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1.
Herein, we report the synthesis, characterisation, and application of three aluminium alkyl complexes, [κ2-{NHIRP(Ph)NDipp}AlMe2] (R = Dipp (2a), Mes (2b); tBu (2c), Dipp = 2,6-diisopropylphenyl, Mes = mesityl, and tBu = tert-butyl), supported by unsymmetrical imino-phosphanamide [NHIRP(Ph)NDipp] [R = Dipp (1a), Mes (1b), tBu (1c)] ligands as molecular precursors for the catalytic synthesis of guanidines using carbodiimides and primary amines. All the imino-phosphanamide ligands 1a, 1b and 1c were prepared in good yield from the corresponding N-heterocyclic imine (NHI) with phenylchloro-2,6-diisopropylphenylphosphanamine, PhP(Cl)NHDipp. The aluminium alkyl complexes 2a, 2b and 2c were obtained in good yield upon completion of the reaction between trimethyl aluminium and the protic ligands 1a, 1b and 1c in a 1 : 1 molar ratio in toluene via the elimination of methane, respectively. The molecular structures of the protic ligands 1b and 1c and the aluminium complexes 2a, 2b and 2c were established via single-crystal X-ray diffraction analysis. Complexes 2a, 2b and 2c were tested as pre-catalysts for the hydroamination/guanylation reaction of carbodiimides with aryl amines to afford guanidines at ambient temperature. All the aluminium complexes exhibited a high conversion with 1.5 mol% catalyst loading and broad substrate scope with a wide functional group tolerance during the guanylation reaction. We also proposed the most plausible mechanism, involving the formation of catalytically active three-coordinate Al species as the active pre-catalyst.

Three aluminium alkyl complexes, [κ2-{ImRNP(Ph)NDipp}AlMe2] (2a–2c), supported by unsymmetrical imino-phosphanamide were synthesised and utilised as competent precatalysts for the hydroamination of carbodiimides under ambient conditions.  相似文献   

2.
Global challenges prompt the world to modify its strategies and shift from a fossil-fuel-based economy to a bio-resource-based one with the production of renewable biomass chemicals. Different processes exist that allow the transformation of raw biomass into desirable bio-based products and/or energy. In this work different biochars that were obtained as a by-product from birch chip fast pyrolysis and carbonization were used as is or chemically/physically treated. These sulfonated carbon catalysts were compared to a commercially available sulfonated styrene-divinylbenzene macroreticular resin (Dowex 50W X8). Characterisation (water content and pH value, FTIR, base titration, element analysis and N2 desorption) was done to evaluate the obtained sulfonated biocarbon catalysts. Catalytic activity was tested using cellobiose (CB) hydrolysis and acetic acid esterification. For the catalytic CB hydrolysis, we tested the reaction temperature, time and CB and catalyst mass ratios. The determined optimal conditions were 120 °C and 24 h, with CB and catalyst mass ratio 1 : 5. The highest glucose yield was observed for biochar obtained from the birch chip fast pyrolysis process (BC_Py-H2SO4) – 92% within 24 h for 120 °C. Comparably high glucose yield was observed for biochar that was obtained in birch chip carbonization (BC_Carbon-H2SO4) – 86% within 24 h for 120 °C.

In this work different biochars that were obtained as a by-product from birch chip fast pyrolysis and carbonization were used as is or chemically/physically treated. The characterisation was done using CB hydrolysis and acetic acid esterification.  相似文献   

