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   449篇
  免费   20篇
  国内免费   3篇
化学   328篇
晶体学   2篇
力学   23篇
数学   44篇
物理学   75篇
  2023年   3篇
  2022年   18篇
  2021年   34篇
  2020年   32篇
  2019年   32篇
  2018年   34篇
  2017年   32篇
  2016年   47篇
  2015年   10篇
  2014年   35篇
  2013年   43篇
  2012年   24篇
  2011年   24篇
  2010年   22篇
  2009年   16篇
  2008年   13篇
  2007年   9篇
  2006年   8篇
  2005年   7篇
  2004年   4篇
  2003年   1篇
  2002年   1篇
  2001年   3篇
  2000年   2篇
  1999年   1篇
  1998年   1篇
  1996年   2篇
  1994年   1篇
  1991年   2篇
  1986年   1篇
  1980年   2篇
  1979年   1篇
  1978年   1篇
  1976年   5篇
  1969年   1篇
排序方式: 共有472条查询结果,搜索用时 10 毫秒
111.
Three new oxime‐based palladacycles, namely [Pd{C,N‐C6H4{C(Me)?NOH}‐2}(dppm)]ClO4 ( 1 ), [Pd2{C,N‐C6H4{C(Me)?NOH}‐2}2(dppe)2(μ‐dppe)](ClO4)2 ( 2 ) and [Pd{C,N‐C6H4{C(Me)?NOH}‐2}(dppmS2)]ClO4 ( 3 ), were synthesized by the reaction of dinuclear oxime complex [Pd{C,N‐C6H4{C(Me)?NOH}‐2}(μ‐Cl)]2 with different diphosphine ligands (dppm, dppe and dppmS2). The synthesized complexes were characterized using Fourier transform infrared, 31P NMR, 1H NMR and 13C NMR spectroscopic methods and elemental analyses, and their molecular structures were elucidated using X‐ray crystallography. The structure of 2 is worthy of note as it is the first oxime palladacycle where there are both bridging (P–) and chelating (P^P) dppe ligands, giving rise to a dinuclear complex. The palladium atom is in a five‐coordinate, square pyramidal P3NC environment, while in 3 the palladium atom is in a distorted square planar environment, coordinated by the oxime ligand and a chelating (S^S) dppmS2 ligand. These complexes were employed as efficient catalysts for the Suzuki–Miyaura cross‐coupling reaction of several aryl bromides with phenylboronic acid. The in vitro cytotoxicity of the compounds was also evaluated against human tumour cell lines (HT29, A549 and HeLa) using the MTT assay method. The results indicate that the dinuclear complex 2 has greater catalytic and anticancer activity in comparison with the mononuclear complexes 1 and 3 .  相似文献   
112.
A convenient, one-pot, three-component regioselective synthesis of novel 2,2′-(1,4-phenylene)-bis-(3-aryl-2-substituted imino-4-aryl-3H-thiazole) derivatives from 1,4-phenylene diisothiocyanate, aryl amines, and various phenacyl bromide, and also the regioselective synthesis of 3-alkyl-2-(aryl imino)-4-cyclopropyl-5-(2′-fluorophenyl)-thiazole derivatives from alkylisothiocyanate, aryl amines, and 2-bromo-2-(2-fluorophenyl)-1-cyclopropylethanone in the presence of poly-4-vinyl pyridine as heterogenous basic catalyst are described. This efficient method produced the products at room temperature with excellent yields (82–96%). The structures of all products were characterized by spectral and elemental analyses. The antimicrobial activity of the synthesized compounds was evaluated against Salmonella enterica, Micrococcus luteus, Bacillus subtilis, and Pseudomonas aeruginosa.  相似文献   
113.

The extraction behavior of Nd(III) and Eu(III) with 0.05 mol dm−3 furosemide in benzyl alcohol as single acidic extractant and then with equimolar (0.05 mol dm−3) synergic mixture of furosemide as acidic extractant and tribenzylamine as neutral donor in benzyl alcohol has been studied from aqueous solutions of pH 1 to 6. The effect of various parameters and of various cations and anions on the extraction of these metal ions was investigated. The composition of the extracted adducts was determined by slope analysis method that came out to be [(M(FS)2)+ (CH3COO)] and [M(FS)3·3TBA] where M = Nd(III) and Eu(III).

