Palladium-catalyzed vinylation of indoles with vinyl ethers via deoxygenative coupling

Indole is a promising heteroarene in many natural products and pharmaceuticals;therefore, various synthetic methods for indole functionalizations have arisen in recent years. Herein, we report a Pd-catalyzed deoxygenative coupling for the N-vinylation of indoles by employing vinyl ethers. The vinylated indoles could be readily prepared in good to excellent yields with N1-regioselectivity regardless of the electronic characteristics and substitution patterns of indole substrates. Some indole-based pharmaceutical molecules, such as gramine, evodiamine, rutaecarpine, and melatonine, are also successfully vinylated. Moreover, carbazoles and indazoles are shown to participate. Additionally, vinylated indole can readily transform into structurally interesting indole derivatives.

固体磷酸催化竹屑液化的反应机理

固体磷酸为催化剂液化竹屑制备生物基多元醇,利用FT-IR、GC-MS、NMR等技术和方法对液化产物组成进行了表征,研究其反应机理。研究结果表明:Vinyl ethyl carbitol等烯烃类的生成主要是通过固体磷酸催化PEG400一端脱去羟基形成的,而戊二酸物质等物质主要是由固体磷酸催化纤维素等生物质通过氧化重排而形成,除此之外,固体磷酸还解决液化产物酸值高的问题。

Innovative approach to boosting the chemical stability of AZ31 magnesium alloy using polymer-modified hybrid metal oxides

Meeting the demands of complex and advanced applications requires the development of high-performance hybrid materials with unique properties.However,the integration of polymeric frameworks with MgO/WO_(3) composite layers faces challenges due to the lack of understanding of the formation mechanism and the challenge of determining the impact of self-assembled architecture on anticorrosive properties.In this study,we aimed to enhance the corrosion resistance of the MgO layer produced by plasma electrolysis(PE)of AZ31 Mg alloy by incorporating WO_(3) with partially phosphorated poly(vinyl alcohol)(PPVA).Two types of porous MgO layers were produced using the PE process with an alkaline-phosphate electrolyte,one with and one without WO_(3) nanoparticles,which were subsequently immersed in an aqueous solution of PPVA.Incorporating PPVA into the WO_(3)-MgO layer resulted in hybrids being deposited in a fragmented manner,creating a“laminar reef-like structure”that sealed most of the structural defects in the layer.The PPVA-sealed WO_(3)-based coating exhibited superior corrosion resistance compared to the other samples.Computational analyses were employed to explore the mechanism underlying the formation of PPVA/WO_(3) hybrids on the MgO layer.These findings suggest that PPVA-WO_(3)-MgO hybrid coatings can potentially improve corrosion resistance in various fields.

A comparative study for petroleum removal capacities of the bacterial consortia entrapped in sodium alginate,sodium alginate/poly(vinyl alcohol),and bushnell haas agar

The purpose of this study was to identify and compare the degradation efficiencies of free and entrapped bacterial consortia(Staphylococcus capitis CP053957.1 and Achromobacter marplatensis MT078618.1)to different polymers such as Sodium Alginate(SA),Sodium Alginate/Poly(Vinyl Alcohol)(SA/PVA),and Bushnell Haas Agar(BHA).In addition to SA and SA/PVA,which are cost-effective,non-toxic and have different functional groups,BHA,which is frequently encountered in laboratory-scale studies but has not been used as an entrapment material until now.Based on these,the polymers with different surface morphologies and chemical compositions were analyzed by SEM and FT-IR.While the petroleum removal efficiency was higher with the entrapped bacterial consortia than with the free one,BHA-entrapped bacterial consortium enhanced the petroleum removal more than SA and SA/PVA.Accordingly,the degradation rate of bacterial consortia entrapped with BHA was 2.039 day^(-1),SA/PVA was 1.560,SA was 0.993,the half-life period of BHA-entrapped bacterial consortia is quite low(t_(1/2)=0.339)compared with SA(t_(1/2)=0.444)and SA/PVA(t_(1/2)=0.697).The effects of the four main factors such as:amount of BHA(0.5,1,1.5,2,2.5,3 g),disc size(4,5,6,7,8 mm),inoculum concentration(1,2.5,5,7.5,10 mL),and incubation period on petroleum removal were also investigated.The maximum petroleum removal(94.5%)was obtained at≥2.5 mL of bacterial consortium entrapped in 2 g BHA with a 7 mm disc size at 168 h and the results were also confirmed by statistical analysis.Although a decrease was observed during the reuse of bacterial consortium entrapped in BHA,the petroleum removal was still above 50%at 10th cycle.Based on GC-MS analysis,the removal capacity of BHA-entrapped consortium was over 90%for short-chain n-alkanes and 80%for medium-chain n-alkanes.Overall,the obtained data are expected to provide a potential guideline in cleaning up the large-scale oil pollution in the future.Since there has been no similar study investigating petroleum removal with the bacterial consortia entrapped with BHA,this novel entrapment material can potentially be used in the treatment of petroleum pollution in advanced remediation studies.

