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991.
992.
The aim of this study was to examine the role of the lateral peterygoid muscle in the reconstruction of the shape of the condyle during healing of a sagittal fracture of the mandibular condyle. Twenty adult sheep were divided into 2 groups: all had a unilateral operation on the right side when the anterior and posterior attachments of the discs were cut, and an oblique vertical osteotomy was made from the lateral pole of the condyle to the medial side of the condylar neck. Ten sheep had the lateral pterygoid muscle cut, and the other 10 sheep did not. Sheep were killed at 4 weeks (n=2 from each group), 12 weeks (n=4), and 24 weeks (n=4) postoperatively. Computed tomograms (CT) were taken before and after operations. We dissected the joints, and recorded with the naked eye the shape, degree of erosion, and amount of calcification of the temporomandibular joint (TMJ). In the group in which the lateral peterygoid muscle had not been cut the joints showed overgrowth of new bone and more advanced ankylosis. Our results show that the lateral pterygoid muscle plays an important part in reconstructing the shape of the condyle during the healing of a sagittal fracture of the mandibular condyle, and combined with the dislocated and damaged disc is an important factor in the aetiology of traumatic ankylosis of the TMJ.  相似文献   
993.
Both adsorption and photocatalysis are considered to be effective methods for removing organic contaminants from dye wastewater. In this study, the construction of 3D skeletons based on the nanoparticles ZnO and ABS/TPU/calcium silicate (CaSiO3) (shortened as ATC) were fabricated via fused deposition molding (FDM) technology. Characterization by scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) depicted that ZnO nanospheres had been successfully grown on the 3D skeleton surface with an enlarged specific surface area. As the results of the RhB adsorption and photocatalytic degradation experiments showed, the removal ratio of RhB onto the ZnO-ATC skeleton was as high as 97.94% and the synergistic effect of adsorption and photocatalysis greatly shortened the RhB degradation time under ultraviolet light irradiation. The nanocomposites synthesized in this study showed a significant removal ability for organic pollutants, and could effectively overcome the limitation of the secondary removal of photocatalysts.

Enhanced synergistic effect of photocatalytic and adsorption was realized through the system constructed of ZnO nanoparticle loaded 3D skeleton.  相似文献   
994.
An efficient and highly diastereoselective synthesis of 2-substituted benzo[b]azepin-5-ol via stereocontrolled addition of Grignard reagents to oxa-bridged benzazepines has been developed. The reaction proceeds efficiently starting from versatile skeletons with mild reaction conditions as well as simple operation. Furthermore, 2-substituted benzazepinones could been obtained by simple Dess–Martin oxidation in excellent yields.

An efficient and highly diastereoselective synthesis of 2-substituted benzo[b]azepin-5-ol via stereocontrolled addition of Grignard reagents to oxa-bridged benzazepines has been developed.

Benzofused azepines, a unique family of seven-member aza-heterocycles, are widely found in numerous bioactive molecules, natural products and pharmaceuticals.1–4 This is due to their chemotherapeutic properties, and exhibiting interesting biological activities,5–9 for instance, competitive vasopressin receptor antagonist (tolvaptan),10–12 antidepressants (mianserin),13 zilpaterol (beef improvement agent),14 ACE inhibitor (benazepril)15 (Fig. 1).Open in a separate windowFig. 1Selected examples containing a benzazepine skeleton.Consequently, tremendous efforts have recently been dedicated to developing new methodologies to construct the benzazepine derivatives. Typically, the benzazepine skeletons could be assembled by expansion of smaller rings, rearrangements,16,17 Dieckmann cyclization,18,19 transition-metal-catalyzed coupling, ring closure metathesis,15,20,21 and others.22–25 Nevertheless, most of these protocols are limited to highly engineered starting materials, expensive catalysts and hazardous handling, obviously expeditious strategies for the diverse construction of benzazepine backbones from readily available starting materials, remains highly attractive and challenging.Diversity-oriented synthesis (DOS), defined as a powerful synthetic strategy to the libraries of diverse highly valuable molecules from one parent compound,26,27 is therefore well-suited for the timely design and execution of parallel (library) synthesis.28 In recent years, our group focused on the development of a more facile and efficient diversity-oriented synthesis strategy for the generation of this class of 7-membered heterocyclic compounds.29–31 This newly introduced ene-type cyclization reaction was used to prepare a series of bridged aromatic fused azepines,29 as a versatile building block, which could be transformed into structurally different ring systems through selective ring opening of the cyclic acetals (Scheme 1A).30,31Open in a separate windowScheme 1Our previous work (A) and this work (B).As an extension of our ongoing work toward the synthesis of the azepine skeleton, we suggested a new