堇青石负载Fe、Mo催化剂用于合成气合成乙烯

以堇青石为载体,采用浸渍法制备了表面多孔的堇青石负载Fe-Mo催化剂,并利用SEM、FT-IR、XRD、EDX、XPS等对催化剂的结构和形貌进行表征。研究表明,用在450℃氩气气氛下焙烧所制备的Fe-Mo催化剂催化合成乙烯的效果最明显。此外,在常压条件下,研究了不同温度、空速、合成气比例对合成乙烯的影响,结果表明,在450℃、H2/CO为2、反应空速为2.0L/g cat·h时,CO转化率达到63.5%,乙烯的选择性达到46.3%。Fe-Mo催化剂对合成气合成乙烯具有高转化效率,可望为工业生产乙烯提供新的参考与依据。     

Synthesis,Structures, and Properties of Lanthanide Complexes with Pyrimidine‐2‐carboxylic Acid

Six lanthanide complexes [Ln(pmc)₂NO₃]_n [Hpmc = pyrimidine‐2‐carboxylic acid, Ln = La ( 1 ), Pr ( 2 )], [Ln(pmc)₂(H₂O)₃]NO₃ · H₂O [Ln = Eu ( 3 ), Tb ( 4 ) Dy ( 5 ), Er ( 6 )] were synthesized by the reactions of lanthanide nitrate and pyrimidine‐2‐carboxylic acid in water at room temperature. These complexes were characterized by single‐crystal X‐ray diffraction analysis, elemental analysis, IR, circular dichroism (CD) and fluorescence spectra. Structure analysis shows that complexes 1 and 2 are isostructural with P4₃2₁2 space group, whereas isostructural complexes 3 – 6 belong to the P2₁/c space group. In complexes 1 and 2 , the central metal atoms are coordinated by nitrates and pmc^–, which are self‐assembled to construct a 3D porous network with 6₂.6₂.6₂.6₂.6₂.6₂ (6⁶) topology. In complexes 3 – 6 , H₂O and pmc^– ligands are coordinated and the complexes exhibit a one‐dimensional zigzag chain, which is further expanded into a 3D structure by hydrogen bonding. In addition, the circular dichroism of 1 and 2 proves that the two complexes are both chiral with achiral ligand of Hpmc. Luminescent measurements of compounds 3 – 5 indicate that the characteristic fluorescence of Eu³⁺, Tb³⁺, and Dy³⁺ are observed.     

Sensitive DNA-hybridization biosensors based on gold nanoparticles for testing DNA damage by Cd(II) ions

A DNA biosensor was constructed by immobilizing a 20-mer oligonucleotide probe and hybridizing it with its complementary oligomer on the surface of a glassy carbon electrode modified with gold nanoparticles. The properties of the biosensor and its capability of recognizing its complementary sequence were studied by electrochemical impedance spectroscopy. The oxidative stress caused by cadmium ions can be monitored by differential pulse voltammetry using the cobalt(III)tris(1,10-phenanthroline) complex and methylene blue as electrochemical indicators. The biosensor is capable of indicating damage caused by Cd(II) ions in pH 6.0 solution. The results showed that the biosensor can be used for rapid screening for DNA damage.

低量镱掺杂TiO2纳米光催化剂的溶胶-溶剂热制备及光活性

利用溶胶-溶剂热技术制备了锐钛矿型Yb掺杂和未掺杂TiO2纳米粒子,以亚甲基蓝(MB)溶液在紫外光和可见光照射下的光催化脱色率评价其光活性,考察了溶剂热温度、Yb掺杂量和焙烧温度对样品光活性的影响;结合XRD,BET,XPS,FT-IR,DRS和PL表征手段,探讨了Yb掺杂对TiO2光活性的影响机制.结果表明,低量Yb掺杂不仅显著提高TiO2的紫外光活性,也明显提高其可见光活性.Yb掺杂调整TiO2带隙内部电子分布状态,有效抑制光生e-/h+复合,提高量子效率;并且增加表面羟基,增大比表面积,改善表面织构特性,致使紫外光活性提高.然而Yb掺杂并未引起紫外吸收带边红移,其可见光活性的提高应归因于Yb掺杂强化了表面吸附染料的敏化作用.     

