全文获取类型
收费全文 | 4422篇 |
免费 | 197篇 |
国内免费 | 1218篇 |
专业分类
化学 | 5430篇 |
晶体学 | 25篇 |
力学 | 24篇 |
综合类 | 24篇 |
数学 | 13篇 |
物理学 | 321篇 |
出版年
2024年 | 6篇 |
2023年 | 17篇 |
2022年 | 64篇 |
2021年 | 59篇 |
2020年 | 112篇 |
2019年 | 99篇 |
2018年 | 101篇 |
2017年 | 161篇 |
2016年 | 195篇 |
2015年 | 148篇 |
2014年 | 164篇 |
2013年 | 457篇 |
2012年 | 244篇 |
2011年 | 235篇 |
2010年 | 243篇 |
2009年 | 297篇 |
2008年 | 294篇 |
2007年 | 261篇 |
2006年 | 262篇 |
2005年 | 254篇 |
2004年 | 234篇 |
2003年 | 180篇 |
2002年 | 185篇 |
2001年 | 170篇 |
2000年 | 171篇 |
1999年 | 166篇 |
1998年 | 138篇 |
1997年 | 138篇 |
1996年 | 118篇 |
1995年 | 114篇 |
1994年 | 123篇 |
1993年 | 101篇 |
1992年 | 100篇 |
1991年 | 55篇 |
1990年 | 44篇 |
1989年 | 36篇 |
1988年 | 33篇 |
1987年 | 15篇 |
1986年 | 9篇 |
1985年 | 7篇 |
1984年 | 5篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 5篇 |
1978年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有5837条查询结果,搜索用时 5 毫秒
201.
Carl F. Brunius Ulrica Edlund Ann‐Christine Albertsson 《Journal of polymer science. Part A, Polymer chemistry》2002,40(21):3652-3661
This work is devoted to the design of a novel family of hydrosoluble biomaterials: poly(N‐vinyl‐2‐pyrrolidone) (PVP)‐based graft copolymers. A synthesis route has been elaborated in which ω‐functionalized PVP is prepared via chain‐transfer radical polymerization, end‐group modified, and subsequently grafted onto a polyhydroxylated backbone, typically dextran or poly(vinyl alcohol). The resulting graft copolymer biomaterials are designed for use in various biomedical applications, particularly as materials with a stronger potential for plasma expansion than already existing products have. The graft copolymers are potentially degradable because the PVP grafts are connected to the polyol backbone via a hydrolytically labile carbonate or ester linkage. The degradation of the graft copolymers was performed in vitro over a period of 6 weeks. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3652–3661, 2002 相似文献
202.
Synthesis, characterization and protein adsorption behaviors of PLGA/PEG di-block co-polymer blend films 总被引:1,自引:0,他引:1
A series of poly(D,L-lactic-co-glycolic acid) (PLGA)/poly(ethyleneglycol) (PEG) di-block copolymers were synthesized by ring-opening polymerization of D,L-lactide and glycolide with different molecular weights of monomethoxy polyethyleneglycol (mPEG) 750, 2000 and 5000 as an initiator. The bulk properties of these co-polymers were characterized by using 1H NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry (DSC). Electron spectroscopy for chemical analysis (ESCA) results, in which the blend films with the di-block copolymers showed increasing surface oxygen atomic percentage with increasing PEG chain length, indicate that PEG chain segment in the di-block copolymers is surface oriented and enriched onto the surface of the blend films. The extent of protein adsorption onto the surface of these blend films was studied, using iodine radio-labeled human serum albumin, gamma globulin and human growth hormone. The protein adsorption amount was reduced for the blend films prepared with PLGA/PEG 750 and 2000 di-block copolymers, but increased to a great extent for PLGA/PEG 5000 di-block copolymer. This is due to the increased water uptake capacity of the blend film, which absorbed more protein molecules into a swollen polymer matrix in addition to surface adsorption. 相似文献
203.
Dr. Marcella Chiari Francesco Damin Alessandra Melis Roberto Consonni 《Electrophoresis》1998,19(18):3154-3159
New copolymers of acrylamide and β-D -glucopyranoside were synthesized and characterized. The different reactivity of the two monomers towards radical polymerization meant we could control the growth of the polymer chains whose length was inversely related to the number of glucose residues incorporated in the copolymers. The properties of these polymers were investigated in the separation of oligonucleotides and double-stranded DNA by capillary electrophoresis (CE) in coated and uncoated capillaries. The new copolymers were a suitable matrix for CE due to their high-resolving capacity and low viscosity. We also looked into the advantages of a new method of dynamic suppression of electroosmotic flow based on the addition of small amounts (0.03–0.05%) of dimethylacrylamide to the sieving and to the running buffer. A complete test was run on the reproducibility and efficiency of separations carried out in a permanently and dynamically coated capillary, and the advantages and disadvantages of the two methods were compared. 相似文献
204.
