全文获取类型
收费全文 | 2782篇 |
免费 | 55篇 |
国内免费 | 13篇 |
专业分类
化学 | 2072篇 |
晶体学 | 18篇 |
力学 | 57篇 |
数学 | 343篇 |
物理学 | 360篇 |
出版年
2020年 | 19篇 |
2019年 | 19篇 |
2018年 | 13篇 |
2017年 | 21篇 |
2016年 | 34篇 |
2015年 | 36篇 |
2014年 | 46篇 |
2013年 | 133篇 |
2012年 | 114篇 |
2011年 | 130篇 |
2010年 | 70篇 |
2009年 | 48篇 |
2008年 | 137篇 |
2007年 | 132篇 |
2006年 | 131篇 |
2005年 | 133篇 |
2004年 | 118篇 |
2003年 | 75篇 |
2002年 | 100篇 |
2001年 | 38篇 |
2000年 | 44篇 |
1999年 | 39篇 |
1998年 | 28篇 |
1997年 | 34篇 |
1996年 | 57篇 |
1995年 | 36篇 |
1994年 | 42篇 |
1993年 | 38篇 |
1992年 | 31篇 |
1991年 | 36篇 |
1990年 | 29篇 |
1989年 | 23篇 |
1988年 | 30篇 |
1987年 | 27篇 |
1986年 | 23篇 |
1985年 | 51篇 |
1984年 | 51篇 |
1983年 | 42篇 |
1982年 | 60篇 |
1981年 | 58篇 |
1980年 | 65篇 |
1979年 | 50篇 |
1978年 | 59篇 |
1977年 | 41篇 |
1976年 | 34篇 |
1975年 | 48篇 |
1974年 | 45篇 |
1973年 | 30篇 |
1972年 | 23篇 |
1968年 | 17篇 |
排序方式: 共有2850条查询结果,搜索用时 62 毫秒
991.
Julien Massue Karima Benelhadj Siwar Chibani Boris Le Guennic Denis Jacquemin Pascal Retailleau Gilles Ulrich Raymond Ziessel 《Tetrahedron letters》2014
The multi-step synthesis, structural and optical properties of original luminescent borate complexes derived from 2-(2′-hydroxybenzofuran)benzoxazole (HBBO) are reported. Functionalization at position 3 of the benzofuran ring was readily achieved through an electrophilic cyclization key step followed by a Sonogashira cross-coupling reaction. The optical properties of the resulting boron difluoride dyes highlight different photophysical behaviors depending on the nature of the substitution at position 3 of the benzofuran core (tBu-phenylacetylene or NnBu2-phenylacetylene). The NnBu2-phenylacetylene moiety favors a sizeable intramolecular charge transfer as evidenced by a strong solvatochromism; a feature further confirmed by ab initio calculations. 相似文献
992.
In this paper, we investigated the procedure of noise assessment in the study of nocturnal noise exposure during sleep in the home situation. The use of two different timeframes (fixed from 11 PM to 07 AM versus personal “Time in Bed” period) was explored as well as the relation between indoor and outdoor noise levels and between the actual and estimated noise levels. Noise recordings were performed inside and outside the bedroom of 24 subjects living in high density road traffic noise areas in the Brussels’ Capital Region during seven consecutive days. Indoor and outdoor noise indicators LAeq, LAmax and individual noise events were analysed. Subjects completed a daily sleep log in which the Time in Bed period was assessed. The results indicate that, for outdoor noise assessment, the use of an average LAeq might not be sufficient to reflect well the noise levels during the sleep period. For indoor measurements, significant differences were found in the comparison between both timeframes (LAeq: T = 16; p < .001). Considering the relation between indoor and outdoor measurements, low correlations (r = .49; p < .001) were found even when the location of the bedroom as a mediating factor was accounted for (street side; r = .52; p < .001). Therefore, from our study, caution is needed when relying on outdoor noise measurements for the evaluation of sleep disturbances. Furthermore, one needs to be aware of the weak correspondence between indoor and outdoor noise levels in the discussion of what a harmonized noise indicator for the evaluation of noise exposure and sleep disturbances should consist of. 相似文献
993.