Polyurethane Hybrid-Based Wood Adhesive: Review

Based on commercially available polyvinyl alcohol (PVA) stabilised polyvinyl acetate (PVAc), emulsion adhesives are neither heat nor moisture-resistant and show weak strength at high relative humidity and high temperatures. Pre- or post-crosslinking is another method used to manufacture a conventional vinyl-based homopolymers or copolymers system with improved water resistance. Vinyl neodecanoate (VeoVa), N-methylolacrylamide (NMA), Methacrylamide, methacrylic acid (MAA), and other self-crosslinking comonomers are typically inserted to produce highly water-resistant vinyl based homopolymers or copolymers. Additionally, organic crosslinkers like glyoxal, glutaraldehyde, citric acid, tartaric acid, and the like, as well as inorganic crosslinkers like acidic metal salts like aluminium chloride, aluminium nitrate, boric acid, and the like, can be used to prepare the highly water-resistant vinyl based homopolymers or copolymers. It is also possible to combine the self-crosslinking comonomers with the organic crosslinkers. Recently, a different hybrid chemistry has been developed that improves lap shear strength, has outstanding water resistance, good durability, and doesn’t require any additional crosslinker agents. Two distinct polymers were combined to develop hybrid polymers. They usually involve mixing an organic polymer with a polymer. There are many capping agents that are used for polyurethanes to produce acrylics that are capped with polyurethane and used as an oligomer in PVAc wood glue. Here, in this paper, we reviewed the different hybrid chemistry based on polyurethane chemistry for wood bonding applications.

gem-Difluorovinylation of alkynyl bromoarenes via dual nickel-/palladium-catalyzed crosselectrophile coupling

A dual nickel-/palladium-catalyzed gem-difluorovinylation of alkynyl bromoarenes is presented.This method proceeds smoothly to afford various dihydrobenzofuran compounds containing gem-difluorovinyl fragments with excellent stere-oselectivities in moderate to excellent yields.This strategy also features good functional group tolerance.Mechanistic studies reveal that the C-OTs bond and C-Br bond are selectively oxidative-added by nickel and palladium complexes respec-tively,and palladium is the center metal in the reductive elimination step.

Embolization of brain arteriovenous malformations with squid co-polymer embolic material:Initial experience

Objective:To analyze the safety and effectiveness of the ethylene-vinyl alcohol copolymer(EVOH)liquid embolic agent Squid(Emboflu,Switzerland)for the treatment of brain arteriovenous malformations.Materials and procedures:Between April 2015 and July 2017,46 embolization treatments for brain arteriovenous malformations(BAVM)were performed in 25 patients using two Squid formulations(18 and 12).Six female and 19 male patients with a mean age of 34 years(range,9–62 years)were included.A total of 46 procedures were performed.The BAVMs were classified as Spetzler-Martin gradeⅡin 4 procedures,Ⅲin 27 procedures,and 1V in 15 procedures.Among the 25 patients,15 presented with hemorrhage,5 with seizures,and 5 with headache and neurology.The BAVMs were located in the temporal lobe in 5 patients,parietal lobe in 7 patients,frontal lobe in 3 patients,posterior fossa in 6 patients,basal ganglia in 3 patients,and parasagittal lobe in 1 patient.Results:The obliteration rate of the BAVMs ranged from 10%to 100%,with a mean of 33%.Most patients underwent their first or second embolization procedure.Four patients(8%)developed intracranial bleeding post procedure,with one death(2%).One patient(2%)experienced a seizure during the procedure;however,no intracranial bleeding was observed.Seven patients(15%)experienced perforations during catheter manipulation.One case(2%)of fractured catheter was recorded,but no significant complications were observed.The average volume of copolymer injected was 0.6 ml per nidus.Thirteen procedures used the Squid-12 formulation,29 procedures used the Squid-18 formulation,and 3 procedures used a combination of Squid-12 and-18 formulations.Conclusion:Squid is a safe and effective embolic agent for treating BAVMs.

