首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   202篇
  免费   17篇
  国内免费   6篇
化学   174篇
晶体学   2篇
力学   13篇
数学   18篇
物理学   18篇
  2023年   3篇
  2022年   24篇
  2021年   9篇
  2020年   9篇
  2019年   11篇
  2018年   7篇
  2017年   7篇
  2016年   16篇
  2015年   8篇
  2014年   13篇
  2013年   24篇
  2012年   11篇
  2011年   20篇
  2010年   10篇
  2009年   6篇
  2008年   16篇
  2007年   8篇
  2006年   6篇
  2005年   3篇
  2004年   8篇
  2002年   2篇
  1999年   1篇
  1995年   1篇
  1994年   1篇
  1933年   1篇
排序方式: 共有225条查询结果,搜索用时 15 毫秒
81.
Polydichlorophosphazenes (PDCP) were synthesized through ring opening polymerization of hexachlorocyclotriphosphazene (HCCP). The polymerization behavior of HCCP under varying conditions of time and amount of catalyst was investigated. The chlorine atoms in polydichlorophosphazenes (PDCP) were substituted with p-oxybenzaldehyde and (or) diethylamine to synthesize poly[bis(p-oxybenzaldehyde diethylamino)phosphazenes](PPOBADEAP), poly[bis(p-oxybenzaldehyde)phosphazenes] (PPOBAP) and poly[bis(diethyl amino) phosphazenes] (PDEAP). The supporting evidence for the success of this synthesis was provided by nuclear magnetic resonance (1H-NMR, and 31P-NMR), gel permeation chromatography (GPC), and energy-dispersive X-ray spectroscopy (EDAX). The self-assembly behavior of PPOBADEAP, PPOBAP and PDEAP was observed in different solvents by the same concentration of polymers. The optical microscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images indicated that PPOBADEAP formed various morphologies in different solvents while PPOBAP and PDEAP did not show self-assembly behavior at the same conditions.  相似文献   
82.
Insulin, a peptide that has been used for decades in the treatment of diabetes, has well-defined properties and delivery requirements. Liposomes, which are lipid bilayer vesicles, have gained increasing attention as drug carriers which reduce the toxicity and increase the pharmacological activity of various drugs. The molecular interaction between (uncharged lipid) dipalmitoyl phosphatidylcholine (DPPC) liposomes and insulin has been characterized by using Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction. The characteristic protein absorption band peaks, Amide I (at about 1660?cm?1) and Amide II band (at about 1546?cm?1) are potentially reduced in the liposome insulin complex. Wide-angle x-ray scattering measurements showed that the association of insulin with DPPC lipid of liposomes still maintains the characteristic DPPC diffraction peaks with almost no change in relative intensities or change in peak positions. The absence of any shift in protein peak positions after insulin being associated with DPPC liposomes indicates that insulin is successfully forming complex with DPPC liposomes with possibly no pronounced alterations in the structure of insulin molecule.  相似文献   
83.
84.
The synthesis of macrocycles with intraannular polar ester groups and extraannular oligo-alkyl groups is described. The compounds exhibit stable liquid crystalline phases showing fan-shaped textures under the polarizing microscope, typical for a columnar order of the molecules. X-ray powder diffraction data of the LC phase indicate that the unit cell contains two symmetry-related units, a feature pointing most probably to a restricted rotation of the macrocycles within a stack. The X-ray data were further supported by solid-state NMR experiments, showing that the rigid core of the compounds does not rotate with kHz or higher frequencies within the column in the LC phase. Apart from the organization of the molecules in the LC phase, the 2D organization of the macrocycles at the solvent-highly oriented pyrolytic graphite (HOPG) interface was investigated and showed that these compounds are capable of nanofunctionalizing the HOPG surface in the multinanometer regime.  相似文献   
85.
De Wael K  Adriaens A 《Talanta》2008,74(5):1562-1567
This work reports on the electrocatalytic oxidation of hydroxide using different central metal ion phthalocyanines and porphyrins immobilized on gold electrodes. The apparent electrocatalytic activity of cobalt phthalocyanine or porphyrin modified electrodes was found to be the greatest among the present series of metal ion macrocycles investigated. Copper and unmetallated phthalocyanine or porphyrin modified electrodes show no electrocatalytic behaviour towards hydroxide, such as bare gold. A possible mechanism for the enhanced reactivity of cobalt ion macrocycles towards the oxygen evolution is given. It is also stated that the electrocatalytic activity towards an adsorbate involves several aspects, such as the coordination state of the central metal ion, the nature of the ligand, the stability of the complexes, the number of d electrons, the energy of orbitals and the strength of the bonding between the central metal ion and the axial ligand.  相似文献   
86.
