首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   35篇
  免费   3篇
  国内免费   1篇
儿科学   1篇
基础医学   3篇
口腔科学   1篇
临床医学   5篇
内科学   11篇
神经病学   2篇
外科学   7篇
预防医学   3篇
药学   3篇
肿瘤学   3篇
  2023年   1篇
  2021年   5篇
  2020年   4篇
  2018年   4篇
  2017年   3篇
  2016年   2篇
  2015年   1篇
  2014年   1篇
  2013年   1篇
  2012年   2篇
  2011年   8篇
  2010年   1篇
  2009年   1篇
  2008年   2篇
  2007年   1篇
  2006年   1篇
  1985年   1篇
排序方式: 共有39条查询结果,搜索用时 31 毫秒
21.
The use of potato peels as a dressing for burn wounds has been reported previously. A technique of preparing bandage rolls with boiled potato peels is now presented, which makes dressing of a burn wound more convenient.  相似文献   
22.
This study compared pulmonary function tests (PFTs) with cardiac, pancreatic and liver iron in 76 thalassemia major (TM) patients. Restrictive lung disease was observed in 16%, hyperinflation in 32% and abnormal diffusing capacity in 3%. While no patients met Global Initiative for Chronic Lung Disease criteria for airways obstruction, there were indicators of small airways disease and air trapping. PFTs did not correlate with somatic iron burden, blood counts or haemolysis. Restrictive lung disease was associated with inflammation. We conclude that TM patients have pulmonary abnormalities consistent with small airways obstruction. Restrictive disease and impaired diffusion are less common.  相似文献   
23.
24.
25.
26.
27.
An in silico method has been used to discover N‐hydroxy‐substituted 2‐aryl acetamide analogs as a new class of HIV‐1 integrase inhibitors. Based on the molecular requirements of the binding pocket of catalytic active site, two molecules (compounds 2 and 4b ) were designed as fragments. These were further synthesized and biologically evaluated. In vitro potency along with docking studies highlighted compound 4b as an active fragment which was further used to synthesize new leads as HIV‐1 integrase inhibitors. Finally, six promising compounds (compounds 5b , 5c , 5e, 6–2c, 6–3b, and 6–5b ) were identified by integrase inhibition assay (>50% inhibition). Based on in vitro anti‐HIV‐1 activity in a reporter gene‐based cell assay system, compounds 5d , 6s , and 6k were found as novel HIV‐1 integrase inhibitors due to its better selectivity index. Additionally, docking study revealed the importance of H‐bond as well as hydrophobic interactions with Asn155, Lys156, and Lys159 which were required for their anti‐HIV‐1 activity.  相似文献   
28.
A Me3SI-mediated simple and efficient protocol for the chemoselective deprotection of acetyl groups has been developed via employing KMnO4 as an additive. This chemoselective deacetylation is amenable to a wide range of substrates, tolerating diverse and sensitive functional groups in carbohydrates, amino acids, natural products, heterocycles, and general scaffolds. The protocol is attractive because it uses an environmentally benign reagent system to perform quantitative and clean transformations under ambient conditions.

A catalytic and practical approach for the selective removal of acetyl groups using various substrates bearing orthogonal moieties has been demonstrated under ambient conditions.