Improving physical properties of poly(vinyl alcohol)/montmorillonite nanocomposite hydrogels via the Hofmeister effect

Hydrogel is a kind of three-dimensional crosslinked polymer material with high moisture content.However,due to the network defects of polymer gels,traditional hydrogels are usually brittle and fragile,which limits their practical applications.Herein,we present a Hofmeister effect-aided facile strategy to prepare high-performance poly(vinyl alcohol)/montmorillonite nanocomposite hydrogels.Layered montmorillonite nanosheets can not only serve as crosslinking agents to enhance the mechanical properties of the hydrogel but also promote the ion conduction.More importantly,based on the Hofmeister effect,the presence of(NH_(4))_(2)SO_(4)can endow nanocomposite hydrogels with excellent mechanical properties by affecting PVA chains'aggregation state and crystallinity.As a result,the as-prepared nanocomposite hydrogels possess unique physical properties,including robust mechanical and electrical properties.The as-prepared hydrogels can be further assembled into a high-performance flexible sensor,which can sensitively detect large-scale and small-scale human activities.The simple design concept of this work is believed to provide a new prospect for developing robust nanocomposite hydrogels and flexible devices in the future.

Graphene quantum dots doped poly(vinyl alcohol)hybrid membranes for desalination via pervaporation

Pervaporation desalination by highly hydrophilic materials such as poly(vinyl alcohol)(PVA)based separation membrane is a burgeoning technology of late years.However,the improvement of membrane flux in pervaporation desalination has been a difficult task.Here,a novel hybrid membrane with doped graphene oxide quantum dots(GOQDs)which is rich in hydrophilic groups and small size into the matrix of PVA was prepared to improve the membrane flux.The membranes structures were described by field emission scanning electron microscopy(FESEM),atomic force microscopy(AFM),Fourier transform infrared(FT-IR),differential scanning calorimetry(DSC),thermogravimetric analysis(TGA)and X-ray diffraction(XRD).And more,Water contact angle,swelling degree,and pervaporation properties were carried out to explore the effect of GOQDs in PVA matrix.In addition,GOQDs content in the hybrid membrane,NaCl concentration,and feed temperature were investigated accordingly.Moreover,the hydrogen bonds between PVA chains were weakened by the interaction between GOQDs and PVA chains.Significantly,the hybrid membrane with optimized doped GOQDs content,200 mg·L^(-1),displays a high membrane flux of 17.09 kg·m^(-2)·h^(-1)and the salt rejection is consistently greater than 99.6%.

Regulating the Localization of Intumescent Flame Retardant for Improving the Flame Retardancy of Ethylene-vinyl Acetate Copolymer Using Polyamide 6 as a Charring Agent

Polyamide 6 (PA6) was employed as a charring agent of intumescent flame retardant (IFR) to improve the flame retardancy of ethylene-vinyl acetate copolymer (EVA). Different processing procedures were used to regulate the localization of IFR in the EVA matrix. Localizations in which IFR was dispersed in the PA6phase or in the EVA phase were prepared. The effect of the localization of IFR on the flame retardancy of EVA was investigated. The limited oxygen index (LOI), vertical burning (UL 94) and cone calorimeter test (CCT)showed that the localization of IFR in the EVA matrix exhibited a remarkable influence on the flame retardancy.Compared with EVA/IFR, a weak improvement in the flame retardancy was observed in the EVA/PA6/IFR blend withthe localization of IFR in the PA6 phase. When IFR was regulated from the PA6 phase to the EVA matrix,a remarkable increase in the flame retardancy was exhibited. The LOI was increased from 27.8%to 32.7%, and the UL 94 vertical rating was increased from V-2 to V-0. Moreover, an approximately 41.36%decrease in the peak heat release rate was exhibited. A continuous and compact intumescent charring layer that formed in the blends with the localization of IFR in the EVA matrix should be responsible for its excellent flame retardancy.

The Promoting Effect of Multifunctional Groups on the Thermal and Mechanical Properties of PVC Materials

The development of PVC materials grafted with mannich base originated from myrcene(P-MAM-g,where the mannich base derived from myrcene is abbreviated as MAM)via green and effective synthetic methods is a good strategy to avoid unacceptable discoloration and deterioration of thermal and mechanical properties caused by autocatalytic dehydrochlorination(DHC)during PVC processing.In this study,MAM with double bonds,amino groups,ester groups,and phospholipid groups was introduced into the chains of PVC to improve the thermal stability of PVC.The experimental results showed that the covalent attachment of MAM to PVC enhanced both the initial and the long-term stability of PVC.The enhanced performance of P-MAM-g compared with unmodified PVC is attributed to the simultaneous introduction of double bonds and amino groups into the PVC structure.The double bonds trapped the unstable chlorine atoms originated from the degradation of the PVC chain and reacted with the labile macromolecular radicals originated from PVC,thus inhibiting the radical degradation of the PVC chain.Furthermore,the amino groups absorbed the HCl produced in the degradation of PVC,inhibiting the adverse effects of HCl.P-MAM-g displayed better intrinsic flexibility and anti-migration ability of organic functional components compared with the control PVC materials.A possible stabilizing mechanism of the P-MAM-g was also presented.