New alternating equimolar copolymers of electrophilic trisubstituted ethylenes, methyl 3-phenyl-2-cyanopropenoate and 2-phenyl-1,1-dicyanoethene, with ethyl, n-butyl, i-butyl, t-butyl, 2-chloroethyl, and phenyl vinyl ethers were prepared by free radical initiation. Chemical compositions of the copolymers are 1 : 1 in broad ranges of monomer ratios. The copolymerization rate of both electrophilic monomers with the vinyl ethers increase in the series 2-chloroethyl > ethyl > phenyl > n-butyl > i-butyl > t-butyl. These variations in the reactivity of the vinyl ethers are discussed in terms of their preferred conformations in donor-acceptor complexes with electrophilic trisubstituted ethylenes. © 1993 John Wiley & Sons, Inc. 相似文献
205.
206.
John Ojur Dennis Mohammed Khalil Mohammed Ali Khalid Hassan Ibnaouf Osama Aldaghri Naglaa F. M. Abdel All Abdullahi Abbas Adam Fahad Usman Yarima Mudassir Hassan Bashir Abubakar Abdulkadir 《Molecules (Basel, Switzerland)》2022,27(17)
In this study, a solution casting method was used to prepare solid polymer electrolytes (SPEs) based on a polymer blend comprising polyvinyl alcohol (PVA), cellulose acetate (CA), and potassium carbonate (K2CO3) as a conducting salt, and zinc oxide nanoparticles (ZnO-NPs) as a nanofiller. The prepared electrolytes were physicochemically and electrochemically characterized, and their semi-crystalline nature was established using XRD and FESEM. The addition of ZnO to the polymer–salt combination resulted in a substantial increase in ionic conductivity, which was investigated using impedance analysis. The size of the semicircles in the Cole–Cole plots shrank as the amount of nanofiller increased, showing a decrease in bulk resistance that might be ascribed to an increase in ions due to the strong action of the ZnO-NPs. The sample with 10 wt % ZnO-NPs was found to produce the highest ionic conductivity, potential window, and lowest activation energy (Ea) of 3.70 × 10–3 Scm–1, 3.24 V, and 6.08 × 10–4 eV, respectively. The temperature–frequency dependence of conductivity was found to approximately follow the Arrhenius model, which established that the electrolytes in this study are thermally activated. Hence, it can be concluded that, based on the improved conductivity observed, SPEs based on a PVA-CA-K2CO3/ZnO-NPs composite could be applicable in all-solid-state energy storage devices. 相似文献
207.
Reducing the use of solvents is an important aim of green chemistry. Using micelles self-assembled from amphiphilic molecules dispersed in water (considered a green solvent) has facilitated reactions of organic compounds. When performing reactions in micelles, the hydrophobic effect can considerably accelerate apparent reaction rates, as well as enhance selectivity. Here, we review micellar reaction media and their potential role in sustainable chemical production. The focus of this review is applications of engineered amphiphilic systems for reactions (surface-active ionic liquids, designer surfactants, and block copolymers) as reaction media. Micelles are a versatile platform for performing a large array of organic chemistries using water as the bulk solvent. Building on this foundation, synthetic sequences combining several reaction steps in one pot have been developed. Telescoping multiple reactions can reduce solvent waste by limiting the volume of solvents, as well as eliminating purification processes. Thus, in particular, we review recent advances in “one-pot” multistep reactions achieved using micellar reaction media with potential applications in medicinal chemistry and agrochemistry. Photocatalyzed reactions in micellar reaction media are also discussed. In addition to the use of micelles, we emphasize the process (steps to isolate the product and reuse the catalyst). 相似文献
208.
以醋酸铀酰为主要试剂, 在负离子检测模式下, 采用电喷雾串联质谱法制备了甲基羟基铀酰负离子. 实验发现, 气相中的甲基羟基铀酰离子与水分子发生分子离子复分解反应, 并用串联质谱法对反应产生的离子性产物进行了结构确认, 提出了反应的可能机理. 热力学计算结果表明, 该反应的ΔGReaction为-473.0 kJ/mol, ΔHReaction为-236.5 kJ/mol, ΔSSystem为0.792 kJ·mol-1·K-1. 该反应的速率常数为2.26 s-1. 相似文献
209.
210.
采用ε-己内酯(CL)开环聚合的方法首先合成树枝状聚(醚-酰胺)基(DPEA)星形聚合物star-PCL,再与异氰酸基封端的PEG(PEG-NCO)偶合制备了两亲性树枝状聚(醚-酰胺)基星形嵌段聚合物star-PCL-b-PEG.利用FT-IR、1H-NMR和GPC分析测试手段对star-PCL-b-PEG的结构进行了表征.通过滴加选择性溶剂的方法,制备了star-PCL-b-PEG以水为介质的类似"平头"聚集体胶束溶液.采用荧光光谱法测得star-PCL-b-PEG水溶液的临界胶束浓度(CMC)为1.623mg/L;采用激光光散射仪测得其在浓度0.15mg/mL和0.5mg/mL的流体力学半径分别为86.2nm和224.6nm,其多分散指数分别为0.115和0.197.透射电镜(TEM)观察发现胶束的形貌受共溶剂的特性,初始聚合物浓度,水含量等因素的影响. 相似文献