The divergent protection–deprotection approach and extensive functional group manipulation continues to serve as an important chemical tool to access biologically potent molecules and complex natural products.1 In particular, the hydroxyl moieties and their derivatives are ubiquitous in natural products and recognized as renowned scaffolds because of the overwhelming number of chemical and biological applications that they can be used in.2,3 The selective and orthogonal protection–deprotection of free hydroxyl group(s) are significant chemical transformations and frequently employed in target-oriented synthesis (TOS).4 Due to the widespread use and relative ease of protection–deprotection, introduction of an O-Ac group to mask the hydroxyl-moiety has remained as a highly reliable and convenient strategy, especially in synthetic carbohydrate chemistry.1–3 However, the chemoselective deprotection of O-Ac in the presence of analogous and sensitive O-protective groups such as benzoyl (Bz) or pivaloyl (Pv) is a notoriously challenging yet important task.1–3Thus, considerable effort has been devoted to developing robust and selective methods for the deprotection of the acetate ester. As outlined in Scheme 1, the cleavage of O-Ac is conventionally performed under a homogeneous reagent system including: (a) Brønsted acids/Lewis acids such as HCl/MeOH,5 HBF4·Et2O,6 BF3·Et2O,7p-TsOH or CSA,8 (b) inorganic/organic basic conditions employing Zemplén hydrolysis (NaOMe/MeOH),1 ammonia solution,9 hydrazine/AcOH/pyridine,10 DBU/PhH,11 guanidine/EtOH/DCM,12 Mg–metal or Mg(OMe)2,13 KCN/EtOH,14 K2CO3/MeOH/H2O,15 NaHCO3/H2O2,16 (c) metallic compounds or oxidants such as MoO2Cl2,17 molecular iodine/MeOH,18a Sm/I2,18b Bu2SnO/heating,19a Bu3SnOMe/DCE.19b Although, the use of heterogeneous catalysts such as CuFe2O4 nanoparticles20 and enzymes21 have also been demonstrated for deacetylation with limited substrate scope. Recently, a tetranuclear zinc cluster, Zn4(OCOCF3)6O has been investigated for use in trans-esterification and deacylation with discriminate selectivity.22Open in a separate windowScheme 1Previous advances, and the Me3SI-catalyzed chemoselective deacetylation developed in this work.Despite the synthetic challenges and demands placed on modern chemistry, advancing green chemical syntheses employing milder and environmentally benign reagent systems remains a constant motivation and is actively pursued. In this context and our continued interest23 developing versatile and selective protocols inspired the development of a simple and chemoselective deacetylation method with remarkable and distinctive synthetic applicability. Recently the dual-reactivity of KMnO4 for selective deacetylation and one-pot deacetylation–oxidation of benzyl-O-acetates under controlled reaction conditions was successfully investigated.23aEmerging from these precedents, the Me3SI-catalyzed, simple and chemoselective removal of O-acetate, an elegant and promising alternative approach for the deprotection of the acetate ester (Scheme 1d) is presented herein. Inspired by recent research,23f an initial experiment employing Me3SI(OAc)2, generated in situ oxidative transfer of the acetyl groups from PhI(OAc)2 to Me3SI, which gave the regioselective 2-iodoglycosylation of enol ether functionality in 3,4,6-tri-O-acetyl-d-glucal (1a) with methanol together with traces of the deacetylated product 1 (23f,g Meanwhile, the reaction using 0.2 equiv. of both Me3SI and NaIO4 was found to suffice for obtaining the complete deacetylation of 1a after 40 min (
EntryCatalyst (equiv.)Additive (equiv.)SolventTimeYieldb
1Me3SI (1.0)PhI(OAc)2 (1.0)MeOH24 hTrace
2Me3SI (1.0)NaIO4 (1.0)MeOH10 min100%
3Me3SI (0.4)NaIO4 (0.4)MeOH30 min100%
4Me3SI (0.2)NaIO4 (0.2)MeOH40 min100%
5Me3SI (0.1)NaIO4 (0.1)MeOH12 h95%
6 n-Bu4NI (0.1)NaIO4 (0.1)MeOH12 h90%
7KI (0.1)NaIO4 (0.1)MeOH12 h50%
8NaI (0.1)NaIO4 (0.1)MeOH16 h90%
9cMe3SOI (0.1)NaIO4 (0.1)MeOH12 hNR
10cMe3SBr (0.1)NaIO4 (0.1)MeOH12 hNR
11c n-Bu4NBr (0.1)NaIO4 (0.1)MeOH12 hNR
12cKBr (0.1)NaIO4 (0.1)MeOH12 hNR
13 Me 3 SI (0.1) KMnO 4 (0.1) MeOH 5 min 100%
14Me3SI (0.1)KMnO4 (0.1)MeCN24 hNR
15Me3SI (0.1)KMnO4 (0.1)Toluene24 hNR
16Me3SI (0.1)KMnO4 (0.1)THF24 hNR
17Me3SI (0.1)KMnO4 (0.1)DCM24 hNR
18Me3SI (0.1)K2S2O8 (0.1)MeOH12 hTrace
19Me3SI (0.1)Oxone (0.1)MeOH12 hTrace
20Me3SI (0.1)KBrO3 (0.1)MeOH12 hTrace
