全文获取类型
收费全文 | 1803篇 |
免费 | 53篇 |
国内免费 | 10篇 |
专业分类
化学 | 1073篇 |
晶体学 | 14篇 |
力学 | 43篇 |
数学 | 430篇 |
物理学 | 306篇 |
出版年
2020年 | 16篇 |
2019年 | 18篇 |
2018年 | 12篇 |
2017年 | 16篇 |
2016年 | 32篇 |
2015年 | 32篇 |
2014年 | 32篇 |
2013年 | 94篇 |
2012年 | 79篇 |
2011年 | 94篇 |
2010年 | 53篇 |
2009年 | 44篇 |
2008年 | 84篇 |
2007年 | 81篇 |
2006年 | 97篇 |
2005年 | 93篇 |
2004年 | 65篇 |
2003年 | 66篇 |
2002年 | 84篇 |
2001年 | 20篇 |
2000年 | 32篇 |
1999年 | 26篇 |
1998年 | 28篇 |
1997年 | 30篇 |
1996年 | 27篇 |
1995年 | 15篇 |
1994年 | 32篇 |
1993年 | 27篇 |
1992年 | 21篇 |
1991年 | 22篇 |
1990年 | 19篇 |
1989年 | 16篇 |
1988年 | 12篇 |
1987年 | 18篇 |
1986年 | 18篇 |
1985年 | 20篇 |
1984年 | 30篇 |
1983年 | 21篇 |
1982年 | 30篇 |
1981年 | 33篇 |
1980年 | 28篇 |
1979年 | 23篇 |
1978年 | 30篇 |
1977年 | 23篇 |
1976年 | 20篇 |
1975年 | 17篇 |
1974年 | 20篇 |
1973年 | 19篇 |
1972年 | 14篇 |
1971年 | 13篇 |
排序方式: 共有1866条查询结果,搜索用时 15 毫秒
91.
Mareike Prüfer Christian Wenger Frank F. Bier Eva-Maria Laux Ralph Hölzel 《Electrophoresis》2022,43(18-19):1920-1933
Dielectrophoresis (DEP) is an AC electrokinetic effect mainly used to manipulate cells. Smaller particles, like virions, antibodies, enzymes, and even dye molecules can be immobilized by DEP as well. In principle, it was shown that enzymes are active after immobilization by DEP, but no quantification of the retained activity was reported so far. In this study, the activity of the enzyme horseradish peroxidase (HRP) is quantified after immobilization by DEP. For this, HRP is immobilized on regular arrays of titanium nitride ring electrodes of 500 nm diameter and 20 nm widths. The activity of HRP on the electrode chip is measured with a limit of detection of 60 fg HRP by observing the enzymatic turnover of Amplex Red and H2O2 to fluorescent resorufin by fluorescence microscopy. The initial activity of the permanently immobilized HRP equals up to 45% of the activity that can be expected for an ideal monolayer of HRP molecules on all electrodes of the array. Localization of the immobilizate on the electrodes is accomplished by staining with the fluorescent product of the enzyme reaction. The high residual activity of enzymes after AC field induced immobilization shows the method's suitability for biosensing and research applications. 相似文献
92.
Poor aqueous solubility of active compounds is a major issue in today’s drug delivery. In this study the smartFilm-technology was exploited to improve the dermal penetration efficacy of a poorly soluble active compound (curcumin). Results were compared to the dermal penetration efficacy of curcumin from curcumin bulk suspensions and nanocrystals, respectively. The smartFilms enabled an effective dermal and transdermal penetration of curcumin, whereas curcumin bulk- and nanosuspensions were less efficient when the curcumin content was similar to the curcumin content in the smartFilms. Interestingly, it was found that increasing numbers of curcumin particles within the suspensions increased the passive dermal penetration of curcumin. The effect is caused by an aqueous meniscus that is created between particle and skin if the dispersion medium evaporates. The connecting liquid meniscus causes a local swelling of the stratum corneum and maintains a high local concentration gradient between drug particles and skin. Thus, leading to a high local passive dermal penetration of curcumin. The findings suggest a new dermal penetration mechanism for active compounds from nano-particulate drug delivery systems, which can be the base for the development of topical drug products with improved penetration efficacy in the future. 相似文献
93.