3.
Liquid fuel intermediates can be produced via aldol condensation reactions through furan aldehydes and ketones driven from biomass. It was found that cerous phosphate (CP) with two different crystal structures (hexagonal and monoclinic structure), which was tailored by different hydrothermal temperature (120 °C for the hexagonal structure and 180 °C for the monoclinic structure) and calcination temperature (900 °C for the monoclinic structure) as a solid acid catalyst, exhibit high catalytic performance in aldol condensation between furfural and acetone. The CP with hexagonal structure gave 89.1% conversion of furfural with 42% yield of 4-(2-furyl)-3-buten-2-one (FAc) and 17.5% of yield of 1,5-di-2-furanyl-1,4-pentadien-3-one (F2Ac), much higher than CP with monoclinic structure. However, both furfural conversion and aldol product yield increased from 82.3% to 96% and from 50.5% to 68.4%, respectively, for CP with the monoclinic structure after calcination owing to the higher amount of acid of catalyst after calcination but decreased continuously for CP with hexagonal structure after calcination because of its rapidly reduced BET surface area and total pore volume. The results indicated that calcination affects significantly the physical–chemical properties of CP catalysts, which influence subsequently the catalytic performance in the aldol condensation reaction. Recycling experiments showed that the catalytic performance after five number runs for CP with monoclinic structure after calcination was acceptable but was not ideal for CP with hexagonal structure owing to its poor hydrothermal stability.

Liquid fuel intermediates can be produced via aldol condensation reactions through furan aldehydes and ketones driven from biomass.  相似文献   

4.
5.
Two new copper(ii) complexes [Cu2(L)2(OAc)2(H2O)2] (1) (L = 3-methyl-5-pyridin-2-yl-1,2,4-triazole) and [CuL2] (2) were prerared and thoroughly studied. The complexes are able to selectively catalyze the oxidation of styrene towards benzaldehyde and of cyclohexane to KA oil. The 2D coordination polymer 1 showed an antiferromagnetic behaviour attributed to the intrachain magnetic coupling.

Two copper(ii) complexes were investigated as catalysts for selective oxidation of styrene to benzaldehyde and of cyclohexane to KA oil.  相似文献   

6.
Fiber-supported catalysts have attracted much attention due to their large specific surface area, high catalytic activity, and good recyclability. Functional polyacrylonitrile fibers were prepared by immersion of polyacrylonitrile fibers at room temperature in an alkaline dopamine (pH = 8.5) aqueous solution which can undergo self-polymerization and reduce silver ions to silver nanoparticles with mild reducibility and adsorption. The surface of the polyacrylonitrile fiber (PAN) was wrapped with a layer of polydopamine (PDA), and silver nanoparticles (Ag NPs) were adsorbed on the surface of PDA, forming an efficient fiber catalyst. The morphology and chemical composition of the catalyst material were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) patterns, and Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). The catalytic activity of the nanocomposite was evaluated for the reduction reaction of 4-nitrophenol using sodium borohydride (NaBH4) at 35 °C with a material molar ratio of 1 : 10 and a fiber loaded catalysis dosage of 40 mg. The liquid phase yield can reach 98% in 30 minutes and can be reused after washing with ethanol. Moreover, the composite material exhibited a good stability up to 10 cycles without a significant loss of its catalytic activity. The results show that the catalyst is easy to recover from the reaction system and has maintained good stability and catalytic activity after many cycles.

Via the help of polydopamine, polyacrylonitrile fiber catalysts functionalized with silver nanoparticles were prepared and employed for the reduction reaction of 4-nitrophenol to 4-aminophenol, with a yield of 98% in 30 minutes, and can be reused for up to 10 cycles.  相似文献   

7.
8.
背景:药物微球因其对特定器官和组织的靶向性及微粒中药物释放的缓释性而成为一种新的给药系统.国内外学者对局麻药缓释给药系统进行了一系列研究,但麻醉性镇痛药的微球制剂末见报道.目的:制各以聚乳酸-羟基乙酸共聚物为载体的吗啡生物可降解缓释微球制剂,并检测其镇痛作用.方法:采用溶剂挥发法制备吗啡聚乳酸-羟基乙酸共聚物微球,并计算其载药量及包封率.将雄性健康SD大鼠以数字表法随机分为3组:空白对照组(皮下注射生理盐水),阳性对照组(皮下注射盐酸吗啡注射剂)和吗啡微球组(皮下注射吗啡聚乳酸-羟基乙酸共聚物微球),利用CO2激光为热刺激进行痛阈测定.结果与结论:制成的吗啡聚乳酸-羟基乙酸共聚物微球为白色粉末,载药量为11.86%,药物包封产率为33%,微球可较明显延长吗啡作用时间至6 h以上.结果说明吗啡聚乳酸-羟基乙酸共聚物微球明显地延长了吗啡释放时间,缓释性好,但未达到预期的理想时间,仍然需要进行改进.  相似文献   