reaction model could be achieved if the suitable nucleophile could be carefully designed. Recently, a couple of efficient approaches to access nitrogen-containing heterocycles has been developed through the nucleophilic addition of cyclic N,O-acetal with Grignard reagents.32–35 Inspired by their excellent studies and to showcase the utility of cyclic N,O-acetal building blocks for the preparation of functionalized azepines, we present a facile approach to a stereoselective synthesis of 2,5-substituted benzazepine derivatives from oxa-bridged benzazepines by Grignard addition. This strategy is complementary to our recently published cascade reaction to prepare the benzazepinone scaffold. Herein, the details of this study is disclosed.Our investigations commenced by exploring nucleophilic addition of 1a, which was readily prepared in two steps via substitution reaction and subsequent ene-type reaction (see the ESI). We started our screening with 1-allyl-2,3,4,5-tetrahydro-1H-2,5-epoxybenzo[b]azepine (1a) as a model substrate for the optimization of the reaction conditions (36,37 We were gratified to find that Grignard reagents could indeed be added with high selectivity (
EntrySolventAdditiveTimeYieldb (%) dr (syn/anti)c
1dTHF10 h0
2dDioxane10 h0
3Et2O30 min922a, 24/76
41,2-Dichloroethane10 min902a, 68/32
5CHCl310 min952a, 66/34
6CH2Cl210 min962a, 69/31
7CH2Cl2MgBr2 (1.2 equiv.)10 min902a, 70/30
8CH2Cl210 min972b, 91/9
9CH2Cl210 min882c, 100/0
Open in a separate windowaReaction conditions: 1a (1 mmol), MeMgBr in 10 mL of solvent at 0 °C under air.bIsolated yield after column chromatography.cDetermined by 1H NMR and X-ray crystallographic analysis.dThe reaction was conducted at 0 °C for 1 h, then at 25 °C for 9 h.However, there was no significant improvement in the diastereoselectivity was observed after the addition of magnesium bromide36 (Fig. 2). From the diffraction pattern, it could be clearly seen that the hydroxyl group and the methyl group are on the same side. The stereochemistry in the rest of the series could be unambiguously assigned by comparison of their NMR spectra with those of syn-2m.Nucleophilic addition with Grignard reagents on cyclic N,O-acetalsa
Entry N,O-AcetalsR1R2R3Time2Yield (%) syn/antib
11aMeHAllyl10 min2a9669/31
21aEtHAllyl10 min2b9791/9
31a i-PrHAllyl7 h2c88100/0
41aCyHAllyl18 h2d83100/0
51aAllylHAllyl10 min2e980/100
61aPhHAllyl10 min2f98100/0
71bMeMeAllyl10 min2g9188/12
81bAllylMeAllyl10 min2h900/100
91cMeClAllyl10 min2i9267/33
101cAllylClAllyl10 min2j910/100
111dMeHMe10 min2k9268/32
121d i-PrHMe5 min2l91100/0
131eMeHH1 h2m8091/9
141eAllylHH10 min2n8175/25
Open in a separate windowaUnless indicated otherwise, the reaction was carried out on 1.0 mmol scale in DCM (10 mL).bDiastereoisomeric ratios were determined by 1H NMR analysis of the mixture, see the ESI for details.Open in a separate windowFig. 2X-ray crystallographic structure of syn-2m.In general, the improved diastereoselectivities were observed with increasing steric bulk of the Grignard reagents, the syn-adduct was the major product in all cases (38–43 Even phenylmagnesium bromide could be added to 1a and provided the adduct in 98% yield and a single syn-adduct (37 7-Substituented substrates (1b, 1c) were also tolerated by this process, as well as Me at the nitrogen atom of the substrate (1d) (Fig. 3 (transition state A).36,44,45 However, this diastereoselectivity for Grignard addition to the N-unsubstituted cyclic N,O-acetal 1a may be attributed to a highly ordered transition state resulting from significant chelation of the alkoxy substituent and imino nitrogen to at least one magnesium cation as shown Fig. 3 (transition state B).46,47Open in a separate windowFig. 3Proposed transition states accounting for the diastereoselectivity.To give the intrinsic versatility of 2-substituted benzo[b]azepin-5-ol and as a complement to our recently published cascade reaction to prepare the benzazepinone scaffold, treatment of the above compounds 2 with Dess–Martin in CH2Cl2 gave the 2-substituted benzazepinones 3 in good to excellent yields ( EntryR1R2R3Time (min)3Yield (%)1HAllylMe303a852HAllylEt303b833HAllyl i-Pr153c864HAllylCy153d805HAllylAllyl153e756HAllylPh153f887MeAllylMe203g888MeAllylAllyl453h769ClAllylMe603i8410ClAllylAllyl603j7811HHMe203k38Open in a separate windowaUnless indicated otherwise, the reaction was carried out on 0.5 mmol scale in DCM (5 mL).The synthetic versatility of 2-substituted benzazepinones has also been explored. The fused tricyclic compound 4 (ref. 48) could also be readily synthesized from 3e. Treatment of 3e with Grubbs II catalyst led to 4 in 95% yield [eqn (1)].1In conclusion, we have demonstrated that the cyclic N,O-acetals were successfully applied to the diastereoselective addition of various Grignard reagents with encouraging levels of stereoselection. In the formation of 2,5-substituted 1-benzazepine derivatives, the reaction proceeds through a ring-opening/nucleophilic addition pathway. These benzo[b]azepin-5-ols then undergo simple Dess–Martin oxidation to afford the 2-substituted benzazepinones in excellent yields. In respect to the easy availability of the starting materials, simple manipulation, mild conditions and high diastereoselectivity, this reaction will be synthetically useful in organic chemistry.  相似文献   
995.