21Me3SI (0.1)NaBO3·H2O (0.1)MeOH12 h40%
22Me3SI (0.1)Na3BO3 (0.1)MeOH12 hTrace
Open in a separate windowaReaction conditions: 1a (1.0 equiv.), salt (0.1 to 1.0 equiv.), additive (0.1 to 1.0 equiv.), solvent (1 mL) in open-air at room temperature.bThe isolated and unoptimized yields, based on the starting material 1a.cIncreasing the amount of both salt and additive up to 1.0 equiv., 24 h. NR = no reaction.Consequently, TOAc-glucal 1a was subjected to various complementary halide salts employing NaIO4 (0.1 equiv.) in MeOH under ambient reaction conditions (Scheme 2. Of the particular note, diverse and commonly used O-protecting groups in d-glucal comprising benzoyl (1b), benzyl (1c), methyl (1d), and tert-butyldimethylsilyl ether (1e) were fully tolerated, thus unambiguously establishing the potential synthetic applicability of the representative chemoselective procedure. Subsequently, the selective deacetylation of several per-O-acetylated glycals: d-galactal (2a), d-rhamnal (3a), l-rhamnal (4a), d-xylal (5a), d-arabinal (6a) and l-arabinal (7a), also disaccharide derived glycals bearing 1,4-glycosidic linkages, for example d-lactal (8a) and d-maltal (9a), were performed successfully to obtain the corresponding products 2–9 in excellent yields.Open in a separate windowScheme 2The study of the substrate scope and a functional group compatibility investigation for the chemoselective deacetylation. Reaction conditions: 1a–23a (1.0 equiv.), Me3SI (0.1 equiv.), additive (0.1 equiv.), MeOH (1 mL), 25 °C under atmospheric pressure, 1–12 h. The isolated and unoptimized yields are shown.Furthermore, the substrates bearing O-TIPS (10a), O-Bn (11a–13a), and 4,6-O-benzylidene (14a) in carbohydrate substrates were uniformly sustained under selective deacetylation conditions giving the hydroxyl products 10–14, respectively, (up to 98% yields). Indeed, the glycosides comprising sensitive O-isopropylidene linkages in d-galactopyranose (15a), d-glucofuranose (16a), d-ribose (17a), and unprotected uridine (18a) were selectively deacetylated to generate the corresponding free-hydroxyl compounds 15–18 in good yields. Importantly, the amino acid derivatives 19a–23a including relatively subtle or labile substituents such as tert-butylcarbamate (Boc), fluorenylmethoxycarbonyl (Fmoc) carbobenzoxy (Cbz), and methyl ester (–CO2Me), underwent efficient chemoselective deacetylation giving the desired products 19–23 in good to excellent yields.Encouraged by these results, the scope of the selective protocol was extended by performing the systematic deacetylation of substrates involving benzylic, alkylic, allylic, phenolic, naphthyl, hetereocyclic, alicyclic, spirocyclic, natural-products, long chain aliphatic, and aminoxy moieties. As illustrated in Scheme 3, a series of substrates enclosing comparatively susceptible and electronically diverse O-protecting groups (O-Ac; 24avs. O-Piv; 24b, O-Boc; 24c, O-Ms; 24d, O-THP; 24e, O-Tr; 24f) were well protected under present conditions, further confirming the effectiveness of the chemoselective method. The Me3SI-catalyzed simple removal of acetyl groups, in menthyl (25a), geranyl (26a), cholesteryl (27a), and diversely substituted aryl substrates 28a–35a, was conducted to efficiently obtain the desired products 25–35 in good-to-excellent yields (90–99%). It is worth noting, that the selective deacetylation for a substrate consisting of two electronically different acetates was accomplished successfully (cleavage of O-acetate vs. N-acetate in 29a).Open in a separate windowScheme 3Extended scope of the Me3SI-catalyzed selective deacetylation. Reaction conditions: 24a–55a (1.0 equiv.), Me3SI (0.1 equiv.), additive (0.1 equiv.), MeOH (1 mL), 25 °C under atmospheric pressure, 1–12 h. The isolated and unoptimized yields are shown.Next, the diversely substituted phenolic or naphthylic O-acetates 36a–42a, eugenyl 43a, vanillyl 44a, and estrone acetate 45a were subjected, under ambient conditions, to access the corresponding free-phenols 36–45 in acceptable yields (72–96%). Likewise, the reaction employing heterocyclic furfuryl acetate (46a), 2-amino-(Cbz)-ethyl acetate (47a), and alicyclic substrates with different ring sizes (five, six, or seven) 48a–50a proceeded smoothly providing the corresponding products 46–50 (80–99% yields). Additionally, long chain aliphatic acetates 51a