全文获取类型
收费全文 | 10203篇 |
免费 | 414篇 |
国内免费 | 79篇 |
专业分类
化学 | 7292篇 |
晶体学 | 61篇 |
力学 | 140篇 |
数学 | 1533篇 |
物理学 | 1670篇 |
出版年
2023年 | 60篇 |
2022年 | 63篇 |
2021年 | 113篇 |
2020年 | 217篇 |
2019年 | 178篇 |
2018年 | 105篇 |
2017年 | 85篇 |
2016年 | 278篇 |
2015年 | 222篇 |
2014年 | 264篇 |
2013年 | 500篇 |
2012年 | 534篇 |
2011年 | 610篇 |
2010年 | 369篇 |
2009年 | 327篇 |
2008年 | 552篇 |
2007年 | 540篇 |
2006年 | 549篇 |
2005年 | 512篇 |
2004年 | 424篇 |
2003年 | 323篇 |
2002年 | 383篇 |
2001年 | 181篇 |
2000年 | 188篇 |
1999年 | 162篇 |
1998年 | 168篇 |
1997年 | 150篇 |
1996年 | 158篇 |
1995年 | 132篇 |
1994年 | 155篇 |
1993年 | 132篇 |
1992年 | 114篇 |
1991年 | 107篇 |
1990年 | 89篇 |
1989年 | 74篇 |
1988年 | 62篇 |
1987年 | 68篇 |
1985年 | 111篇 |
1984年 | 96篇 |
1983年 | 65篇 |
1982年 | 102篇 |
1981年 | 89篇 |
1980年 | 76篇 |
1979年 | 95篇 |
1978年 | 86篇 |
1977年 | 78篇 |
1976年 | 87篇 |
1975年 | 63篇 |
1974年 | 55篇 |
1973年 | 56篇 |
排序方式: 共有10000条查询结果,搜索用时 93 毫秒
141.
Alfred Deege Heribert Husmann Eduard Hübinger Frank Kobor Gerhard Schomburg 《Journal of separation science》1993,16(10):587-593
Complex mixtures of partially alkylated cyclodextrins can be analyzed by both HPLC and high temperature capillary GC. Because of the limited efficiency of LC, suitable analytical and preparative separations can be achieved only with systems of carefully optimized selectivity. Using LC it has been possible to isolate and purify single cyclodextrin species from very complex mixtures of components which contain unreacted hydroxyl groups in addition to the alkoxy groups. Analysis of the reaction mixtures and of fractions taken from LC separations can be performed with advantage by high resolution capillary GC at high temperatures between 300 and 400 °C. The thermal stability of partially alkylated cyclodextrins in high temperature GC is considerably increased by trimethylsilylation of the free hydroxyl groups. Fast atom bombardment mass spectrometry and proton NMR were used to identify species isolated from the preparative LC separations. 相似文献
142.
固相萃取柱上衍生气相色谱-质谱法测定水中烷基酚 总被引:7,自引:0,他引:7
以烷基酚(APs)主要降解产物辛基酚(4-t-OP)、壬基酚(4-n-NP)为研究对象,建立了固相萃取(SPE)柱上衍生化、气相色谱-质谱(GC-MS)法测定水中APs的分析方法。以C18柱为固相萃取柱、N,O-(三甲基硅)三氟乙酰胺(BSTFA)为硅烷化试剂,设计五因素四水平正交实验L16(45),对衍生化影响因素、衍生化溶剂、衍生化时间以及SPE主要影响因素pH值、盐度和洗脱剂进行优化;在优化条件下,方法的回收率(高于80%)和重现性(RSD低于10%)结果令人满意,4-t-OP和4-n-NP的仪器检出限分别为3.35ng/L和6.38ng/L。采用建立的方法,回收率略高于传统的SPE萃取衍生法,具有有机溶剂用量少,方法简单快速、灵敏度高的特点,适用于河水和海水中痕量烷基酚的快速测定。 相似文献
143.
The apparent molal volume and adiabatic compressibilities of some transition metal (Mn2+, Co2+ Ni2+, Cu2+, Zn2+, and Cd2+) sulfates have been determined at 25°C. Values of
to 11.4 cm3-mole–1 and
to 31.3 × 10–4cm3-mole–1-bar–1 at 1 atm were found for the formation of the transition metal sulfate ion pairs. These results are in good agreement with the values obtained from the high-pressure conductance measurements of Fisher et al., Shimizu et al., and Taniguchi et al. The volume and compressibility data indicate that 3.1±0.7 water molecules are lost when transition metals form ion pairs with SO
4
2–
. The fractions of inner-sphere ion pairs (20%) estimated in this study are in good agreement with the values obtained from ultrasonic measurements. 相似文献
144.
Electron micrographs of parallel arrays of negatively stained ramie cellulose protofibrils were analyzed using the two-dimensional digital autocorrelation function (ACF). The method is based upon the statistical analysis of images in real space. The ACF shows strong parallel streaks of high correlation, and the lateral distance between adjacent streaks allows the mean interfibrillar distance to be estimated as 3.7 nm. The intensity profile along the streaks shows a weak modulation with peaks occurring at integral multiples of 3 or 6 nm. These results provide direct evidence that there is a regular axial texture in the protofibrils, and corroborate the conclusions previously drawn from optical diffraction analysis. Using the difference vectors found in the ACF it has been possible to reduce the picture noise level by linear integration, thereby obtaining an enhanced image. A preliminary result obtained in this way suggests that the projected protofibril morphology associated with the observed axial periodicity is a ribbon-like zigzag structure. Possible applications of the method for future work are discussed. 相似文献
145.