Analyzing Precipitation Acidity Changes Post Train Derailment and Vinyl Chloride Release in East Palestine, Ohio: Exploring Biomedical and Environmental Ramifications

This study investigates the aftermath of a significant train derailment and vinyl chloride release incident in East Palestine, Ohio, with a particular focus on the analysis of precipitation acidity changes and the concentration of vinyl chloride in samples. The research seeks to elucidate the complex relationship between industrial accidents, atmospheric chemistry, and their potential implications for human health and the environment. Through meticulous examination of variations in precipitation acidity patterns, this study provides valuable insights into the dispersion and impact of toxic agents in the environment following industrial mishaps. The results underscore the intricate interplay between these factors, highlighting the need for a multidisciplinary approach that bridges the realms of environmental science and biomedical concerns. This research contributes to a growing body of knowledge that addresses the broader consequences of industrial incidents on public health. It underscores the importance of proactive measures, such as enhanced monitoring and surveillance, risk assessment, public education, and regulatory reform, to mitigate the environmental and health risks associated with industrial activities involving hazardous materials. By fostering collaboration between experts and stakeholders, this study advocates for a holistic approach to safeguarding both our environment and the well-being of communities affected by industrial accidents.

Direct synthesis of nitrogen-doped mesoporous carbons for acetylene hydrochlorination

Nitrogen‐doped ordered mesoporous carbon （N‐OMC） catalysts were directly synthesized using SBA‐15 as a hard template and sucrose as a carbon source. Urea, which was used as the nitrogen source, was carbonized with sucrose. A 3.6 wt% nitrogen doping of the carbon framework was achieved, with more than 70%of the nitrogen incorporated as quaternary nitrogen species. Only 0.2 wt% nitrogen doping, with only 32.7% quaternary nitrogen incorporation was obtained in an N‐OMC catalyst （N‐OMC‐T） prepared using a two‐step post‐synthesis method. The acetylene hy‐drochlorination activities of N‐OMC catalysts prepared via the one‐step method were higher than that of the N‐OMC‐T catalyst because of the higher nitrogen loadings.

Effect of Calcination Temperature on La-Modified Al2O3 Catalysts for Vapor Phase Hydrofluorination of Acetylene to Vinyl Fluoride

A La-modified Al2O3 catalyst was prepared with deposition-precipitation method. The effect of calcination temperature on the reactivity for vapor phase hydrofluorination of acetylene to vinyl fluoride. The catalysts calcined at different temperatures were characterized using NH3-TPD, pyridine-FTIR, X-ray diffraction, and Raman techniques. It was found that the calcination process could not only change the structure of these catalysts but also modify the amount of surface acidity on the catalysts. The catalyst calcined at 400 ℃ exhibited the highest conversion of acetylene （94.6%） and highest selectivity to vinyl fluoride （83.4%） and lower coke deposition selectivity （0.72%）. The highest activity was related to the largest amount of surface acidity on the catalyst, and the coke deposition was also related to the total amount of surface acidic sites.

原位微悬浮法纳米二氧化硅/氯醚树脂复合粒子的制备及表征

用硅烷偶联剂KH-570对纳米SiO2进行表面处理,干燥后预先分散于乙烯基异丁基醚中,再通过原位微悬浮聚合法制备了纳米SiO2/氯醚树脂复合粒子;考察了KH-570添加量、pH值和反应时间对纳米SiO2表面接枝率的影响,并用傅里叶变换红外光谱、核磁共振氢谱、差示扫描量热分析、热重分析和透射电子显微镜对纳米SiO2和纳米SiO2/氯醚树脂复合粒子进行了表征.结果表明,纳米SiO2表面改性的最佳条件为：KH-570与纳米SiO2质量比为1.2∶1,pH值为8.0 ～9.0,反应时间为8h;制备出的纳米SiO2/氯醚树脂复合粒子以纳米SiO2为核,其平均粒径为150～ 250 nm,其中核的直径为100～150 nm.

