全文获取类型
收费全文 | 885篇 |
免费 | 61篇 |
国内免费 | 102篇 |
专业分类
化学 | 895篇 |
晶体学 | 14篇 |
力学 | 5篇 |
综合类 | 31篇 |
数学 | 3篇 |
物理学 | 100篇 |
出版年
2024年 | 2篇 |
2023年 | 18篇 |
2022年 | 46篇 |
2021年 | 42篇 |
2020年 | 43篇 |
2019年 | 28篇 |
2018年 | 28篇 |
2017年 | 34篇 |
2016年 | 42篇 |
2015年 | 33篇 |
2014年 | 25篇 |
2013年 | 50篇 |
2012年 | 53篇 |
2011年 | 56篇 |
2010年 | 46篇 |
2009年 | 30篇 |
2008年 | 44篇 |
2007年 | 47篇 |
2006年 | 44篇 |
2005年 | 49篇 |
2004年 | 36篇 |
2003年 | 27篇 |
2002年 | 60篇 |
2001年 | 36篇 |
2000年 | 15篇 |
1999年 | 19篇 |
1998年 | 17篇 |
1997年 | 9篇 |
1996年 | 10篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 8篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 9篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有1048条查询结果,搜索用时 140 毫秒
51.
Baicalin which has multiple biological activities is the main active component of the root of Scutellaria baicalensis Georgi (SBG). Although its isolation and purification by adsorption methods have aroused much interest of the scientific community, it suffered from the poor selectivity of the adsorbents. In this work, an environmentally benign method was developed to prepare ionic liquids (ILs) grafted silica by using IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim]NTf2) and ethanol as reaction media. The IL 1-propyl-3-methylimidazolium chloride ([C3mim]Cl) grafted silica ([C3mim]+Cl−@SiO2) was used to adsorb and purify baicalin from the root extract of Scutellaria baicalensis Georgi (SBG). Experimental results indicated that the adsorption equilibrium can be quickly achieved (within 10 min). The adsorption behavior of [C3mim]+Cl−@SiO2 for baicalin was in good agreement with Langmuir and Freundlich models and the adsorption was a physisorption process as suggested by Dubinin–Radushkevich model. Compared with commercial resins, [C3mim]+Cl−@SiO2 showed the strongest adsorption ability and highest selectivity. After desorption and crystallization, a purity of baicalin as high as 96.5% could be obtained. These results indicated that the ILs grafted silica materials were promising adsorbents for the adsorption and purification of baicalin and showed huge potential in the purification of other bioactive compounds from natural sources. 相似文献
52.
《印度化学会志》2021,98(11):100188
Clean and potable water is a growing concern around the globe. Among the different water pollutants, heavy metal ions pose a serious health concern to all living beings. The quest for new adsorbents to remove heavy metal ions received a boost with the development in the field of metal-organic framework (MOF). The advancement in synthetic strategies and designing of MOF enabled the researchers to tune the adsorption characteristics and tailor the material specific to a heavy metal ion. Similar to MOF, graphene-based two-dimensional and three-dimensional materials are also promising due to the diverse functionalization possibilities and cost-effectiveness. There had been growing interest in applying MOF and graphene-based materials for the removal of heavy metal ions in the past decade. This review summarizes these developments in detail. 相似文献
53.
Selective Extraction of Metal Ions from Aqueous Phase to Ionic Liquids: A Novel Thermodynamic Approach to Separations
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The selective extraction of metals from aqueous mixtures has generally relied on the use of selective ionophores. We present an alternative strategy that exploits a recently developed approach to extraction into an ionic liquid phase, and show that a high degree of control over selectivity can be obtained by tuning the relative concentrations of extraction agents. A thermodynamic model for the approach is presented, and an experimental separation of strontium and potassium ions is performed. It is shown that tuning the concentrations of the species involved can shift the ratio of potassium to strontium in the ionic liquid phase from 4:1 to 3:4. This extraction is performed under mild conditions with relatively common reagents. The result is a proof‐of‐concept for a novel separations scheme that could have great importance in a wide range of technological applications. 相似文献
54.