The purpose of this study was to prospectively compare noninvasive, quantitative measures of vascularity obtained from four contrast enhanced ultrasound (US) techniques to four invasive immunohistochemical markers of tumor angiogenesis in a large group of murine xenografts. Glioma (C6) or breast cancer (NMU) cells were implanted in 144 rats. The contrast agent Optison (GE Healthcare, Princeton, NJ) was injected in a tail vein (dose: 0.4 ml/kg). Power Doppler imaging (PDI), pulse-subtraction harmonic imaging (PSHI), flash-echo imaging (FEI), and Microflow imaging (MFI; a technique creating maximum intensity projection images over time) was performed with an Aplio scanner (Toshiba America Medical Systems, Tustin, CA) and a 7.5 MHz linear array. Fractional tumor neovascularity was calculated from digital clips of contrast US, while the relative area stained was calculated from specimens. Results were compared using a factorial, repeated measures ANOVA, linear regression and z-tests. The tortuous morphology of tumor neovessels was visualized better with MFI than with the other US modes. Cell line, implantation method and contrast US imaging technique were significant parameters in the ANOVA model (p < 0.05). The strongest correlation determined by linear regression in the C6 model was between PSHI and percent area stained with CD31 (r = 0.37, p < 0.0001). In the NMU model the strongest correlation was between FEI and COX-2 (r = 0.46, p < 0.0001). There were no statistically significant differences between correlations obtained with the various US methods (p > 0.05). In conclusion, the largest study of contrast US of murine xenografts to date has been conducted and quantitative contrast enhanced US measures of tumor neovascularity in glioma and breast cancer xenograft models appear to provide a noninvasive marker for angiogenesis; although the best method for monitoring angiogenesis was not conclusively established. 相似文献
994.
Luo Y de Leon E Castro J Lee J Barton JK Kostuk RK Barbastathis G 《Optics letters》2011,36(7):1290-1292
A phase-contrast volume holographic imaging system for three-dimensional contrast enhancement is presented. The system utilizes a spatial filter placed on a conjugate plane to the volume holographic pupil to simultaneously enhance weak phase information at different depths within an object. The proposed system was validated with experimental image data obtained in mouse colon samples and quantitative measurements of modulation transfer function as well. 相似文献
995.
Ramirez SM Diaz YJ Campos R Stone RL Haddad TS Mabry JM 《Journal of the American Chemical Society》2011,133(50):20084-20087
A novel synthetic method was developed for the controlled functionalization of fluorinated polyhedral oligomeric silsesquioxanes (F-POSS), which are useful as low surface energy materials for superhydrophobic and superoleophobic materials. Utilizing triflic acid, open-cage compounds were created and then reacted with a variety of dichlorosilanes to produce functional F-POSS structures possessing alkyl-, aryl-, and acrylate-based moieties. The crystal structure for an endo,endo-disilanol F-POSS compound was determined by single-crystal X-ray diffraction. The chemical structures were confirmed using multinuclear NMR spectroscopy ((1)H, (13)C, (19)F, and (29)Si), FT-IR, and combustion analysis. Dynamic contact angle measurements of these compounds were taken with water and hexadecane. These novel structures were found to possess excellent wetting-resistant behavior, similar to that of the parent F-POSS compound. They are the first well-defined fluorinated nano-building blocks with a controlled level of reactive functionality for the development of new superhydrophobic and superoleophobic materials. 相似文献
996.
A concise, diastereoselective total synthesis of (±)-cortistatin J has been completed in 20 steps from furan. Key steps include an intramolecular [4 + 3] cyclization of a disubstituted furan with a (Z)-2-(trialkylsilyloxy)-2-enal to construct the tetracyclic core and a (Z)-vinylsilane/iminium ion cyclization to form the A ring. 相似文献
997.
