全文获取类型
收费全文 | 13084篇 |
免费 | 1522篇 |
国内免费 | 1156篇 |
专业分类
化学 | 9266篇 |
晶体学 | 101篇 |
力学 | 682篇 |
综合类 | 81篇 |
数学 | 1585篇 |
物理学 | 4047篇 |
出版年
2024年 | 38篇 |
2023年 | 216篇 |
2022年 | 366篇 |
2021年 | 429篇 |
2020年 | 413篇 |
2019年 | 393篇 |
2018年 | 316篇 |
2017年 | 304篇 |
2016年 | 564篇 |
2015年 | 462篇 |
2014年 | 662篇 |
2013年 | 838篇 |
2012年 | 963篇 |
2011年 | 1035篇 |
2010年 | 704篇 |
2009年 | 664篇 |
2008年 | 833篇 |
2007年 | 724篇 |
2006年 | 610篇 |
2005年 | 634篇 |
2004年 | 430篇 |
2003年 | 412篇 |
2002年 | 432篇 |
2001年 | 332篇 |
2000年 | 274篇 |
1999年 | 254篇 |
1998年 | 240篇 |
1997年 | 194篇 |
1996年 | 201篇 |
1995年 | 162篇 |
1994年 | 165篇 |
1993年 | 127篇 |
1992年 | 138篇 |
1991年 | 123篇 |
1990年 | 100篇 |
1989年 | 96篇 |
1988年 | 60篇 |
1987年 | 44篇 |
1986年 | 57篇 |
1985年 | 48篇 |
1984年 | 35篇 |
1983年 | 35篇 |
1982年 | 32篇 |
1981年 | 34篇 |
1980年 | 30篇 |
1979年 | 23篇 |
1978年 | 27篇 |
1977年 | 36篇 |
1976年 | 21篇 |
1974年 | 23篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Pei‐Hong Ni Qi‐Sheng Pan Liu‐Sheng Zha Chang‐Chun Wang Abdelhamid Elaïssari Shou‐Kuan Fu 《Journal of polymer science. Part A, Polymer chemistry》2002,40(4):624-631
A novel, near‐monodisperse, well‐defined ABA triblock copolymer, poly[2‐(dimethylamino)ethyl methacrylate]‐b‐poly(propylene oxide)‐b‐poly[2‐(dimethylamino)ethyl methacrylate], was synthesized via oxyanion‐initiated polymerization. The initiator was a telechelic‐type potassium alcoholate prepared from poly(propylene glycol) and KH in dry tetrahydrofuran. The copolymers produced were characterized by Fourier transform infrared, 1H NMR, and gel permeation chromatography (GPC). GPC and 1H NMR analyses showed that the products obtained were the desired copolymers, with narrow molecular weight distributions (ca. 1.09–1.11) very close to that of the original poly(propylene glycol). 1H NMR, surface tension measurements, and dynamic light scattering all indicated that the triblock copolymer led to interesting aqueous solution behaviors, including temperature‐induced micellization and very high surface activity. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 624–631, 2002; DOI 10.1002/pola.10144 相似文献
992.
Jaroslav Ščudla Klaus-Jochen Eichhorn Miroslav Raab Pavel Schmidt Dieter Jehnichen Liane Häußler 《Macromolecular Symposia》2002,184(1):371-387
The molecular and supermolecular orientation, morphology and structural changes observed during cold drawing of injection moulded isotactic polypropylene modified by specific α, and β nucleating agents were studied by polarised photoacoustic FTIR spectroscopy, wide-angle X-ray diffraction and differential scanning calorimetry. Significantly lower molecular orientation was found in the core of the β-nucleated injection moulded specimens as compared to unmodified and α-nucleated materials. This has been ascribed to the fast growth of the β-crystallites which inevitably dislocates the flow-induced orientation within the crystalline regions and in their vicinity. Moreover, it was found that the presence of the developed β-crystallites distinctly diminishes the efficiency of the orientational solid-state drawing assessed on both levels of the hierarchical structure (molecular and crystalline). This structural observation is directly connected with macroscopic softening effect of the β-phase: lowering the yield stress and flattening the neck shoulder. Thus, the interrelation between the microstructural and macroscopic effects of the β-phase could be described as a feedback process. 相似文献
993.
Wetting behavior of a polymer resin used as matrix on fabric surfaces is one of the key attributes for making high quality
structural composites. Though incorporation of various functionalized nanoparticles can stimulate improvements to many properties
of epoxy resins, there has not been any report on wettability of any nano-modified epoxy on rough inclined fabric surfaces.