In this work, the influence of metallic dopant addition in 10 wt % Ni/γ-Al2O3 catalyst on the material physico-chemical properties and catalytic activity for the toluene steam reforming was studied. Seventeen doped Ni/γ-Al2O3 catalysts were synthesized by the sol–gel process. The aim of this study was to determine which elements were the most suitable for the doping of 10 wt % Ni/γ-Al2O3 catalysts. The influence of the dopants was studied through different physico-chemical techniques. It appeared that some dopants showed lower catalytic performances due to high carbon deactivation. On the contrary, some dopants increased the resistance to coking while also improving the catalytic activity. Different mechanisms were proposed to explain these modifications of catalytic behavior. Among all doped Ni/γ-Al2O3 catalysts, the samples that combined Mn + Mo or Co + Mo dopants showed the best catalytic performances at 650 °C. Both samples showed high toluene reforming activity and low amounts of carbon deposit. 相似文献
55.
Antibody drug conjugates are cytotoxic pharmaceuticals, designed to destroy malignant cells. A cytotoxic molecule is attached to an antibody that binds specific to a cancer‐cell surface. Given the high toxicity of the drugs, strict safety standards have to be kept. For this reason, an antibody drug conjugates model was developed with fluorescein 5‐isothiocyanate as the nontoxic payload surrogate. Due to the similar hydrophobicity, this model is used to establish a suitable purification process and characterization method for antibody drug conjugates. Because of the pH dependent solubility of fluorescein, the hydrophobicity of conjugates can be modulated by the pH value. Based on the complex heterogeneity and hydrophobicity of the conjugates a chromatographic purification is challenging. Hydrophobic interaction chromatography is used for analytical as well as for preparative separation. Because of the increased hydrophobicity of the conjugates compared to native antibody, hydrophobic interaction chromatography often suffer from resolution and recovery problems. Conjugates were separated differing on the number of payloads attached to the antibody. For this matter, the drug–antibody ratio is determined and used as a quantitative term. The conjugates are purified at high recoveries and resolution by step gradients using suitable resins, allowing the separation of the target drug–antibody ratio. 相似文献
56.
Meijuan Xu Zhina Qiao Genshu Huang Mengfei Long Taowei Yang Xian Zhang Minglong Shao Zhenghong Xu Zhiming Rao 《Journal of separation science》2020,43(14):2936-2948
l ‐Arginine has many special physiological and biochemical functions, with wide applications in the food and pharmaceutical industry. Few studies on the purification of l ‐arginine from fermentation broth have been conducted; however, none of them were systematic enough for industrial scale‐up. Therefore, it is necessary to develop a highly efficient and systematic process for the purification of l ‐arginine from fermentation broth. In this study, we screened out a cation exchange resin, D155, having high exchange capacity, high selectivity, and easy elution capacity, and analyzed its adsorption isotherm, thermodynamics, and kinetics using different models. Further, the process parameters of fixed‐bed ion exchange adsorption and elution were optimized, and the penetration curve during the operation was modeled. Based on the fixed‐bed ion‐exchange parameters, a 30‐column continuous ion‐exchange system was designed, and the flow velocity in each zone was optimized. Finally, to obtain a high purity of l ‐arginine, the purification tests were conducted using anion exchange resin 711, and an l ‐arginine yield of 99.1% and purity of 98.5% was obtained. This effective and economical method also provides a promising strategy for separation of other amino acids from the fermentation broth, which is of great significance to the l ‐arginine fermentation industry. 相似文献
57.
A novel, facile, and robust strategy was proposed to increase the pore size and mechanical strength of cryogels. By mixing the monomers of acrylamide and 2‐hydroxyethyl methacrylate as the precursor, a monolithic copolymer cryogel with large interconnected pores and thick pore walls was prepared. Hydrogen bonding between the two monomers contributed to the entanglement and aggregation of the copolymers, thickening the pore walls and resulting in larger pore sizes. Analysis via mercury porosimetry demonstrated that the interconnected pore diameter of the copolymer cryogel ranged from 10‐350 µm, which was far larger than that of the cryogels from one monomer (10‐50 µm). Additionally, the thicker pore walls of the copolymer cryogel improved its mechanical strength. Affinity cryogels were prepared through covalent immobilization using Tris(hydroxymethyl)aminomethane as a coupling agent, and the affinity binding of lysozymes on Tris‐cryogel was evaluated by the Langmuir isothermal adsorption with the maximum adsorption capacity of 360 mg/g. Compared with that of the Tris‐cryogels produced from one monomer, the copolymer Tris‐cryogel exhibited higher adsorption capacity and lysozyme purity, when the chicken egg white solution flowed solely driven by gravity. This work provides a new avenue for designing and developing supermacroporous cryogels for bioseparation. 相似文献
58.