  相似文献   
114.
Because herbal nanoparticles have antimicrobial properties, researchers have tried to synthesize them to aid in increasing the shelf time of food and food products. In this regard, gold nanoparticles (AuNPs) synthesized by plants are particularly important. In this study, fresh and clean leaves of Satureja hortensis were selected for the synthesis of AuNPs. We also evaluated the efficacy of these nanoparticles to increase the shelf life of and remove Escherichia coli O157:H7 and Listeria monocytogenes from minced camel's meat. The nanoparticles were analyzed by UV–visible spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectroscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction tests. The FT-IR spectroscopy results demonstrated that the antioxidant compounds in the plant were the sources of reducing power, reducing gold ions to AuNPs. FE-SEM and TEM images revealed the size of the nanoparticles to be 22.26 nm. The 2,2-diphenyl-1-picrylhydrazyl test revealed similar antioxidant potentials for S. hortensis, AuNPs, and butylated hydroxytoluene. S. hortensis and AuNPs had high cell viability dose-dependently against the human umbilical vein endothelial cell line. At the beginning of the food industry part of this experiment, all samples of control, S. hortensis, and AuNPs were preserved at 4°C for 20 days. During these 20 days, the sensory, chemical, and microbiological parameters were assessed for all samples. AuNPs significantly inhibited the growth of E. coli and L. monocytogenes. In addition, AuNPs significantly increased the protein carbonyl content, thiobarbituric acid reactive substances, pH, peroxide value, total volatile base nitrogen, and sensory attributes (color, odor, and overall acceptability). The best results were seen in AuNPs (1%). These findings reveal that the inclusion of S. hortensis extract improves the solubility of AuNPs, which led to a notable enhancement in their preservative and antibacterial effects.  相似文献   
115.
A ferrocenyl-based, chromophore-containing 1-indanone derivative was synthesized through crotonic condensation between 4-chlorobutylferrocenecarboxaldehyde and 5,6-dimethoxy-1-indanone followed by the nucleophilic substitution of chlorine atom of the obtained dyad with different aromatic and aliphatic amines. The electrochemical and optical properties of the synthesized compounds were investigated to explore the relationship between their structures and optical and electrochemical properties. The bandgaps determined from optical absorption spectra ranged from 2.05 to 2.15 eV. The important electrochemical parameters, including the peak potential separation, peak current ratios, and the dependence of peak currents on the scan rate, were studied. Results showed an electrochemically reversible redox system with diffusion-controlled redox process for the synthesized compounds. The study of quantum chemistry was performed on the synthesized compounds using the density functional theory approach. The B3LYP method and 6-311 G(d) basis set were used for optimizing the structures in the gas phase. The theoretical and experimental results show that these compounds can be considered as candidates to be used in optical applications.  相似文献   
116.
Abstract . A cadmium(II) zero-dimensional supramolecular compound [Cd(L)2(I)2] ( 1 ), {L = 2-picolylamine}, was fabricated by branch tube and sonochemical irradiation techniques. Regardless of the method utilized, the same crystallographic structure is obtained for the complex. To investigate the effects of reaction time and solvent on the creation of [Cd(L)2(I)2] ( 1 ) supramolecule compound, certain tests were designed and four specimens of 1 were fabricated through sonochemical process. Less reaction time led to the creation of smaller particles with mixed morphologies. To prepare cadmium(II) oxide micro-crystals via calcination, four samples were utilized as new precursors. Micro- and nano-sphere of cadmium(II) oxide could be fabricated from 1. The morphology and structure of micro- and nano-crystals were identified by using Scanning Electron Microscopy (SEM), IR spectroscopy, and X-ray powder diffraction (XRD).  相似文献   
117.