9.
A series of polyaniline supported heteropoly acids were prepared through a simple method at room temperature. The obtained heterogeneous catalysts were comprehensively characterized by powder FTIR spectroscopy, UV-vis spectra, NH3 temperature programmed desorption (TPD) and scanning electron microscopy (SEM). The influence of various process parameters such as heteropoly loading (10 to 25 wt%), catalyst amount (3–5%), molar ratio of n-butanol to citric acid (3 to 5), and reaction time (3.5–12 h) have been investigated over heteropoly/polyaniline catalysts with the aim to maximize citric acid conversion and tributyl citrate selectivity. The different catalytic tests has shown that the catalyst exhibits high conversion and selectivity by using the as-prepared heteropoly/polyaniline catalysts for esterification under appropriate conditions. The present method of using 20% heteropoly/polyaniline catalyst for the synthesis of tributyl citrate would be environmentally benign in the reusability of catalyst.

A series of polyaniline supported heteropoly acids were prepared through a simple method at room temperature.  相似文献   

10.
Nano-sized tungsten oxide (WO3) particles, each of which was encapsulated as a core in a hollow silica sphere (WO3@SiO2), were synthesized using calcium tungstate particles as the starting material. The calcium tungstate particles, each of which was covered with a silica shell, were converted to tungstic acid by nitric acid treatment and then to WO3 by heat treatment to obtain WO3@SiO2. A hollow space was formed in WO3@SiO2 between the WO3 core and the SiO2 shell as a result of shrinkage of WO3 during the heat treatment. The thus-obtained WO3@SiO2 was 40 nm in diameter, the WO3 core was 10 nm in diameter, and the silica shell, which was permeable to gas and liquid, was 10 nm in thickness. WO3@SiO2 absorbed visible light to the wavelength of 454 nm, which enabled photocatalytic reaction under visible light; Pt was loaded on the WO3 cores in the photocatalytic reactions. In contrast to Pt-loaded bulk WO3 photocatalysts without an SiO2 shell, Pt-loaded WO3@SiO2 showed continuous and complete decomposition of gaseous acetic acid in air under visible as well as UV irradiation.

We present a procedure for the synthesis of WO3 nanoparticles encapsulated in a hollow silica sphere, and their unique photocatalytic properties.  相似文献   

11.
The production of graphene oxide (GO) in large amounts for commercialization in the chemical industry has been limited because harsh and tedious process conditions are required. In this study, a novel carbon nanomaterial called ‘bottom-up graphene oxide (BGO)’ could be easily prepared for the first time by heat treatment of the mixture of citric acid (CA) and tannic acid (TA) with different weight ratios for the first time. BGO3 prepared using a 50/50 weight ratio of CA/TA was found to have an average lateral size of 250.0 nm and an average thickness of 7.2 nm, and it was further functionalized with cardanol to prepare cardanol functionalized BGO3 (CBGO3) to be used as a filler for the polypropylene (PP) nanocomposite, where cardanol was used to increase the compatibility between BGO3 and PP. The improved mechanical properties and thermal stability of PP nanocomposites containing CBGO3 could be ascribed to the intrinsic mechanical properties of the carbon nanomaterial and the increased compatibility by the attached cardanol on BGO3.