Dr. Luke D. Elliott Dr. Jonathan P. Knowles Dr. Paul J. Koovits Katie G. Maskill Michael J. Ralph Dr. Guillaume Lejeune Lee J. Edwards Richard I. Robinson Ian R. Clemens Brian Cox David D. Pascoe Guido Koch Martin Eberle Malcolm B. Berry Prof. Kevin I. Booker‐Milburn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15226-15232
The use of flow photochemistry and its apparent superiority over batch has been reported by a number of groups in recent years. To rigorously determine whether flow does indeed have an advantage over batch, a broad range of synthetic photochemical transformations were optimized in both reactor modes and their yields and productivities compared. Surprisingly, yields were essentially identical in all comparative cases. Even more revealing was the observation that the productivity of flow reactors varied very little to that of their batch counterparts when the key reaction parameters were matched. Those with a single layer of fluorinated ethylene propylene (FEP) had an average productivity 20 % lower than that of batch, whereas three‐layer reactors were 20 % more productive. Finally, the utility of flow chemistry was demonstrated in the scale‐up of the ring‐opening reaction of a potentially explosive [1.1.1] propellane with butane‐2,3‐dione. 相似文献
94.
Jingxuan Ren Songfeng Han Ashley R. Proctor Danielle E. Desa Gabriel A. Ramirez Vincent Ralph D. Ching-Roa Joseph B. Majeski Irfaan A. Dar Nathaniel E. Barber Amanda M. Forti Danielle S.W. Benoit Regine Choe 《Photochemistry and photobiology》2020,96(2):380-387
Noninvasive monitoring of vascularization can potentially diagnose impaired bone healing earlier than current radiographic methods. In this study, a noncontact diffuse correlation tomography (DCT) technique was employed to measure longitudinal blood flow changes during bone healing in a murine femoral fracture model. The three-dimensional distribution of the relative blood flow was quantified from one day pre-fracture to 48 days post-fracture. For three mice, frequent DCT measurements were performed every other day for one week after fracture, and then weekly thereafter. A decrease in blood flow was observed in the bone fracture region at one day post-fracture, followed by a monotonic increase in blood flow beyond the pre-injury baseline until five to seven days post-fracture. For the remaining 12 mice, only weekly DCT measurements were performed. Data collected on a weekly basis show the blood flow for most mice was elevated above baseline during the first two post-fracture weeks, followed by a subsequent decrease. Torsional strength of the excised femurs was measured for all 15 mice after 7 weeks of healing. A metric based on the early blood flow changes shows a statistically significant difference between the high strength group and the low strength group. 相似文献
95.
Ralph Haist Hans-Georg Mack Alfred Waterfeld Gary L. Gard Heinz Oberhammer 《Journal of Molecular Structure》1996,380(3):213-222
The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF3SO2)2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF3SO2)2CF2 have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*). The calculations predict for both systems two stable conformers with C2 symmetry and one with C1 symmetry. In both compounds structures with C2 symmetry and dihedral angles SOSC ≈ 100° ((CF3SO2)2O) and SCSC≈ 150° ((CF3SO2)2CF2 are lowest in energy. According to the GED analyses the dominant conformer of (CF3SO2)2O2 possesses C2 symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF3SO2)2CF2 only one conformer with C2 symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given. 相似文献
96.
97.
A method is presented for the simultaneous determination of Cr(III) and Cr(VI) in yeast using species-specific double-spike
isotope dilution (SSDSID) with anion-exchange liquid chromatography (LC) separation and sector field inductively coupled plasma
mass spectrometric (SF-ICP-MS) detection. Total Cr is quantitated using ID SF-ICP-MS. Samples were digested on a hot plate
at 95±2 °C for 6 h in an alkaline solution of 0.5 M NaOH and 0.28 M Na2CO3 for the determination of Cr(III) and Cr(VI), whereas microwave-assisted decomposition with HNO3 and H2O2 was used for the determination of total Cr. Concentrations of 2,014±16, 1,952±103 and 76±48 mg kg−1 (one standard deviation, n=4, 3, 3), respectively were obtained for total Cr, Cr(III) and Cr(VI) in the yeast sample. Significant oxidation of Cr(III)
to Cr(VI) (24.2±7.6% Cr(III) oxidized, n=3) and reduction of Cr(VI) to Cr(III) (37.6±6.5% Cr(VI) reduced, n=3 ) occurred during alkaline extraction and subsequent chromatographic separation at pH 7. Despite this significant bidirectional
redox transformation, quantitative recoveries for both Cr(III) and Cr(VI) were achieved using the SSDSID method. In addition,
mass balance between total Cr and the sum of Cr(III) and Cr(VI) concentrations was achieved. Method detection limits of 0.3,
2 and 30 mg kg−1 were obtained for total Cr, Cr(VI) and Cr(III), respectively, based on a 0.2-g sub-sample. 相似文献
98.