In order to screen out Saccharomyces cerevisiae suitable for table grape fermentation, and compare it with commercial Saccharomyces cerevisiae in terms of fermentation performance and aroma producing substances, differences of fermentation flavor caused by different strains were discussed. In this experiment, yeast was isolated and purified from vineyard soil, 26s rDNA identification and fermentation substrate tolerance analysis were carried out, and the causes of flavor differences of wine were analyzed from three aspects: GC-MS, PCA and sensory evaluation. The results showed that strain S1 had the highest floral aroma fraction, corresponding to its high production of ethyl octanoate and other substances, and it had the characteristics of high sugar tolerance. The fruit sensory score of S3 wine was the highest among the six wines. Through exploration and analysis, it was found that compared with commercial Saccharomyces cerevisiae, the screened strains had more advantages in fermenting table grapes. The flavor of each wine was directly related to the growth characteristics and tolerance of its strains. 相似文献
59.
Mihail Mihaylov Elena Ivanova Videlina Zdravkova Stanislava Andonova Nikola Drenchev Kristina Chakarova Radoslav Kefirov Rositsa Kukeva Radostina Stoyanova Konstantin Hadjiivanov 《Molecules (Basel, Switzerland)》2022,27(1)
The transition to a hydrogen economy requires the development of cost-effective methods for purifying hydrogen from CO. In this study, we explore the possibilities of Cu/ZSM-5 as an adsorbent for this purpose. Samples obtained by cation exchange from aqueous solution (AE) and solid-state exchange with CuCl (SE) were characterized by in situ EPR and FTIR, H2-TPR, CO-TPD, etc. The AE samples possess mainly isolated Cu2+ cations not adsorbing CO. Reduction generates Cu+ sites demonstrating different affinity to CO, with the strongest centres desorbing CO at about 350 °C. The SE samples have about twice higher Cu/Al ratios, as one H+ is exchanged with one Cu+ cation. Although some of the introduced Cu+ sites are oxidized to Cu2+ upon contact with air, they easily recover their original oxidation state after thermal treatment in vacuum or under inert gas stream. In addition, these Cu+ centres regenerate at relatively low temperatures. It is important that water does not block the CO adsorption sites because of the formation of Cu+(CO)(H2O)x complexes. Dynamic adsorption studies show that Cu/ZSM-5 selectively adsorbs CO in the presence of hydrogen. The results indicate that the SE samples are very perspective materials for purification of H2 from CO. 相似文献
60.
Tehrim Motiwala Blessing Oluebube Akumadu Sbahle Zuma Mbalenhle Sizamile Mfeka Wanping Chen Ikechukwu Achilonu Khajamohiddin Syed Thandeka Khoza 《Molecules (Basel, Switzerland)》2022,27(1)
Caseinolytic proteins (Clp), which are present in both prokaryotes and eukaryotes, play a major role in cell protein quality control and survival of bacteria in harsh environmental conditions. Recently, a member of this protein family, ClpK was identified in a pathogenic strain of Klebsiella pneumoniae which was responsible for nosocomial infections. ClpK is linked to the thermal stress survival of this pathogen. The genome wide analysis of Clp proteins in Klebsiella spp. indicates that ClpK is present in only 34% of the investigated strains. This suggests that the uptake of the clpk gene is selective and may only be taken up by a pathogen that needs to survive harsh environmental conditions. In silico analyses and molecular dynamic simulations show that ClpK is mainly α-helical and is highly dynamic. ClpK was successfully expressed and purified to homogeneity using affinity and anion exchange chromatography. Biophysical characterization of ClpK showed that it is predominantly alpha-helical, and this is in agreement with in silico analysis of the protein structure. Furthermore, the purified protein is biologically active and hydrolyses ATP in a concentration- dependent manner. 相似文献