The effect of lateral size and surface characteristics of CBGO on the physical properties of polypropylene nanocomposites was studied.  相似文献   

12.
High reaction rate and easy availability make green synthesis of metal nanoparticles noticeable. In the present study, gold nanoparticles with wide applications in different fields were synthesized by an ecofriendly method at room temperature using Stachys lavandulifolia extract as the reducing agent. Properties of the synthesized gold nanoparticles (GNP) were identified by different analytical techniques including: UV-Vis absorption spectroscopy verified presence of Au NPs in the solution while functional groups of its extract and synthesized Au NPs were determined by FT-IR. Its crystalline analysis with a fcc plane was verified by X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS) determined elements in the sample. Surface morphology, diverse shapes and sizes of the Au NPs were shown by scanning electron microscopy (SEM), atomic force microscopy (AFM), and transmission electron microscopy (TEM). Beginning and end destruction temperatures of the Au/S. lavandulifolia NPs were determined by thermal gravimetric analysis (TGA). The Au nanoparticles were capped with extracts, preventing them from oxidation and agglomeration and were used as an efficient heterogeneous nanocatalyst for a three-component reaction of amines, aldehydes, and alkynes (A3 coupling). A diverse range of propargylamines were obtained in good yields. Furthermore, the separation and recycling of Au/S. lavandulifolia NPs was very simple, effective, and economical.

High reaction rate and easy availability make green synthesis of metal nanoparticles noticeable.  相似文献   

13.
14.
In this work, a “green” and facile method for synthesis of hierarchical ZSM-5 zeolite was presented by combination of a bio-mesoporogen and a dry gel conversion (DGC) process. ZSM-5 zeolite with high hierarchy factors and excellent mesoporosity was synthesized by adding hydroxypropylmethylcellulose (HPMC), which originated from cellulose biomass, to a zeolitic synthetic gel. The obtained zeolite samples were analyzed by X-ray diffraction (XRD), nitrogen adsorption–desorption (BET) and scanning electron microscopy (SEM) to determine their properties. The influence of crystallization time on the crystallinity of ZSM-5 zeolite was investigated. Moreover, the results showed that HPMC as a pore directing agent is an important factor for the formation of hierarchical zeolite with high mesoporosity. The as-prepared ZSM-5 sample with high pore volume, large surface area and abundant accessible acid sites, which seriously improves diffusion efficiency and catalytic activity, exhibited high catalytic performance in the benzylation reaction.

A “green” and facile method for synthesis of hierarchical ZSM-5 zeolite was presented using a combination of a bio-mesoporogen and a dry gel conversion (DGC) process.  相似文献   

15.
背景:包覆层的存在能够阻止纳米粒子氧化、晶体长大、腐蚀和团聚,并赋予特殊的性能.目的:制备SiO2/Ni核壳结构纳米粒子,并评估复合粉体的磁性能.设计、时间及地点:观察性实验,于2005-11/2006-03在大连理工大学纳米复合材料研究实验室完成.材料:应用直流电弧等离子体法制备纳米镍粉,硅酸钠由天津市石英钟厂霸州市化工分厂生产.方法:以硅酸钠为主要原料,通过液相沉淀法在纳米镍粉表面包覆了一层SiO2.主要观察指标:应用X射线衍射仪、傅里叶红外光谱仪、透射电镜、振动样品磁强计、热重分析仪等对复合粉体的结构、形貌和磁性能进行检测.结果:SiO2以非晶态的形式包覆在纳米镍粒子表面,形成了核壳结构,降低了纳米粉体的团聚现象.经SiO2包覆后纳米镍粉氧化温度由287℃提高到385℃.磁性分析结果表明,粉体包覆前由于表面氧化层(NiO)的存在,粉体的磁滞回线偏移;包覆后的粉体由于SiO2的存在,饱和磁化强度降低,矫顽力升高.结论:成功制备了SiO2/Ni核壳结构纳米粒子,SiO2的包覆提高了纳米粉体的抗氧化性,且纳米镍粉具有很好的铁磁性能,矫顽力升高.  相似文献   

16.
Anti-3-hydroxy 5-androstene carbonic acid (etiocholenic acid) antiserum was obtained by immunizing rabbits with anetiocholenic acid-polylysine complex. Anticholesterol succinate antiserum was also prepared by immunizing rabbits with a cholesterol succinate-polylysine complex. The cross reactivities of these antisera were examined by means of radioimmunoassay system, immunolysis of liposome and passive hemagglutination reaction. Anti-etiocholenic acid antiserum was specific against the structure of ring A of cholesterol and the nature of OH group at C3 position and anti-cholesterol succinate antiserum was specific against the side chain similar to that of cholesterol.  相似文献   