The migration of acetochlor from feed to milk     
Xue Qin  Yujun Jiang  Zhenghui Wang  Chaoxin Man  Shiqian Fu  Sihan Chen  Xinyan Yang  Tao Yang  Dongyan Zhang  Linyao Li  Edward M. Fox  Wei Zhang 《RSC advances》2020,10(72):44344
Acetochlor has been widely used globally for its effective weed control, but the dietary intake of associated residues by people has become a major concern nowadays. Milk is regarded as the best solvent to dissolve pesticides due to its fat-rich characteristic. In this study, we aimed to evaluate the transfer of acetochlor from feed to raw milk. Twenty lactating Australian Holstein cows were randomly chosen and divided into 1 control group and 3 treatment groups, feeding acetochlor at the dosages of 0, 0.45, 1.35 and 4.05 g per day during the treatment period. The concentration of acetochlor residues in raw milk was detected by QuEChERS together with a gas chromatography-mass spectrometry (GC-MS) method. The results showed that the highest concentrations of acetochlor residues in raw milk for the three treatment groups had a positive correlation with the dosage levels and the transfer efficiency of the low dose group was only 0.080%, higher than those of the other two groups. Besides, the national estimated daily intake (NEDI) of acetochlor from milk is 1.67 × 10−5 mg kg−1, which is 0.08% of the ADI. Overall, we concluded that the risk of acetochlor residues in milk was low, but high-dose acetochlor had a larger impact on milk quality and low-dose acetochlor had potential risks.

Acetochlor has been widely used globally for its effective weed control, but the dietary intake of associated residues by people has become a major concern nowadays.  相似文献   
996.
多模式神经电生理检测对脊髓手术患者神经功能状态的评估分析及其影响因素     
沈强  朱玲  白雪  于绍斌  刘凤欣 《武警医学》2019,30(9):756-759
 目的 使用肌电图(electromyography,EMG)、体感诱发电位(somatosensory evoked potential,SEP)与运动诱发电位(motor evoked potentials,MEP)多模式方法检测手术前后神经系统的多种电生理信号,探讨患者神经功能状态。方法 收集100例患者作为研究对象,术中监测患者双下肢的SEP与MEP情况;术后6个月复查患者EMG。结果 术中SEP波幅与潜伏期在较稳定情况下,MEP监测中42例患者术中的D波波幅发生降低未超过50%,22例患者出现D波波幅突然下降且超过50%。Pearson相关性分析结果表明,术中出血量与SEP及MEP波幅与潜伏期的改变具有相关性。术后复查,各组患者的腓总神经与胫神经的NCV与DL均有显著改善,异常组患者的改善情况明显低于其他四组。结论 使用EMG、SEP与MEP多模式神经电生理检测可以去除干扰因素,为脊髓手术提供客观、有价值的诊疗依据。  相似文献   
997.
Probing Changes in Lung Physiology in COPD Using CT,Perfusion MRI,and Hyperpolarized Xenon-129 MRI     
Kun Qing  Nicholas J. Tustison  John P. Mugler  Jaime F. Mata  Zixuan Lin  Li Zhao  Da Wang  Xue Feng  Ji Young Shin  Sean J. Callahan  Michael P. Bergman  Kai Ruppert  Talissa A. Altes  Joanne M. Cassani  Y. Michael Shim 《Academic radiology》2019,26(3):326-334
  相似文献   
998.