and 52a, a spirocycle bearing sensitive dioxa moiety 53a, sterically hindered adamantyl 54a, and aminoxy-O-acetate 55a were competent, when used in the applied protocol, of producing their corresponding hydroxyls 51–55 in satisfactory yields (90–99%).To gain further insight into the Me3SI-promoted deacetylation, the reaction of TOAc-glucal 1a was performed with equimolar amounts of trimethylsulfonium iodide and an additive (0.1 equiv. each) employing deuterated methanol (CD3OD) as the solvent (Fig. 1). The 1H-NMR analyses of the crude reaction mixture revealed the presence of a distinctive resonance which was due to an anomeric proton (δ 6.42 dd, J1-2 = 6.10, 1.4 Hz, H-1) and other characteristic chemical shifts which conformed with that of the desired product 1′ (tri-O-2H-d-glucal).Open in a separate windowFig. 1Experiments with deuterated methanol and 1H-NMR analyses, used to provide mechanistic rationalization for Me3SI-promoted deacetylation.With no variance, the acetyl protons of methyl acetate (CH3CO-OCD3) were found at δ 2.10 (s, 9H) which potentially resulted from the methanolysis of the acetate groups with CD3OD. In addition, substantial amounts of trimethylsulfonium hydroxide species were observed consistently at δ 3.05 as a singlet (vs. Me3SI at δ 1.56),24 and this established the role of trimethylsulfonium iodide in selective and simple cleavage of acetates. A set of control experiments were performed to identify the possible intermediate iodine species in this transformation. The studies revealed the absence of molecular iodine in the present reaction conditions as confirmed by a negative starch solution test (the color did not change to an intense blue color).24 Indeed, the standard Me3SI-mediated deacetylation reaction employing a common radical scavenger such as TEMPO (a stable aminooxy radical) or 2,6-di-tert-butyl-4-methylphenol (BHT) preceded smoothly, and further ruled out a radical pathway in the process. Although, attempting a reaction of TOAc-glucal 1a using a catalytic amount of iodine in methanol solvent was inconsistent (50–60% conversion) resulting in the mono-deacetylation of the primary acetate (6-OAc) even after a prolonged reaction time (48 h).18a It is worth noting that the characteristic Lewis acidity of molecular iodine (I2) has been exploited in the selective O-Ac as well N-Boc protection of diverse substrates.25Based on the previously mentioned experimental observations and with reference to precedents in the literature, a plausible mechanistic rationalization for a Me3SI-catalyzed reaction is postulated in Scheme 4. Initially, KMnO4 showed rapid disproportionation, resulting in permanganic acid (HMnO4 ↔ H+ + MnO4) and potassium methoxide (KOMe ↔ K+ + MeO) ions in the presence of methanol, which was attributed to the reducing behavior of methanol in the present system.26 The main oxidizing reagent Mn(vii)O4 was capable of inverting the polarity of the reactivity of the halide salt Me3SI in slightly acidic conditions which resulted in the iodate (I+) species [A], and was disproportionate to Mn(iv)O2 and H2O. The reduced Mn(iv) species would then readily oxidize back to the higher Mn(vi)O4 in a slightly basic medium (KOMe/H2O) under the normal atmosphere26c and this was likely to facilitate the release of trimethylsulfonium hydroxide. Meanwhile, the incipient electrophilic intermediate [A] initiated from the oxidation of Me3SI coordinated with the oxygen atoms of the carbonyl functionality (CH3CO2–) in the acetate compound [1a] to generate a transient species [B].25b,25c,27 This significantly induced the polarization of the C Created by potrace 1.16, written by Peter Selinger 2001-2019 O double bond and increased the electrophilicity of the carbonyl carbon as well contributing towards the bond lengthening of the carbonyl C Created by potrace 1.16, written by Peter Selinger 2001-2019 O moiety in [B].Open in a separate windowScheme 4A plausible mechanism for Me3SI-promoted selective deacetylation.Subsequent coordination of the K+ ion with alkyl-oxygen (RO) and attack of methoxide (MeO) as the nucleophile on the electrophilic carbon in [B], would then eventually produce the tetrahedral intermediate [C]. Following the elimination of the penultimate transient species [D] and simultaneously trapping of the respective alkoxide ion (RO) in a hydrolytic