In this research work, wetting behavior of a previously developed nano-epoxy resin modified by a type of reactive graphitic
nanofibers (r-GNFs) was investigated. The observation results revealed that a unique wetting behavior was discovered from
the nano-epoxy on rough fabric surfaces due to the contribution of the r-GNFs. Based on this dramatically improved wettability
of the epoxy, a concept of dry–wet contact model was proposed to interpret the different wetting phenomenon observed from
the nano-epoxy and that of the pure epoxy. The improved wetting characteristics of the nano-epoxy system will be essential
for enabling future energy efficient infusion processing for manufacturing high quality and high-performance structural composite
applications. 相似文献
994.
Gabor Butora Ning Qi Wenlang Fu Truyen Nguyen Hsueh‐Cheng Huang Ian W. Davies 《Angewandte Chemie (International ed. in English)》2014,53(51):14046-14050
The cytosolic conversion of therapeutically relevant nucleosides into bioactive triphosphates is often hampered by the inefficiency of the first kinase‐mediated step. Nucleoside monophosphate prodrugs can be used to bypass this limitation. Herein we describe a novel cyclic‐disulfide class of nucleoside monophosphate prodrugs with a cytosol‐specific, reductive release trigger. The key event, a charge‐dissipating reduction‐triggered cyclodeesterification leads to robust cytosolic production of the cyclic 3′,5′‐monophosphate for downstream enzymatic processing. The antiviral competence of the platform was demonstrated with an O‐benzyl‐1,2‐dithiane‐4,5‐diol ester of 2′‐C‐methyluridine‐3′,5′‐phosphate. Both in vitro and in vivo comparison with the clinically efficacious ProTide prodrug of 2′‐deoxy‐2′‐α‐fluoro‐β‐C‐methyluridine is provided. The cytosolic specificity of the release allows for a wide range of potential applications, from tissue‐targeted drug delivery to intracellular imaging. 相似文献
995.
Xiu‐Li Hao Yuan‐Yuan Ma Dr. Yong‐Hui Wang Long‐Yang Xu Dr. Fu‐Chen Liu Mao‐Mao Zhang Prof. Yang‐Guang Li 《化学:亚洲杂志》2014,9(3):819-829
Investigation into a hydrothermal reaction system with transition‐metal (TM) ions, 1,4‐bis(1,2,4‐triazol‐1‐lmethyl)benzene (BBTZ) and various charge‐tunable Keggin‐type polyoxometalates (POMs) led to the preparation of four new entangled coordination networks, [CoII(HBBTZ)(BBTZ)2.5][PMo12O40] ( 1 ), [CuI(BBTZ)]5[BW12O40] ? H2O ( 2 ), [CuII(BBTZ)]3[AsWV3WVI9O40] ? 10 H2O ( 3 ), and [CuII5(BBTZ)7(H2O)6][P2W22Cu2O77(OH)2] ? 6 H2O ( 4 ). All compounds were characterized by using elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The mixed valence of W centers in compound 3 was further confirmed by using XPS spectroscopy and bond‐valence sum calculations. In the structural analysis, the entangled networks of 1 – 4 demonstrate zipper‐closing packing, 3D polythreading, 3D polycatenation, and 3D self‐penetration, respectively. Moreover, with the enhancement of POM negative charges and the use of different TM types, the number of nodes in the coordination networks of 1 – 4 increased and the basic metal–organic building motifs changed from a 1D zipper‐type chain (in 1 ) to a 2D pseudorotaxane layer (in 2 ) to a 3D diamond‐like framework (in 3 ) and finally to a 3D self‐penetrating framework (in 4 ). The photocatalytic properties of compounds 1 – 4 for the degradation of methylene blue under UV light were also investigated; all compounds showed good catalytic activity and the photocatalytic activity order of Keggin‐type species was initially found to be {XMo12O40}>{XW12O40}>{XW12?nTMnO40}. 相似文献
996.
Dr. Damien Hudry Dr. Christos Apostolidis Dr. Olaf Walter Dr. Arne Janßen Dr. Dario Manara Dr. Jean‐Christophe Griveau Dr. Eric Colineau Dr. Tonya Vitova Tim Prüßmann Dr. Di Wang Dr. Christian Kübel Dr. Daniel Meyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10431-10438
Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non‐conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium‐based nanomaterials. Here we show that ultra‐small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2(NO3)2] ? 3 H2O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X‐ray diffraction (PXRD), X‐ray absorption fine structure (XAFS), X‐ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. 相似文献
997.