Enhanced separation performance of PVDF/PVP-g-MMT nanocomposite ultrafiltration membrane based on the NVP-grafted polymerization modification of montmorillonite (MMT)

A novel hydrophilic nanocomposite additive (PVP-g-MMT), coupling of hydrophilic modifier, self-dispersant, and pore-forming agent (porogen), was synthesized by the surface modification of montmorillonite (MMT) with N-vinylpyrrolidone (NVP) via "grafting from" polymerization in the presence of H(2)O(2)-NH(3)·H(2)O as the initiator, and then the nanocomposite membrane of poly(vinylidene fluoride) (PVDF) and PVP-g-MMT was fabricated by wet phase inversion onto clean glass plates. The existence and dispersion of PVP-g-MMT had a great role on structures, morphologies, surface composition, and chemistry of the as-prepared nanocomposite membranes confirmed by varieties of spectroscopic and microscopic characterization techniques, all of which were the correlated functions of PVP-g-MMT content in casting solution. By using the dead-end filtration of protein aqueous solution, the performance of the membrane was evaluated. It was seen that all of the nanocomposite membranes showed obvious improvement of water flux and proper BSA rejection ratio, compared to the control PVDF membrane. Meanwhile, dynamic BSA fouling resistance and flux recovery properties were also greatly enhanced due to the changes of surface hydrophilicity and morphologies. All the experimental results indicated that the as-prepared PVDF nanocomposite membranes showed better separation performances than the control PVDF membrane. Hopefully, the demonstrated method of hydrophilic nanocomposite additive synthesis would be applied for commonly hydroxyl group-containing inorganic nanoparticles, which was favorable to fabricate hydrophilic nanoparticle-enhanced polymer membranes for water treatment.     

Natural orbital Fukui function and application in understanding cycloaddition reaction mechanisms

A new condensed form of the Fukui function, the natural orbital Fukui function (NOFF), is proposed and derived from natural bond orbital occupancy. It is defined as the change in natural bond orbital occupancy upon electronic perturbation (electron addition to, or depletion from, a molecular system). Applying NOFF to a series of cycloaddition reactions (e.g., [4 + 2] and [2 + 1] cycloadditions) illustrates the effectiveness of the concept in interpreting bond breakage and formation mechanisms.     

Bijective soft set decision system based parameters reduction under fuzzy environments

Gong et al. (2010) and Xiao et al. (2010) have proposed the notion of bijective soft set and exclusive disjunctive soft set, respectively, which is a subtype of soft set. On the basis of their work, this paper extends these notions to fuzzy environments, and formulates the concept of bijective fuzzy soft set, which can deal with more uncertain problems. Moreover, this paper proposes two parameters reduction algorithms: one (Algorithm 1) is based on bijective fuzzy soft system, and the other (Algorithm 2) takes weight of an element into consideration. Since the threshold plays an important role in these algorithms, we proposed an algorithm (Algorithm 3) to decide the optimal value of threshold specially. Afterwards, an example analysis of the two parameters reduction algorithms is given and the result shows that the two algorithms lead to the same parameters reduction of a bijective fuzzy soft system. Since Algorithm 2 considers the detail weights of elements, thus it can be used in more uncertain problems, such as time series analysis problems, than Algorithm 1.     

磷酸钾中和法邻甲酚羧化反应的绿色合成

以邻甲酚和二氧化碳为原料,以磷酸钾为中和剂一步羧化合成邻甲基水杨酸及相关产物。探讨了反应条件对产率的影响。实验结果表明,当磷酸钾与邻甲酚物料比为2.5∶1,反应温度150 ℃,反应压力3.0 MPa时,羧化反应产物总收率达到95.4%,同时邻甲基水杨酸收率也达到最大。与传统碳酸钾中和法相比,磷酸钾中和法产物在后处理过程中无二氧化碳放出,后处理过程中的磷酸根可制备为磷酸钾使用,新工艺是一条绿色化工路线。     

PIII‐Chelation‐Assisted Indole C7‐Arylation,Olefination, Methylation,and Acylation with Carboxylic Acids/Anhydrides by Rhodium Catalysis

Rhodium‐catalyzed C7‐selective decarbonylative arylation, olefination, and methylation of indoles with carboxylic acids or anhydrides by C?H and C?C bond activation have been developed. Furthermore, C7‐acylation products can also be generated selectively at a lower reaction temperature in the developed system. The key to the high reactivity and regioselectivity of this transformation is the appropriate choice of an indole N‐PtBu₂ chelation‐assisted group. This method has many advantages, including easy access and removal of the directing group, the use of cheap and widely available coupling agents, no requirement of an external ligand or oxidant, a broad substrate scope, high efficiency, and the formation of a sole regioisomer.     

自然轨道福井函数和成键活性描述符应用于解释苯硫醌和1, 3-二烯的[2+4]和[4+2]环加成反应中的成键机理

苯硫醌与脂肪族烯烃可以发生[2+4]和[4+2]环加成反应。为了解释这些环加成反应中的成键过程,本文使用了自然轨道福井函数(NOFF)与成键活性描述符。自然轨道福井函数揭示了苯硫醌和脂肪族烯烃的键或轨道的亲电性,表明电子供体的成键轨道和电子受体的反键/成键轨道之间发生了电子转移,然后成环,在这一过程中有两个共价键形成,得到了环状产物。成键活性描述符表明共价键比较容易在一个分子中具有较大f_k1⁺值的k1原子与另一个分子中具有较大f_k2^-值的k2原子之间形成。自然轨道福井函数与成键活性描述符都可以有效解释苯硫醌与1, 3-二烯之间的[2+4]与[4+2]环加成反应的机理。