Cyclization of 2‐furan‐2‐yl‐4‐mercapto‐6‐methylpyrimidine‐5‐carbonitrile 1 with ethyl chloroacetate gave o‐aminoester thienopyrimidine derivative 3 , which was reacted with a variety of reagents to give a series of novel thienopyrimidines including tetrazolyl thienopyrimidine, pyrrolylthienopyrimidine, pyrimidothienotriazine, and thienodipyrimidines. Some of the synthesized compounds were tested for their antibacterial activities against Gram‐positive and Gram‐negative bacteria.  相似文献   
87.
88.
89.
Nanotechnology is one of the most recent technologies. It is uncertain whether the production of small-size nanoparticles (NPs) can be achieved through a simple, straightforward, and medicinally active phytochemical route. The present study aimed to develop an easy and justifiable method for the synthesis of Ag, Au, and their Ag/Au bimetallic NPs (BNPs) by using Hippeastrum hybridum (HH) extract, and then to investigate the effects of Ag, Au, and their Ag/Au BNPs as antimicrobial and phytotoxic agents. Ag, Au, and their Ag/Au BNPs were characterized by UV-visible spectroscopy, FT-IR spectroscopy, XRD, EDX, and SEM analysis. XRD analysis conferring to the face of face-centered cubic crystal structure with an average size of 13.3, 10.72, and 8.34 nm of Ag, Au, and Ag/Au BNPs, respectively. SEM showed that Ag, Au, and Ag/Au BNPs had spherical morphologies, with calculated nano measurements of 40, 30, and 20 nm, respectively. The EDX analysis confirmed the composition of elemental Ag signal of the HH-AgNPs with 22.75%, Au signal of the HH-AuNPs with 48.08%, Ag signal with 12%, and Au signal with 38.26% of the Ag/Au BNPs. The Ag/Au BNPs showed an excellent antimicrobial efficacy against Gram-positive Staphylococcus aureus, Actinomycetes meriye, Bacillus cereus, Streptococcus pyogenes, Methicillin-resistant Staphylococcus aureus, Micrococcus luteus, Streptococcus pneumonia, and Gram-negative Klebsiella pneumonia, Escherichia coli, and Serratia marcescens bacterial strains, as well as against three fungal strains (Aspergillus niger, Aspergillus fumigatus, and Aspergillus flavus) compared to HH extract, HH-AgNPs, and HH-AuNPs. However, further investigations are recommended to be able to minimize potential risks of application.  相似文献   
90.
Megaporous adsorbents were prepared based on nonwoven polyethylene terephthalate (PET) fabrics and functionalized by covalent modification with polyvinylamine (PVAm) or monotriazinyl-β-cyclodextrin-substituted polyvinylamine (PVAm-MCT-β-CD). Mechanical properties of the resulting fabrics were maintained, as judged by tensile strength tests and scanning electron microscopy. Exceptional porosity (≥82%) and preserved hydrodynamic characteristics (Pe ≥ 63) indicated excellent structural stability when packed. The performance of the constructed adsorbents was evaluated with high molecular weight (proteins) and low molecular weight (dyes) model compounds. The static binding capacity (SBC) for bovine serum albumin (BSA) was 79.7 ± 1.3 and 92.9 ± 8.2 mg/g for PVAm-modified and PVAm-MCT-β-CD-modified fabrics, respectively. The mentioned materials also adsorbed Orange II, an acidic dye (92.4 ± 2.6 and 101.9 ± 2.6 mg/g, respectively), indicating that the hydrophobicity was a prevailing binding mechanism operating at a pH close to isoelectric point. SBC for lysozyme and toluidine blue O (TBO, a basic dye) onto PVAm-MCT-β-CD functionalized PET was 52.7 ± 5.1 and 73.3 ± 0.6 mg/g, respectively. TBOs have also shown some affinity for PVAm functionalized PET, but this was most likely to be mediated by hydrophobicity. On the other hand, operating at a superficial velocity of 90 cm/h, dynamic binding capacity for BSA was 11.4 ± 3.5 and 2.5 ± 0.6 mg/g indicating the importance of possible aggregation mechanisms during protein binding at equilibrium. Thus, PET-based adsorbents require further functional improvement for chromatography applications. However, the easy-to-construct, scalable nonwoven adsorbents deserve further attention as a potential alternative to packed-bed-chromatography adsorbents.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号