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991.
A copper‐catalyzed cascade reaction of N‐H insertion and oxidative aromatization has been developed. 2‐Arylaminophenols have been prepared in moderate to high yields from the diazo substrates. Moreover, this newly established methodology allows efficient access to natural 1‐oxygenated carbazole alkaloids, such as glycozolicine and murrayafoline A.  相似文献   
992.
Recently, more and more rhodamine derivatives have been used as fluorophores to construct sensors due to their excellent spectroscopic properties. A rhodamine-based fluorescent and colorimetric Fe3+ chemosensor 3’,6’-bis(ethylamino)-2-acetoxyl-2’,7’-dimethyl-spiro[1H-isoindole-1,9’-[9H]xanthen]-3(2H)-one (RAE) was designed and synthesized. Upon the addition of Fe3+, the dramatic enhancement of both fluorescence and absorbance intensity, as well as the color change of the solution, could be observed. The detection limit of RAE for Fe3+ was around 7.98 ppb. Common coexistent metal ions showed little or no interference in the detection of Fe3+. Moreover, the addition of CN could quench the fluorescence of the acetonitrile solution of RAE and Fe3+, indicating the regeneration of the chemosensor RAE. The robust nature of the sensor was shown by the detection of Fe3+ even after repeated rounds of quenching. As iron is a ubiquitous metal in cells and plays vital roles in many biological processes, this chemosensor could be developed to have applications in biological studies.  相似文献   
993.
The polarized Raman spectra of the upper part of a thin ice Ih film were obtained in the range of 150 cm−1 to 3800 cm−1. The spectra showed clear polarization dependence; several new peaks were also observed. The longitudinaloptic–tranverseoptic (LO–TO) splitting of the mode near 220 cm−1 in the translational vibration region was experimentally confirmed at 133 K. The Fermi resonance between the bending overtone (around 3270 cm−1) and symmetry stretching fundamental (around 3350 cm−1) in the stretching vibration region appeared at nearly the same temperature. Results showed that ice XI (i.e. proton‐ordered phase of ice Ih) slowly formed in the upper part of a thin ice Ih film without KOH as the temperature gradually decreased below 133 K. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   
994.
Two new chemically stable metalloporphyrin-bridged metal-catechol frameworks, InTCP-Co and FeTCP-Co, were constructed to achieve artificial photosynthesis without additional sacrificial agents and photosensitizers. The CO2 photoreduction rate over FeTCP-Co considerably exceeds that obtained over InTCP-Co, and the incorporation of uncoordinated hydroxyl groups, associated with catechol, into the network further promotes the photocatalytic activity. The iron-oxo coordination chain assists energy band alignment and provides a redox-active site, and the uncoordinated hydroxyl group contributes to the visible-light absorptance, charge-carrier transfer, and CO2-scaffold affinity. With a formic acid selectivity of 97.8 %, FeTCP-OH-Co affords CO2 photoconversion with a reaction rate 4.3 and 15.7 times higher than those of FeTCP- Co and InTCP-Co, respectively. These findings are also consistent with the spectroscopic study and DFT calculation.  相似文献   
995.
Wu  Lei  Su  Huijuan  Liu  Qi  Sun  Libo  Sun  Xun  Zhao  Lijun  Qi  Caixia 《Kinetics and Catalysis》2022,63(5):498-504
Kinetics and Catalysis - Using a modified deposition-precipitation method, a series of Au–Mo/ZSM-5 catalysts with different Au loadings were prepared. The XRD, nitrogen adsorption-desorption,...  相似文献   
996.
Xiang  Wang-Kai  Xie  Qing  Xu  Shan-Shan  Sun  Chen-Xuan  Yu  Cheng-Tao  Zheng  Ying  Pan  Peng-Ju 《高分子科学》2022,40(6):567-575