17.
Cu nanoparticles are more active catalytically than CuO nanoparticles, which have been widely studied as catalysts for organic synthesis, electrochemistry, and optics. However, Cu nanoparticles are easily agglomerated and oxidized in air. In this research, columnar, flower-like, bubble-like and teardrop-shaped Cu/GO nanocomposites were fabricated via a water-solvent thermal method and high temperature calcination technique using deionized water (H2O), methanol (CH3OH), ethanol (CH3CH2OH) and ethylene glycol (EG) as the solvent, respectively. The structures, the morphology and the catalytic performance and catalytic mechanism for thermal decomposition of ammonium perchlorate (AP) of the Cu/GO nanocomposites have been studied by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), nitrogen adsorption tests (BET), simultaneous thermogravimetry-differential scanning calorimetry (TGA/DSC) and thermogravimetric couplet with Fourier transform infrared spectroscopy (TGA–FTIR), respectively. The experimental results show that the morphology of the Cu/GO nanocomposites has a significant effect on the surface area and the teardrop-shaped Cu/GO nanocomposites have the largest specific surface area and the best catalytic performance among them. When 5 wt% of the Cu/GO nanocomposites was added, the decomposition temperature of AP decreased from 426.3 °C to 345.5 °C and the exothermic heat released from the decomposition of AP increased from 410.4 J g−1 to 4159.4 J g−1. In addition, the four morphological Cu/GO nanocomposites exhibited good stability, their catalytic performance for thermal decomposition of AP remained stable after 1 month in air. Excellent catalytic performance and stability were attributed to the strong catalytic activity of pure metal nanoparticles, and GO can accelerate electron movement and inhibit the agglomeration of nanoparticles, as well as the multiple effects of inhibiting the oxidation of Cu nanoparticles in air. Therefore, it has important application potential in high-energy solid propellant.

Cu nanoparticles are more active catalytically than CuO nanoparticles, which have been widely studied as catalysts for organic synthesis, electrochemistry, and optics.  相似文献   

18.
In this study, annealing carbon fibres with boron and FeCl3·6H2O at elevated temperatures was demonstrated as a novel route to coat carbon fibres with boron nitride (BN) nanosheets. The effect of annealing temperature on the thickness and microstructure of BN coating was investigated. Results showed that BN coating hardly formed at 1000 °C, and uniform BN coating was achieved at 1100 °C and 1200 °C. However, further increasing the temperature to 1250 °C triggered the formation of discretely distributed BN particles on the surface of the BN coating in addition to the formation of a uniform BN coating. The BN coating and particles were constructed by numerous BN nanosheets with a bending and crumpling morphology. The thickness of the BN coating increased with increasing annealing temperature. The oxidation resistance of the carbon fibres dramatically enhanced after BN nanosheets were coated onto the carbon fibre surface. Moreover, given the low dielectric loss tangent of BN, the BN coating can improve the impedance matching of carbon fibres and enhance the microwave-absorbing property of carbon fibres significantly.

The coating of BN nanosheets on carbon fibers could enhance the anti-oxidation and microwave absorbing properties of carbon fibers significantly.  相似文献   