Robin L. Garrell John C. Smyth Frank R. Fronczek Richard D. Gandour 《Journal of inclusion phenomena and macrocyclic chemistry》1988,6(1):73-78
Single crystal X-ray analysis of the 2:1 acetonitrile complex of 18-crown-6 is reported. Crystals of the complex are monoclinic,P21/n, witha=9.123(3),b=8.524(3),c=13.676(4) Å, =104.68(3)°, andD
c
=1.118 g cm–3 forZ=2. The complex lies on a center of symmetry, with the crown in theD
3d conformation. Methyl groups of the acetonitrile molecules have weak interactions with the crown oxygen atoms, and are tilted 31.7° from the host's threefold axis. Methyl hydrogen atoms are rotationally disordered about the acetonitrile axis.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82057 (12 pages). 相似文献
146.
147.
Samuel Melaku Rita Cornelis Frank Vanhaecke Richard Dams Luc Moens 《Mikrochimica acta》2005,150(3-4):225-231
A simple, sensitive and inexpensive method for the speciation of Cr(VI) and Cr(III) in river and industrial wastewater was developed, optimized and validated. Samples were collected, filtered and then chromium species were determined in the filtrate. In the filtrate, total Cr was determined directly by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). A portion of the filtered sample was buffered to pH 6.4, extracted with Amberlite LA-2/MIBK and finally Cr(VI) was determined in the organic extract and Cr(III) in the aqueous phase using GFAAS. The method was evaluated by analysis of the certified reference material, CRM 544, and good accuracy was obtained. The limit of detection for Cr(VI) and Cr(tot)/Cr(III) was found to be 0.30 and 0.08 µg L−1, respectively, and a precision expressed as relative standard deviation of better than 11% was achieved for nine replicates. A number of water samples from the Tinishu Akaki River, Ethiopia, and wastewater samples from a chemical plant in Germany, were analysed. In addition to the GFAAS method, Cr(tot) was also determined using ICP-MS (in CRM 544, lyophilized water, and Tinishu Akaki River water samples) and Cr(tot) and Cr(VI) using UV-VIS spectrophotometry (in CRM 544 and industrial wastewater samples). Good agreement between the different methods was found. 相似文献
148.
Watson MD Jäckel F Severin N Rabe JP Müllen K 《Journal of the American Chemical Society》2004,126(5):1402-1407
Cyclophanes with the largest-to-date polycyclic aromatic hydrocarbon (hexa-peri-hexabenzocoronene, HBC) to be entrained in such a structural motif are reported. The two disks are covalently captured by intermolecular ring-closing olefin metathesis of dienes in good yield. DSC, optical microscopy, and WAXD show the new cyclophanes to self-assemble to thermotropic columnar liquid crystal mesophases similar to monomeric analogues. Solution spectroscopic studies reveal that the two disks within a single unit lie face-to-face, with a small average lateral offset. Self-assembly into two-dimensional crystals at a solid-liquid interface was visualized by STM, and the electrical properties of single molecules were assessed by scanning tunneling spectroscopy revealing a diode-like behavior which is similar to that previously reported for single HBC disks, laying the groundwork for future electrical interrogations of dynamic molecular complexes. 相似文献
149.
Collison D Goodgame DM Hitchman MA Lippert B Mabbs FE McInnes EJ 《Inorganic chemistry》2002,41(11):2826-2833
Multifrequency continuous wave EPR spectra (4-34 GHz) on a powder of the title compound are consistent with a spin-triplet state. This arises from interaction between centrosymmetrically related pairs of copper(II) ions in the solid. The spectra at all frequencies have been simulated with a single set of spin-Hamiltonian parameters. The results show that there is noncoincidence between the principal axes of the g-matrices on each copper center and those of the zero-field splitting (D) tensor. This noncoincidence is a single rotation of 33 degrees +/- 2 degrees. The parameters from the powder spectra have been verified by a subsequent single-crystal EPR study which yielded the spin-Hamiltonian parameters g(XX) = 2.074, g(YY) = 2.093, g(ZZ) = 2.385, D(XX) = +/-0.0228 cm(-1), D(YY) = +/-0.0211 cm(-1), D(ZZ) = -/+0.0439 cm(-1) with Euler angles of alpha = 179 degrees, chi = 33.4 degrees, and gamma = 328 degrees. Analysis of the zero-field splitting tensor in terms of exchange indicates that the interaction between the pairs of copper(II) ions is almost entirely dipolar in origin. This study shows that multifrequency EPR spectroscopy on powders, coupled with spectrum simulation, can detect and measure noncoincidence between the principal axes of the g-matrix and zero-field splitting tensor, and does not necessarily require the presence of metal hyperfine interactions. 相似文献
150.
The synthesis of 4-(methylthio)-1H-imidazo[4,5-c]pyridine 2′-deoxy-β-D -ribonucleosides 2 and 9 and the conversion of the N1-isomer 2 into the 2′,3′-didehydro-2′,3′-dideoxyribonucleoside 3a or (via 7 ) 3-deaza-2′-deoxyadenosine ( 1 ) is described. Phosphonate building blocks of 1 were employed in solid-phase synthesis of self-complementary base-modified oligonucleotides. Their properties were studied with regard to duplex stability and hydrolysis by the restriction enzyme Eco RI. 相似文献