Portable paper‐based device for quantitative colorimetric assays relying on light reflectance principle 下载免费PDF全文
This paper presents a novel paper‐based analytical device based on the colorimetric paper assays through its light reflectance. The device is portable, low cost (<20 dollars), and lightweight (only 176 g) that is available to assess the cost‐effectiveness and appropriateness of the original health care or on‐site detection information. Based on the light reflectance principle, the signal can be obtained directly, stably and user‐friendly in our device. We demonstrated the utility and broad applicability of this technique with measurements of different biological and pollution target samples (BSA, glucose, Fe, and nitrite). Moreover, the real samples of Fe (II) and nitrite in the local tap water were successfully analyzed, and compared with the standard UV absorption method, the quantitative results showed good performance, reproducibility, and reliability. This device could provide quantitative information very conveniently and show great potential to broad fields of resource‐limited analysis, medical diagnostics, and on‐site environmental detection. 相似文献
998.
Ultra‐performance liquid chromatography coupled with electrospray ionization/quadrupole time‐of‐flight mass spectrometry for the rapid analysis of constituents in the traditional Chinese medical formula Danggui San 下载免费PDF全文
In this work, ultra‐performance LC with ESI quadrupole TOF‐MS (UPLC–ESI‐Q‐TOF‐MS) and automated MetaboLynx analysis was used to rapidly separate and identify the chemical constituents of Danggui San, a traditional Chinese medical formula. The analysis was performed on a Waters UPLC BEH C18 column using a gradient elution system. A hyphenated ESI and Q‐TOF analyzer was used for the determination of the accurate mass of the protonated or deprotonated molecule and fragment ions in both positive and negative modes. Based on retention times, accurate mass, and the mass spectrometric fragmentation characteristics, a total of 47 compounds distributed over the chemical groups of phthalides, flavonoids, monoterpene glycosides, sesquiterpenoids, phenolics, and alkaloids, were simultaneously separated within 18 min and identified or tentatively elucidated in Danggui San for the first time. UPLC–ESI‐Q‐TOF‐MS analysis revealed the complexity of the chemical composition of this formula. The method developed is rapid, accurate, reliable, and highly sensitive to characterize the chemical constituents of Danggui San. 相似文献
999.
Jian‐Hua Zou Da‐Liang Zhu Fei‐Fei Li Fu‐Song Li He Wu Qiao‐Yun Li Gao‐Wen Yang Ping Zhang Yun‐Xia Miao Jian Xie 《无机化学与普通化学杂志》2014,640(11):2226-2231
Reactions of three tetrazole containing carboxylic acid ligands, namely, Hpztza, Htzpya, and Hpytza [Hpztza = 5‐(2‐pyrazinyl)tetrazole‐2‐acetic acid, Htzpya = 3‐(5‐tetrazolyl)pyridine‐1‐acetic acid, Hpytza = 5‐(3‐pyridyl)tetrazole‐2‐acetic acid] with NdCl3 · 6H2O under hydrothermal conditions, afforded the complexes [Nd(pztza)2(H2O)6] · pztza · 3H2O ( 1 ), [Nd2(tzpya)2(H2O)12]Cl4 · 2H2O ( 2 ), and [Nd(pytza)2Cl(H2O)2] ( 3 ). The compounds were structurally characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. X‐ray diffraction analyses revealed that compound 1 displays a mononuclear structure, 2 shows a dinuclear structure, and 3 features a 1D polymeric chain structure via pytza as linker. Furthermore, the luminescent properties investigated at room temperature in the solid state show that compound 2 has an obvious decrease in its luminescence, when compared to the ligand. 相似文献
1000.
合成并通过单晶衍射表征了3个稀土配合物[LaL2(NO3)3]·CH3CN(1),[Ln(L)(NO3)3(H2O)](Ln=Tb(2),Dy(3),L=N-苯基-2-(5-氯-8-喹啉氧基)乙酰胺)。在配合物1中,十二配位的La(Ⅲ)离子采取扭曲的二十面体配位构型,分别与来自2个酰胺配体L的4个氧原子和2个氮原子,及3个双齿配位硝酸根配位。配合物2和3的结构与拥有相同有机配体的Pr、Nd、Sm、Eu、Gd和Er配合物同构。在每个配合物中,十配位的稀土离子与来自1个配体L的2个氧原子和1个氮原子,3个双齿配位硝酸根和1个水分子配位,拥有扭曲的双帽四方反棱柱配位构型。固态配合物2和3在可见区发射强荧光。 相似文献