthesis of spiropyrans,spiroxanthenes, and spiropyrimidines

Immobilization of metal ions onto inorganic supports has very interesting biological, industrial, and catalysis applications. In this study, CoFe₂O₄@SiO₂@PUF@Zn(OAc)₂ nanostructure was successfully fabricated by immobilization of zinc acetate on the surface of poly(urea-formaldehyde) supported on magnetic CoFe₂O₄@SiO₂ nanoparticles through a layer-by-layer assembly. The structure of hybrid nanoparticles was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, energy-dispersive X-ray spectroscopy, inductively coupled plasma atomic emission spectroscopy, vibrating sample magnetometry, Brunauer–Emmett–Teller surface area analysis, scanning electron microscopy, and transmission electron microscopy. Zinc-poly(urea-formaldehyde) supported on magnetic nanoparticles (MNPs@SiO₂@PUF@Zn) was successfully used for the synthesis of spirooxindolopyran and spirooxindoloxanthene derivatives in aqueous medium as an environmentally benign condition. High yields, short reaction times, green solvent, reusability without significant reduction in catalytic activity, and simple separation of the catalyst using an external magnet along with environmental compatibility are some benefits of this procedure.     

Stepwise optimization and sensitivity improvement of green micellar electrokinetic chromatography method to simultaneously determine some fluoroquinolones and glucocorticoids present in various binary ophthalmic formulations

A sensitive micellar electrokinetic chromatography method is presented to simultaneously quantify ofloxacin, gatifloxacin, dexamethasone sodium phosphate and prednisolone acetate. The method has the advantages of being rapid, accurate, reproducible, ecologically acceptable and sensitive. The electrophoretic separation utilized 20 mm borate buffer as background electrolyte with pH 10.0 ± 0.1 and 50 mm sodium dodecyl sulfate as a micelle forming molecule. A capillary tube (50 μm i.d., 33 cm) of fused silica was used and on-column diode array detection at 243 nm for dexamethasone sodium phosphate and prednisolone acetate, and 290 nm for ofloxacin and gatifloxacin. Various factors were optimized such as the background electrolyte (type, concentration and pH), addition of sodium dodecyl sulfate and its concentration, detection wavelength, applied voltage and injection parameters. The studied drugs were efficiently separated in 6.2 min, at 20 kV with high resolution. The greenness of the method was estimated using an eco-scale tool and the presented method was found to have excellent green characteristics. The method was validated in conformance with International Conference on Harmonization guidelines, with acceptable accuracy, precision and selectivity. The suggested method can be employed for the economic analysis of the four drugs in dissimilar binary combinations of eye drops saving solvents and chemicals.     

Lipase‐Supported Metal–Organic Framework Bioreactor Catalyzes Warfarin Synthesis

A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase‐supported metal–organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors.     

Development of a PRiME cartridge purification method for rapid determination of malachite green and leucomalachite green in Chinese softshell turtle

A high‐throughput PRiME (process, robustness, improvements, matrix effects, ease of use) sample purification procedure was developed to simplify the multiple steps of traditional SPE in extracting the malachite green and leucomalachite green in Chinese softshell turtle (Pelodiscus sinensis). The sample loading volume, extracting solvent type, and pH value of the employed PRiME hydrophilic‐lipophilic balance cartridge for sample purification were optimized to be 3 mL, acetonitrile, and pH 5, respectively. In comparison with traditional SPE, the PRiME process is cost‐effective, solvent‐saving, and simple to operate, which only consists of a passing through step without traditional sorbent conditioning and impurity washing. Afterward, eluate was analyzed by ultra‐performance liquid chromatography‐tandem mass spectrometry, and the proposed method was validated for linearity (R² > 0.9992), intraday precision (2.44–3.22%), interday precision (3.28–6.58%), sensitivity (LOD ≤ 0.18 μg/kg and, LOQ ≤ 0.60 μg/kg), and recovery (88.7–94.1%, RSD < 6.79%). The results indicated that the PRiME technique can simplify the sample preparation procedure by avoiding the tedious steps, such as conditioning, washing, etc. It would be of significant interest for environmental and food safety applications in the market of Chinese softshell turtle and related products.     