White Emitters by Tuning the Excited‐State Intramolecular Proton‐Transfer Fluorescence Emission in 2‐(2′‐Hydroxybenzofuran)benzoxazole Dyes
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Karima Benelhadj Wenziz Muzuzu Dr. Julien Massue Dr. Pascal Retailleau Dr. Azzam Charaf‐Eddin Dr. Adèle D. Laurent Prof. Denis Jacquemin Dr. Gilles Ulrich Dr. Raymond Ziessel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(40):12843-12857
The synthesis, structural, and photophysical properties of a new series of original dyes based on 2‐(2′‐hydroxybenzofuran)benzoxazole (HBBO) is reported. Upon photoexcitation, these dyes exhibit intense dual fluorescence with contribution from the enol (E*) and the keto (K*) emission, with K* being formed through excited‐state intramolecular proton transfer (ESIPT). We show that the ratio of emission intensity E*/K* can be fine‐tuned by judiciously decorating the molecular core with electron‐donating or ‐attracting substituents. Push–pull dyes 9 and 10 functionalized by a strong donor (nNBu2) and a strong acceptor group (CF3 and CN, respectively) exhibit intense dual emission, particularly in apolar solvents such as cyclohexane in which the maximum wavelength of the two bands is the more strongly separated. Moreover, all dyes exhibit strong solid‐state dual emission in a KBr matrix and polymer films with enhanced quantum yields reaching up to 54 %. A wise selection of substituents led to white emission both in solution and in the solid state. Finally, these experimental results were analyzed by time‐dependent density functional theory (TD‐DFT) calculations, which confirm that, on the one hand, only E* and K* emission are present (no rotamer) and, on the other hand, the relative free energies of the two tautomers in the excited state guide the ratio of the E*/K* emission intensities. 相似文献
998.
Raymond J. Ritchie 《Photochemistry and photobiology》2013,89(5):1143-1162
Photosynthetic bacteria are attractive for biotechnology because they produce no oxygen and so H2‐production is not inhibited by oxygen as occurs in oxygenic photoorganisms. Rhodopseudomonas palustris and Afifella marina containing BChl a can use irradiances from violet near‐UV (VNUV) to orange (350–650 nm) light and near‐infrared (NIR) light (762–870 nm). Blue diode‐based pulse amplitude modulation technology was used to measure their photosynthetic electron transport rate (ETR). ETR vs Irradiance curves fitted the waiting‐in‐line model—ETR = (ETRmax × E/Eopt) × exp (1 ? E/Eopt). The equation was integrated over pond depth to calculate ETR of Afifella and Rhodopseudomonas in a pond up to 30 cm deep (A376, 1 cm = 0.1). Afifella saturates at low irradiances and so photoinhibition results in very low photosynthesis in a pond. Rhodopseudomonas saturates at ≈15% sunlight and shows photoinhibition in the surface layers of the pond. Total ETR is ≈335 μmol (e?) m?2 s?1 in NUV + photosynthetically active radiation light (350–700 nm). Daily ETR curves saturate at low irradiances and have a square‐wave shape: ≈11–13 mol (e?) m?2 day?1 (350–700 nm). Up to 20–24% of daily 350–700 nm irradiance can be converted into ETR. NIR is absorbed by water and so competes with the bacterial RC‐2 photosystem for photons. 相似文献
999.
During the past decade, methyl 7-(5-oxocyclopentenyl)heptanoate (6) has been frequently used as a key intermediate in prostaglandin synthesis.1 Although keto ester 6 can be readily obtained by treatment of traumatic acid (5) with polyphosphoric acid followed by esterification with methanolic hydrochloric acid,2 this approach is not attractive for large-scale synthesis due to the expense of the latter natural product (5). Recently Salomon and Reuter have reported1 an alternate route to synthon 6 based on a starting material derived from aleuritic acid, a major component of shellac. 相似文献
1000.
Net Promoter Score, touted as the “single customer metric you need” and calculated from customers' answer to one simple question about their loyalty, has been in use since 2003 and adopted in a wide variety of settings. However, it has not lived up to its claimed benefits. This article evaluates the NPS approach in terms of its positive and negative results. This article is for people interested in NPS, still considering implementing NPS in their company, or interested in its technical underpinnings. It points out the benefits and shortcomings and explains why, and it describes what can be done to achieve the outcomes NPS theory claimed it would produce, but has not. The article is written in two parts for quite distinct audiences: firstly, for executives and managers who need customer data and information to make marketing decisions; and secondly, for market researchers, statisticians, and business analysts who are responsible for capturing and providing reliable, understandable, and meaningful customer data to the executives and managers who need the information. Consequently, the two sections are written in two different styles. The first section takes the form of a summary for managers and executives of our findings and recommendations in language aimed at business leaders; the second section provides a detailed analysis and critical review of NPS for market researchers, statisticians, and business analysts. Both sections present a better solution than NPS for understanding what customers value, delivering the best value to customers, winning market share, and creating truly loyal customers. 相似文献