environment would unambiguously lead to the formation of the respective alkanol (ROH) [1] with the liberation of potassium methoxide. The proposed intermediate [D] finally displaced the corresponding methyl acetate (CH3CO2Me) by releasing the required iodate species [A] which presumably participated in another catalytic cycle en route to the selective deacetylation process.In summary, a catalytic and practical procedure for chemoselective deacetylation with a general substrate scope employing environmentally benign reagents under ambient reaction conditions is reported. It is worth noting that the catalytic protocol is broadly applicable to numerous substrates, including carbohydrates, amino acids, and natural products, tolerating orthogonal and sensitive groups (esters, ethers, silyl ethers, carbamates, carboxybenzyl, mesyl, 2-tetrahydropyranyl, trityl, aldehydes, and also alkenes). Furthermore, the method is advantageous as it involves a safe and convenient reaction, ensuring smooth and quantitative conversion as well as preventing trans-esterification.  相似文献   
29.
The efficacy of an integrated neuromuscular inhibition technique on upper trapezius trigger points in subjects with non-specific neck pain: a randomized controlled trial     
Amit V Nagrale  Paul Glynn  Aakanksha Joshi  Gopichand Ramteke 《Journal of Manual and Manipulative Therapy》2010,18(1):37-43
Currently, large levels of practice variability exist regarding the clinical deactivation of trigger points. Manual physical therapy has been identified as a potential means of resolving active trigger points; however, to date the ideal treatment approach has yet to be elucidated. The purpose of this clinical trial was to compare the effects of two manual treatment regimens on individuals with upper trapezius trigger points. Sixty patients, 19–38 years of age with non-specific neck pain and upper trapezius trigger points, were randomized into one of two, 4 week physical therapy programs. One group received muscle energy techniques while the second group received an integrated neuromuscular inhibition technique (INIT) consisting of muscle energy techniques, ischemic compression, and strain–counterstrain (SCS). Outcomes including a visual analog pain scale (VAS), the neck disability index (NDI), and lateral cervical flexion range of motion (ROM) were collected at baseline, 2 and 4 weeks after the initiation of therapy. Results revealed large pre–post-effect sizes within the INIT group (Cohen’s d  =  0.97, 0.94 and 0.97). Additionally, significantly greater improvements in pain and neck disability and lateral cervical flexion ROM were detected in favor of the INIT group (0.29–0.57, 0.57–1.12 and 0.29–0.57) at a 95% CI respectively. The findings of this study indicate the potential benefit of an integrated approach in deactivating upper trapezius trigger points. Further research should be performed to investigate the long-term benefits of the current treatment approach.  相似文献   
30.
Bacteriology of the burn wound at the Bai Jerbai Wadia Hospital for children, Mumbai, India��A 13-year study, Part I-Bacteriological profile     
Shankar Srinivasan  Arvind M. Vartak  Aakanksha Patil    Jovita Saldanha 《Indian Journal of Plastic Surgery》2009,42(2):213-218

Aim:

To study which organisms were prevalent in our burn unit and their antibiotic sensitivity pattern in brief.

Method:

Microbiological data of 1534 patients admitted to the burns unit of the Bai Jerbai Wadia Hospital for Children, Mumbai over a period of 13 years (1994-2006) was reviewed retrospectively. A total of 9333 swabs were cultured and antibiotic sensitivities to the isolated organisms determined. The age group of patients admitted to our facility ranged from one month to 15 years.

Result:

Klebsiella was the predominant organism in our set-up (33.91%), closely followed by Pseudomonas (31.84%). The antibiotic sensitivities of the isolated organisms are discussed in detail in the text.

Conclusion:

Every treatment facility has microorganisms unique to it and these change with time. It is therefore of paramount importance to have an in-depth knowledge of the resident organisms and their antibiotic sensitivity pattern so that infection-related morbidity and mortality are improved.  相似文献   
[首页] « 上一页 [1] [2] 3 [4] 下一页 » 末  页»
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号