Ralph A. Zehnder Robert A. Renn Matthias Zeller Jason A. Carr Nathan C. McMullen 《Journal of Molecular Structure》2011,985(1):109-119
Various lanthanide open framework materials incorporating the terephthalate (TP) entity were prepared using hydrothermal synthesis methods at a moderate temperature of 170 °C. The compounds Nd2(TP)3(H2O)4(1), Er2(TP)3(H2O)4(2), Yb2(TP)3(H2O)2(3), Yb2(TP)3(H2O)6(4), and Yb2(TP)3(H2O)8·2H2O (5), were characterized by single crystal structural analysis and FT-IR spectroscopy. While compounds 1 and 2 have been reported before on the basis of powder X-ray diffraction, the structural characterization of any ytterbium terephthalate species is unprecedented. Compounds 1-5 crystallize in triclinic settings with space group P-1. The compounds are compared with their previously reported Er and Tb-counterparts and the reduction of the dimensionality of the resulting networks from 3D over 2D to 1D with increasing level of hydration is discussed. Compounds 1, 2, and 3 with the lowest water content assemble in three-dimensional network lattices. Compounds 4 and 5, however, form 2D layered systems and 1D rod like chains, respectively, which are held together by hydrogen bonds originating from coordinating H2O. The crystal lattices of the 3D networks experience higher levels of tension as can be seen by increasing out-of-plane torsion with regard to the terephthalate carboxylate groups. Moreover, there seems to be a correlation between the level of strain on the aromatic ligands and the reduction of the number of carboxylate oxygen atoms that are part of the coordination polyhedra. 相似文献
99.
Ralph Weissleder David D. Stark Guillermo Elizondo Peter F. Hahn Carolyn Compton Sanjay Saini Jack Wittenberg Joseph T. Ferrucci 《Magnetic resonance imaging》1988,6(6):675-681
Thirteen patients with biopsy proven hepatic lymphoma (2 Hodgkin, 11 Non-Hodgkin) and a control group of 15 patients with hepatic metastases were analyzed quantitatively and qualitatively by MRI. Focal hepatic lymphoma was most reliably detected (eight of eight patients) and appeared hypointense relative to liver on T1 weighted (CNR − 7.4 ± 2.3) and hyperintense on T2 weighted (CNR + 8.4 ± 2.9) images. The mean T1 and T2 relaxation times of focal hepatic lymphoma (T1 = 832 ± 234 msec, T2 = 84 ± 16 ms) differed significantly from adjacent non-tumorous liver (T1 = 420 ± 121 ms, T2 = 51 ± 9 ms; p < 0.05), however CNR values and relaxation times were similar to those of hepatic metastases. Diffuse hepatic lymphoma (microscopic periportal infiltration) was undetectable by MRI in three patients by either morphologic features or quantitative criteria. A mixed pattern of hepatic lymphoma (focal lesions and diffuse infiltration) showed focal areas of slightly decreased signal intensity on T1 weighted images (CNR = −1.7 ± 0.4) while T2 weighted images revealed multiple regions of focal hyperintensity (CNR = +13.3 ± 8.4) superimposed on a diffusely hyperintense liver. Our experience demonstrates that either T1 or T2 weighted techniques are useful in detecting focal and that T2 weighted techniques are useful in detecting mixed hepatic lymphoma. Conventional image derived relaxation time measurements and quantitative parameters were of no additional diagnostic value. 相似文献
100.
Cucurbituril‐mediated immobilization of fluorescent proteins on supramolecular biomaterials 下载免费PDF全文
Olga J. G. M. Goor Ralph P. G. Bosmans Luc Brunsveld Patricia Y. W. Dankers 《Journal of polymer science. Part A, Polymer chemistry》2017,55(21):3607-3616
The reversible introduction of functionality at material surfaces is of interest for the development of functional biomaterials. In particular, the use of supramolecular immobilization strategies facilitates mild reaction and processing conditions, as compared to other covalent analogues. Here, the engineering of multicomponent supramolecular materials, beyond the use of a single supramolecular entity is proposed. Cucurbit[8]uril (Q8) mediated host–guest chemistry is combined with hydrogen bonding supramolecular 2‐ureido‐4‐pyrimidinone (UPy)‐based materials. The modular incorporation of a UPy‐additive that presents one guest to incorporate into the Q8 host allows for selective supramolecular functionalization at the water–polymer material interface. Supramolecular ternary complex formation at the material surface was studied by X‐ray photoelectron spectroscopy, which as a result of large overlap in atomic composition of the different components showed minor changes is surface composition upon complex formation. Surface MALDI‐ToF MS measurements revealed useful insights in the formation of complexes. Protein immobilization was monitored using both fluorescence spectroscopy and quartz crystal microbalance with dissipation monitoring, which successfully demonstrated ternary complex formation. Although proteins could selectively be immobilized onto the surfaces, control of the system's stability remains a challenge as a result of the dynamicity of the host–guest assembly. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3607–3616 相似文献