SiNWs:Tb3+的光学稳定性及Si纳米线对其发光特性的影响

荧光纳米材料不但具备纳米材料的优势，同时还具有优异的光学性质，被广泛应用于荧光标记、离子识别、荧光免疫分析、光学成像和医学诊断等方面。因此，荧光纳米材料的制备、结构分析和荧光特性等方面的研究备受人们的关注。为了获得发光强度大、荧光量子效率高和制备过程可控的Si基荧光纳米材料，实验进一步研究了Si纳米线对样品发光特性的影响和样品的光学稳定性。首先，基于固-液-固生长机制，在反应温度为1 100 ℃、N₂气流量为1 500 sccm、生长时间为15～60 min等工艺条件下，分别以“抛光”和“金字塔”织构表面的单晶Si(100)为衬底，生长出不同长度和分布的Si纳米线；以Au或Au-Al合金膜层作为金属催化剂，生长出密度分别约为108和1010 cm-2的Si纳米线；然后，利用L4514自动控温管式加热炉，基于高温固相法，在温度为1 100 ℃、掺杂时间为60 min和N₂气流量为1 000 sccm等工艺条件下，以高纯Tb₄O₇(99.99%)粉末为稀土掺杂剂对不同Si纳米线衬底进行稀土掺杂，制备一系列的荧光纳米材料SiNWs:Tb3+样品；室温下利用Hitachi F-4600型荧光分光光度计，固定激发光波长为243 nm、激发光狭缝为2.5 nm、发射光狭缝为2.5 nm、扫描波长范围为450～650 nm、光电倍增管(photomultiplier lube, PMT)电压为600 V等参数下，测量了不同样品的光致发光特性；最后，实验测试了该荧光纳米材料的光学稳定性，如时间(0～30 d)、温度(300～500 K)、酸碱(pH 1和11)、抗光漂白(0～120 min)等稳定性以及水溶性和分散性。结果显示，在衬底为“金字塔”织构表面上、生长时间为30 min、以Au为金属催化剂等条件下制备的Si纳米线为Tb3+掺杂衬底时，SiNWs:Tb3+的绿光发射强度较大，其发光强峰值位于554 nm，属于能级5D₄→7F₅的跃迁，另外在波长为494，593和628 nm出现了三条发光谱带，它们分别属于能级5D₄→7F₆，5D₄→7F₄和5D₄→7F₃的跃迁。另外，样品展示出了优异的时间、温度、酸碱和抗光漂白等光学稳定性，同时还具有良好的水溶性和分散性。如温度升高到500 K时，光发射强度仅降低了约8.9%左右；抗光漂白能力较强，用波长为365 nm、功率为450 W的紫外光源照射120 min，样品的绿光发射强度无衰减；酸、碱稳定性好，在pH 1的强酸(HCl)溶液中120 min未见衰减，在pH 11的强碱(NaOH)溶液中15 min内衰减较小, 随后发光强度出现了缓慢下降的趋势；当60 min后，样品的发光强度变得极其微弱。分析认为，在SiNWs:Tb3+表面有一层SiO₂包覆层，而NaOH溶液容易和SiO₂发生化学反应，随着时间延长SiO₂层被破坏，故样品发光强度降低；样品溶于水中放置30 d未见沉淀物，发光亮度均匀且分散性较好。在研究了制备温度、气体流量和掺杂时间等工艺条件之后，深入研究了Si纳米线自身变化对Tb3+绿光发射的影响。该材料展示出了良好的光学稳定性、水溶性和分散性，使其作为荧光标记物具有一定的应用价值。     

Recyclable and reusable Pd(OAc)2/PPh3/PEG‐2000 system for homocoupling reaction of arylboronic acids under air without base

A stable and efficient Pd(OAc)₂/PPh₃/PEG‐2000 catalytic system for homocoupling of arylboronic acids has been developed. In the presence of Pd(OAc)₂ and PPh₃, the homocoupling reaction of arylboronic acids was carried out smoothly in PEG‐2000 at 70 °C under air without base to afford a variety of symmetric biaryls in good to excellent yields. The isolation of the products was readily performed by extraction with diethyl ether, and the Pd(OAc)₂/PPh₃/PEG‐2000 system could be easily recycled and reused six times without significant loss of catalytic activity. Copyright © 2014 John Wiley & Sons, Ltd.