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11.
Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine 下载免费PDF全文
Diego García‐Gómez Encarnación Rodríguez‐Gonzalo Rita Carabias‐Martínez 《Biomedical chromatography : BMC》2015,29(8):1190-1196
In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
12.
The effect of Re addition on the microstructure and hardening behaviour of the dual two-phase Ni3Al (L12) and Ni3V (D022) intermetallic alloy was investigated by scanning electron microscopy, transmission electron microscopy and Vickers hardness test. The two-phase eutectoid microstructure accompanying the Re-rich precipitates were observed in the channel region of the alloys in which Re substituted for Ni but not in those in which Re substituted for Al and V. The concomitant addition of Nb (or Ta) with Re more stabilized the two-phase eutectoid microstructure and consequently more induced the fine precipitates in the channel region. The annealing at temperatures below the eutectoid temperature was necessary to induce the fine precipitates in the channel region and thereby result in the precipitation hardening. The fine precipitation in the channel region and related hardening was attributed to the alloying feature so that Re is soluble in the A1 (fcc) phase at high temperatures and becomes less soluble in the two intermetallic phases decomposed from the A1 phase at low temperatures. 相似文献
13.
《河南师范大学学报(自然科学版)》2015,(6):76-80
基于异烟肼分子结构中的酰肼基具有较强的还原性,可将Fe~(3+)还原为Fe~(2+),选择水合红菲绕啉二磺酸钠作为Fe~(2+)的显色剂,建立了可见分光光度法测定异烟肼的新方法.在最佳实验条件下,异烟肼的浓度在0.04~3.2μg·mL-1范围内符合比尔定律,表观摩尔吸光系数ε=1.14×104 L·mol~(-1)·cm~(-1),检测限为0.033μg·mL~(-1).方法可用于异烟肼片剂和尿样中异烟肼含量的测定. 相似文献
14.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献
15.
Padavattan Govindaswamy Patrick J. Carroll Yurij A. Mozharivskyj Mohan Rao Kollipara 《Journal of Chemical Sciences》2006,118(4):319-326
The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl2(κ1-P-PPh2Py)]3 and [(η5-C5Me5) IrCl2(ϰ1-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+
5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+
6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+
8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3 and [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+
7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+
8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as
analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3, [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+
6 are established by single-crystal X-ray diffraction methods 相似文献
16.
CO2跨临界循环系统润滑油分析 总被引:4,自引:0,他引:4
为保证CO2跨临界循环系统的稳定运行,选择与之相适应的润滑油,在分析摩擦润滑特性的基础上,采用实验数据对比的方法,对POE、PAG、PAO和烷基芳香烃4类合成润滑油在CO2跨临界循环系统中的混合性、流动性、可溶性、黏度、长期稳定性及润滑性等性能进行了分析,结果表明POE类润滑油是CO2跨临界循环系统的一种相对较好的选择。 相似文献
17.
目的:探讨乙酰胆碱对人胃粘膜上皮细胞和胃腺癌细胞内Ca2 、Mg2 浓度的影响。方法:利用大型生化分析仪,检测了乙酰胆碱作用后培养的人胃粘膜上皮细胞和胃腺癌细胞内Ca2 、Mg2 的浓度。结果:与正常胃粘膜上皮细胞比较,胃腺癌细胞内Ca2 、Mg2 浓度偏低(P>0 01)。在乙酰胆碱作用下,胃粘膜上皮细胞内Ca2 浓度升高(P<0 01),Mg2 浓度降低(P<0 01);胃腺癌细胞仅有Ca2 浓度升高(P<0 05),Mg2 浓度无变化。阿托品能阻断乙酰胆碱的作用(P<0 05)。结论:乙酰胆碱对胃粘膜上皮细胞和胃腺癌细胞的作用是通过毒蕈碱受体实现的。 相似文献
18.
在探索综合性大学中教师教育的培养模式研究过程中,根据教师教育双专业的特性,实施了综合性大学师范本科教育3+1课程方案和培养模式的研究与实践.并以化学教师教育培养为例对3+1模式的作了具体说明. 相似文献
19.
关于图的第二特征标R2(G) 总被引:10,自引:2,他引:8
毛建树 《青海师范大学学报(自然科学版)》2004,(1):18-22
对任意图G,h(G,x)表示图G的伴随多项式,R2(G)表示图G的第二特征标,本文刻画了R2(G)=-2,-1,0,1,2的全部连通图。 相似文献
20.
电气自动化成套装置种类繁多,并广泛应用于电力系统.结合现场实际商业运行期所积累的经验,并根据市场预测以及目前工控机发展动态,提出了采用APCI5000工业控制计算机实现电气自动化成套装置设计的最佳方案. 相似文献