Stereocomplex (SC) crystallization has been an effective way to improve the physical performances of stereoregular polymers. However, the competition between homo and SC crystallizations can lead to more complicated crystallization kinetics and polymorphic crystalline structure in stereocomplexable polymers, which influences the physical properties of obtained materials. Herein, we select the medium-molecular-weight (MMW) poly(L-lactic acid)/poly(D-lactic acid) (PLLA/PDLA) asymmetric blends with different PDLA fractions (fD=0.01–0.5) as the model system and investigate the effects of fD and crystallization temperature (Tc) on the crystallization kinetics and polymorphic crystalline structure. We observe the fractionated (i.e., multistep) crystallization kinetics and the formation of peculiar β-form homocrystals (HCs) in the asymmetric blends under quiescent conditions, which are strongly influenced by both fD and Tc. Precisely, crystallization of β-form HCs is favorable in the MMW PLLA/PDLA blends with high fD (≥0.2) at a low Tc (80–100 °C). It is proposed that the formation of metastable β-form HCs is attributed to the conformational matching between β-form HCs and SCs, and the stronger constrain effects of precedingly-formed SCs in the early stage of crystallization. Such effects can also cause the multistep crystallization kinetics of MMW PLLA/PDLA asymmetric blends in the heating process.

  相似文献   
997.
Yin  Jin  Ouyang  Qing-Feng  Sun  Zhao-Bo  Wu  Feng-Yang  Liu  Qian  Zhang  Xi-Xi  Xu  Ling  Lin  Hao  Zhong  Gan-Ji  Li  Zhong-Ming 《高分子科学》2022,40(6):593-601

Components of co-continuous phase can form an interpenetrating network structure, which has great potential to synergistically improve the mechanical properties of the blends, and to impart the functional blends superior electrical conductivity and permeability. In this work, the effects of shear rates (50–5000 s?1) at different temperatures on the phase morphology, phase size and lamellar crystallites of biodegradable co-continuous polybutylene terephthalate (PBAT)/polybutylene succinate (PBS) blend are quantitatively investigated. The results show that the above features of the PBAT/PBS have a strong dependence on the shear flow and thermal field. The co-continuous phase of the blend is well maintained at 130 °C. Interestingly, this phase structure transforms into a “sea-island” structure at 160 °C, which gradually recovers to a co-continuous phase when the shear rate increases from 1000 s?1 to 5000 s?1. The phase size decreases with the increase of shear rate both at 130 °C and 160 °C due to the refinement and deformation of phase structures caused by strong shear stress. Unexpectedly, a unique phenomenon is observed that the shear-induced lamellar crystallites are oriented perpendicular to shear direction in the range of 500–5000 s?1 at 130 °C, while the orientation of lamellar crystallites at 160 °C is along the shear direction within the whole range of shear rates. The degree of orientation for the PBAT/PBS blend crystals increases first and then decreases at both temperatures above. In addition, the range of shear rate has reached the level in the industrial processing. Therefore, this work has important guiding significance for the regulation of the co-continuous phase structure and the performance for the blend in the practical processing.

  相似文献   
998.
Journal of Inclusion Phenomena and Macrocyclic Chemistry - The condensation reaction of mono-amido-functionalized pillar[5]arenes with tere- and iso-phthaloyl diisothiocyanates in acetone under...  相似文献   
999.
Research on Chemical Intermediates - Dichlorobenzonitriles are important organic intermediates for the production of many fine chemicals and are produced most economically and environment-friendly...  相似文献   
1000.
二甲氧基甲烷(Dimethoxymethane, DMM)作为一种基础有机化学品, 在树脂、溶剂、燃料等领域具有广泛用途. 传统合成方法采用甲醇甲醛缩合, 反应效率比较低. 亚硝酸甲酯(CH3ONO)是一种性质活泼的气体, 可由甲醇、O2、NO在无需催化剂的条件下获得, 其反应活性比甲醇高很多. 通过亚硝酸甲酯在常压条件下催化分解可以高效制备DMM. 本工作系统研究了不同类型分子筛的酸性对亚硝酸甲酯催化分解制备DMM的影响规律, 催化活性顺序为: NaY (97%)=HY (97%)>HZSM-5 (90%)>Hβ (89%)>NaZSM-5 (18%)>Naβ (6%), DMM选择性顺序为: NaY (53%)>HY (12%)=Naβ (12%)>NaZSM-5 (7%)>Hβ (4%)>HZSM-5 (3%), 其中NaY分子筛是一种性能优异的亚硝酸甲酯分解制备DMM的催化剂. 通过X射线衍射(XRD)、比表面及孔隙度分析(BET)、扫描电子显微镜(SEM)、吡啶红外(Py-FTIR)等结构表征手段, 发现分子筛的酸性位点是促进亚硝酸甲酯分解的活性中心, 而Na+和Al物种的Lewis酸是高选择性生成DMM的关键. 本工作可为DMM提供一种新的高效合成路线.  相似文献   
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