辐照改性聚乙烯醇缩甲醛精密过滤材料的制备与性能分析

聚乙烯醇缩甲醛过滤材料具有气孔细微、过滤精度高、通量大、无纤维脱落等特点,在精密过滤领域具有广阔的应用空间。本研究以聚乙烯醇PVA-1799和甲醛为主要原料,季戊四醇三丙烯酸酯为改性剂,利用γ射线辐照技术制备了改性聚乙烯醇缩甲醛(Poly(vinyl formal),PVF)过滤材料,对材料的泡孔结构、力学性能、尺寸稳定性、吸水率、耐水性能及耐油性能进行了测试与表征。结果表明,材料的孔径小于300μm,拉伸断裂强度达到3.01 MPa,撕裂强度达到13.23 MPa;以辐射技术所制备的泡沫材料尺寸稳定性良好,具有更佳的力学性能和耐油耐水性能。采用辐照技术能够简化PVF过滤材料生产工艺,减少无机酸和甲醛用量,减轻环境污染。

聚乙烯醇纳米纤维的制备与静电纺丝工艺研究

近年来,利用高压静电纺丝技术开发生物医用材料制品已成为研究的热点。本实验利用高压电纺丝技术制备了聚乙烯醇(PVA)纳米纤维,研究了PVA溶液静电纺丝过程中PVA浓度,纺丝电压和收集板距离等电纺工艺参数对PVA纤维形成及其微观形貌的影响。实验结果表明,PVA纤维直径随着电纺溶液浓度的增加而增加;当电压从15 kV增加至25 kV时,纤维直径逐渐下降;电压从25 kV增加至30 kV时纤维直径反而开始增加;收集板间距离增加纤维直径也相对的减小。PVA纤维在浓度20%,电压25 kV,收集板距离15 cm,流速0.2 ml/h的工艺条件下形貌和直径最佳,静电纺丝过程也最稳定。

Removal of manganese from waste water by complexation-ultrafiltration using copolymer of maleic acid and acrylic acid

Copolymer of maleic acid and acrylic acid （PMA-100）, combining with polyvinyl butyral （PVB） ultrafiltration membrane was used for the removal of Mn（II） from waste water by complexation-ultrafiltration. The carboxylic group content of PMA-100 and the rate of complexation reaction were measured. Effects of the mass ratio of PMA-100 to Mn（II） （n）, pH, background electrolyte, etc on the rejection rate （R） and permeate flux （J） were investigated. The results show that carboxylic group content of PMA-100 is 9.5 mmol/g. The complexation of Mn（II） with PMA-100 is rapid and completed within 5 min at pH 6.0. Both R and J increase with pH increasing in the range of 2.5-7.0, and R increases with the increase of n at pH 6.0 while J is little affected. The background electrolyte leads to the decrease of R, and CaCl2 has much greater effect on R than NaCl at the same ionic strength.

Nutrient Release Characteristics of Vinyl Chloride-Vinyl acetate Copolymers Coated SlowRelease Nitrogen Fertilizer and Its Effect on Soil Mineral Nitrogen

[Objective] The aim was to explore release characteristics of vinyl chlo- ride-vinyl acetate copolymer controlled-release N fertilizer and the effects on minerat nitrogen in soils. [Method] Vinyl chloride-vinyl acetate copolymer and hydroxyl-modi- fied VCNAc were taken as coating materials to prepare slow release fertilizer. Nutri- ent release characteristics of VC/VAc slow release fertilizer was evaluated by water immersion method and the effects of VC/VAc slow release fertilizer on mineral ni- trogen were researched by pot experiment. [Result] The release periods of VC-VAc controlled-release urea and hydroxyl-modified VC/VAc coated urea were 60 and 50 d, respectively. Furthermore, the content of ammonium nitrogen reached the peak on the 30th d and the content of nitrate nitrogen reached the peak on the 60th d in soils in treatments with VCNAc and hydroxyl-modified VC/VAc; the content of nitrate nitrogen rose again on the 120th d in the treatment with VC/VAc. In terms of wheat yield, different treatments showed insignificant differences and rice yield in the treatment with VCNAc was significantly higher than that in the treatment with hy- droxyl-modified VCNAc （P〈0.05）. [Conclusion] The release days of slow controlled- release fertilizer vary upon pot experiment method and water immersion method. Slow controlled-release fertilizer is not suitable for monoculture, due to long fertilizer efficiency, but multiple cropping would be optimal for its role to be fully exploited.

PBT替代钢材提高塑料窗框保温性

据“Modern Plastics Worldwide，2008，85（85）：28”报道，2008年4月在德国Nuremberg举办的世界最大的门和窗框展览会上，德国窗框生产厂和型材加工厂Alupast公司推出新的窗框系统Vinyl Ideal 4000，优点为保温性好，性价比高。