过表达脑源性神经营养因子的神经干细胞移植对受照海马内神经营养因子的影响          下载免费PDF全文
钟雪  张奇贤  张洁  陈列松  田野 《中华放射医学与防护杂志》2019,39(4):241-246
目的 探讨过表达脑源性神经营养因子(BDNF)的神经干细胞(NSCs)移植入放射性脑损伤大鼠模型后,对海马内神经营养因子水平及小胶质细胞活化的影响。方法 从胎鼠脑中分离海马神经干细胞并进行培养。选用绿色荧光蛋白(GFP)-慢病毒、GFP-BDNF-慢病毒感染神经干细胞。将SD大鼠按随机数表法分为4组:健康对照组、单纯照射组(R组)、照射后GFP修饰的神经干细胞移植组(R+NSCs组)、照射后GFP-BDNF修饰的神经干细胞移植组(R+BDNF-NSCs组)。全脑单次20 Gy照射后1个月将神经干细胞移植入大鼠双侧海马内。移植后2和8周检测海马组织中BDNF、胶质源性神经营养因子(GDNF)、神经生长因子(NGF)的表达情况;免疫荧光染色观察小胶质细胞活化情况。结果 移植后2和8周时,与R组相比,R+BDNF-NSCs组海马组织中BDNF、NGF蛋白表达均水平明显增高(P<0.05);移植后8周R+NSCs组和R+BDNF-NSCs组活化的小胶质细胞与R组相比并未显著减少(P>0.05)。结论 过表达BDNF的神经干细胞移植后促进BDNF、NGF的产生,增加了辐射暴露后的海马内神经营养因子水平。  相似文献   
999.
舒血宁注射液联合阿托伐他汀治疗老年慢性硬膜下血肿的临床研究     
李学  王增光 《现代药物与临床》2017,32(8):1433-1436
目的探讨舒血宁注射液联合阿托伐他汀治疗慢性硬膜下血肿的临床疗效。方法选取2016年1月—2017年1月在天津医科大学总医院滨海医院治疗的慢性硬膜下血肿患者76例,依据治疗方案的差别分为对照组(38例)和治疗组(38例)。对照组口服阿托伐他汀钙片,20 mg/次,1次/d。治疗组在对照组的基础上静脉滴注舒血宁注射液,20 mL加入5%葡萄糖溶液250 mL,1次/d。两组患者均治疗30 d。评价两组患者临床疗效,同时比较治疗前后两组患者CSS和ADL评分以及血肿量和血清学指标。结果治疗后,对照组和治疗组的总有效率分别为81.58%、97.37%,两组比较差异具有统计学意义(P0.05)。治疗后,两组CSS评分与血肿量均显著降低,ADL评分升高,同组比较差异具有统计学意义(P0.05);且治疗组CSS和ADL评分及血肿量均显著优于对照组,两组比较差异具有统计学意义(P0.05)。治疗后,两组血清神经元特异性烯醇化酶(NSE)、基质金属蛋白酶-9(MMP-9)、脑源性神经营养因子(BDNF)水平显著降低,同组比较差异具有统计学意义(P0.05);且治疗组上述血清学指标明显低于对照组,两组比较差异具有统计学意义(P0.05)。结论舒血宁注射液联合阿托伐他汀治疗慢性硬膜下血肿临床疗效显著,可有效改善神经功能和促进血肿吸收,具有一定的临床推广应用价值。  相似文献   
1000.
影响药物毒性神经病理学评价质量的主要因素     
屈哲  林志  吕建军  霍桂桃  杨艳伟  张頔  张硕  霍艳  耿兴超  王雪  李波 《现代药物与临床》2017,40(9):1348-1354
神经毒性是许多药物或化合物常见的毒副作用。在新药研发早期要进行神经毒性筛选。对于可能通过血脑屏障影响神经系统的小分子药物或疫苗类的生物制品在临床前安全性评价中要进行非人灵长类动物的神经毒性评价。毒性病理学或神经病理学评价是临床前药物神经毒性评价的金标准。针对影响药物毒性神经病理学评价质量的几个主要因素,包括神经病理学评价的一般策略、最佳的评价时机、特殊的神经组织屏障系统、神经组织病理制片中的取材方法以及人工假象对神经病理学诊断的干扰,进行详细的解析,以期为我国神经毒性评价指导原则的制定和药物非临床神经毒性研究提供参考。  相似文献   
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