MoS2 has been commonly used as a catalyst in hydrodesulfurization (HDS) of petroleum cuts in crude oil refineries. In this study, the synthesis of unsupported MoS2 and Co-promoted MoS2 nanosheets produced from molybdenum oxide and thiourea is reported. The synthesized samples were characterized by using x-ray fluorescence, x-ray diffraction, Brunauer–Emmett–Teller (BET), temperature-programmed reduction, thermal gravimetric analysis, and transmission electron microscopy methods, and then they were utilized for HDS of diesel through a fixed-bed catalytic reactor. Results indicated that a cobalt promoter affected both the number and the performance of active sites of the molybdenum sulfides, and the activity of the promoted MoS2 catalyst was consistently higher than that of the MoS2 catalyst. More significantly, the activity of the promoted catalyst was slightly declined during 48 h continuous HDS reaction, which indicated the stability of this catalyst. Additionally, during 12 h of test run, the HDS activity of the promoted catalyst was about 60% higher than MoS2 one.  相似文献   
118.
In this study, combined technique of solid-phase extraction based on multi-walled carbon nanotubes with bio-coacervation extraction (SPE-MWCNT-BCAE) has been developed as a new sample preparation method for the determination of atrazine from water samples. The proposed method involves two steps: analyte enrichment on the solid sorbent and subsequently elution of the analyte by an appropriate solvent. Multi-walled carbon nanotubes (MWCNTs) were used as the sorbent. They have high specific surface area, nano-scale structure and high diffusion rate. The second step is based on the use of bioaggregates for analyte re-enrichment, which consists of biosurfactants and ionic liquid. This method follows the principles of green chemistry. Parameters affecting the extraction efficiency were optimized. Under optimum conditions, the enrichment factor was 176. The linear dynamic range (LDR) and limit of detection (LOD) were 2–100 µg L?1 and 0.66 µg L?1, respectively. The relative standard deviation (RSD) for six replicate measurements was 3.8%. The method was applied to the determination of ultratrace levels of atrazine in environmental water samples with satisfactory results.  相似文献   
119.
Drug delivery vectors for nucleic acid therapeutics (NATs) face significant barriers for translation into the clinic. Spherical nucleic acids (SNAs) – nanoparticles with an exterior shell made up of DNA strands and a hydrophobic interior – have recently shown great potential as vehicles to improve the biodistribution and efficacy of NATs. To date, SNA design has not taken advantage of the powerful chemical modifications available to NATs. Here, we modify SNAs with 2′-deoxy-2′-fluoro-d-arabinonucleic acid (FANA-SNA), and show increased stability, enhanced gene silencing potency and unaided uptake (gymnosis) as compared to free FANA. By varying the spacer region between the nucleic acid strand and the attached hydrophobic polymer, we show that a cleavable DNA based spacer is essential for maximum activity. This design feature will be important when implementing functionalized nucleic acids into nanostructures for gene silencing. The modularity of the FANA-SNA was demonstrated by silencing two different targets. Transfection-free delivery was superior for the modified SNA compared to the free FANA oligonucleotide.

Optimizing FANA modified spherical nucleic acids (FANA-SNAs) for highly efficient delivery of nucleic acid therapeutics.  相似文献   
120.
Microorganisms are highly regarded as a prominent source of natural products that have significant importance in many fields such as medicine, farming, environmental safety, and material production. Due to this, only tiny amounts of microorganisms can be cultivated under standard laboratory conditions, and the bulk of microorganisms in the ecosystems are still unidentified, which restricts our knowledge of uncultured microbial metabolism. However, they could hypothetically provide a large collection of innovative natural products. Culture-independent metagenomics study has the ability to address core questions in the potential of NP production by cloning and analysis of microbial DNA derived directly from environmental samples. Latest advancements in next generation sequencing and genetic engineering tools for genome assembly have broadened the scope of metagenomics to offer perspectives into the life of uncultured microorganisms. In this review, we cover the methods of metagenomic library construction, and heterologous expression for the exploration and development of the environmental metabolome and focus on the function-based metagenomics, sequencing-based metagenomics, and single-cell metagenomics of uncultured microorganisms.  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