19.
背景:低温快速成型技术具有支架成型可控性、保持材料生物学活性和易于实现支架材料的三维多孔立体结构等优势,被迅速用于骨组织工程支架的制备。目的:采用低温快速成型制备聚乙二醇改性聚乳酸-乙醇酸/纳米羟基磷灰石复合支架,并检测其性能。方法:采用低温快速成型设备分别制备聚乙二醇改性聚乳酸-乙醇酸/纳米羟基磷灰石与聚乳酸-乙醇酸/纳米羟基磷灰石复合支架,通过电镜观察支架超微结构,以介质(乙醇)浸泡法测定支架孔隙率,采用电子试验机检测支架力学性能;将两种支架材料分别与大鼠成骨细胞共培养,培养12 h采用沉淀法检测细胞黏附率,培养1,3,5,7,9,12 d采用CCK-8法检测细胞增殖。结果与结论:两组支架孔径均在理想范围内并具有较高孔隙率,但聚乙二醇改性聚乳酸-乙醇酸/纳米羟基磷灰石支架的孔径波动范围大,孔径均值较聚乳酸-乙醇酸/纳米羟基磷灰石支架小且部分有闭塞现象。聚乙二醇改性聚乳酸-乙醇酸/纳米羟基磷灰石支架的细胞黏附率及表面细胞增殖活性高于聚乳酸-乙醇酸/纳米羟基磷灰石支架(P<0.05),力学性能低于聚乳酸-乙醇酸/纳米羟基磷灰石支架(P<0.05)。表明聚乙二醇改性聚乳酸-乙醇酸/纳米羟基磷灰石复合支架具有良好的细胞相容性。  相似文献   

20.
Tramadol, an analgesic with mean potency one tenth that of morphine is used regularly for the treatment of chronic and postoperative pain. Previous reports have indicated that tramadol may induce seizure activity when given together with a selective serotonin reuptake inhibitor (SSRI). Therefore, its major mode of action may be questioned which purportedly is due to binding with the opioid receptor and partly due to the inhibition of monoamine reuptake.We therefore set out to study its potential in inducing seizure activity and to quantify its effect on EEG-power spectra and on the central modulation of sensory afferents in awake and trained dogs (n=7). In order to demonstrate if opioid receptors mediated these effects, incremental doses of tramadol were given which was followed by naloxone for possible reversal. After a wash-out period the same animals were exposed to graded doses of alfentanil, a pure mu-receptor agonist. Again this was followed by the opioid antagonist naloxone for reversal.The electroencephalogram (EEG) and the event-related evoked potentials (SEP) were used to demonstrate possible excitatory effects. In order to derive the SEP the front paw was stimulated electrically (Digi Stim II trade mark ) while the evoked potentials were picked up contralaterally from the somatosensory cortex using stick-on electrodes. 256 sweeps were averaged (Lifescan) and the peak-to-peak amplitude was measured to demonstrate CNS excitation compared to control (%). Additionally, the raw electroencephalogram was viewed for epileptogenic changes and its power computed into the various power bands alpha, beta, delta und theta using FFT over a time epoch of 60 s. Following control, graded doses of either tramadol (2-5-10 mg/kg i.v.) or alfentanil (10-30-60 microg/kg i.v.) were given every 15 min while the EEG and the SEP were recorded. Thereafter naloxone (20 microg/kg i.v.) was injected for reversal.Tramadol did not suppress the amplitude of the SEP at any dose. High doses (>5 mg/kg i.v.) resulted in an increase (+100%) of the amplitude of the evoked potential. This was accompanied by short-term muscle fibrillations, and a short-term spike-and-wave activity in the EEG followed by a long-lasting theta-dominance. These effects could not be reversed by naloxone. In contrast to tramadol, alfentanil induced a dose-related depression of amplitude in the SEP with a maximum of 82% suggesting a depressive effect of modulation of afferents in the sensory cortex. This effect was fully naloxone reversible and was followed by a rebound in amplitude of the SEP together with an increase in fast beta-waves in the EEG.Tramadol very little mediates its central action via the mu-opioid receptor as the present effects were not naloxone reversible. Consistent with the results is the very low affinity of tramadol to the opioid receptor which is several thousand times less than that of morphine. Most likely, inhibition of central norepinephrine and serotonin reuptake as well as the reduction in 5-HT-turnover may contribute to the effects of tramadol. Due to the monoamine reuptake inhibition an increase in transmission may result, triggering off excitatory phenomena with spike-and-wave activity in the CNS. Such excitatory effects, however, may only be seen when tramadol is used in doses exceeding the therapeutic range.  相似文献   

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