催化的端炔C-H键与α,β-不饱和-γ-内酰胺的亲核加成反应

吡咯啉酮是一类重要的五元杂环,广泛存在于许多天然产物、生物活性分子和高聚物中.在众多吡咯啉酮衍生物中,5-炔基-2-吡咯啉酮引起了化学家们广泛的关注.因为这种分子结构不仅存在于具有潜在治疗作用的药物分子(如眼部降压药、α7乙酰胆碱受体激动剂、抗惊厥和消炎药物)中,也存在于许多天然产物中,例如刺桐类生物碱和多环类生物碱.鉴于此,人们发展了许多合成这类化合物的方法.目前文献报道最多的方法是炔基负离子对5-位具有离去基团的吡咯啉酮化合物的亲核取代反应.离去基团主要有苯硫基、1-苯并咪唑基和烷氧基等.但是这些方法操作步骤繁琐,产生大量的副产物,原子经济性不高.
　　本课题组发展了一例新型的端炔C–H键与α,β-不饱和-γ-内酰胺的亲核加成反应,合成了一系列5-炔基-2-吡咯啉酮衍生物.该反应以环状N-酰亚胺正离子为反应活性中间体,反应条件温和,操作简便.据我们所知,这是一例原子经济地合成5-炔基-2-吡咯啉酮衍生物的新方法.环状N-酰亚胺正离子是一类高活性的亲电试剂,广泛应用于构建含氮杂环体系.本课题组利用这一策略实现了一系列C–C和C–N成键反应.基于此,本文原位形成环状N-酰亚胺正离子,以端炔作为亲核试剂,与其发生亲核加成反应,合成了一系列5-炔基-2-吡咯啉酮衍生物,原子经济性为100%.
　　首先,我们以5 mol%TsOH为Br?nsted酸,考察了Lewis酸效应对反应收率的影响.结果表明, Al(OTf)3给出最好的反应收率,不加Lewis酸没有亲核加成产物生成.然后,我们以5 mol%Al(OTf)3为Lewis酸,考察了Br?nsted酸效应对反应收率的影响.结果表明, HAuCl4·4H2O给出最佳的反应收率54%,不加Br?nsted酸也没有亲核加成产物生成.值得一提的是,当HAuCl4·4H2O为单一催化剂,不加Al(OTf)3时,反应收率也达到55%.然后,我们以HAuCl4·4H2O为催化剂,考察了溶剂效应和反应温度对反应收率的影响.结果表明,四氯乙烷(TTCE)为反应最佳的溶剂,50 oC反应最佳.为了进一步提高反应收率,我们又考察了催化剂用量对反应收率的影响.结果表明,10 mol%的催化剂给出最佳的反应收率60%.进一步优化反应条件,我们没有得到更好的结果.因此最佳的反应条件： N-苄基-α,β-不饱和-γ-内酰胺1(0.4 mmol),苯乙炔2a (1.2 mmol), HAuCl4·4H2O (10 mol%), TTCE (2.0 mL),50 oC下反应15 h.
　　在确定了最佳的反应条件后,我们对端炔类底物的适用性进行了考察.结果表明,给电子的苯乙炔表现出较高的反应活性;弱吸电子的苯乙炔也表现出较高的反应活性;强吸电子的苯乙炔则抑制反应的发生;位阻效应对该反应没有明显影响;杂环端炔也给出中等以上的收率;然而,简单脂肪端炔不能给出相应的亲核加成产物.
　　本文发展了一例催化的端炔C–H键与α,β-不饱和-γ-内酰胺的亲核加成反应.该反应以环状N-酰亚胺正离子为关键中间体.反应条件温和,操作简便.构建了一种以中等的收率(45%–76%)合成一系列5-炔基-2-吡咯啉酮衍生物的方法.     

Tribotronic Phototransistor for Enhanced Photodetection and Hybrid Energy Harvesting

Tribotronics is a new field developed by coupling triboelectricity and semiconductor, which can drive triboelectric‐charge‐controlled optoelectronic devices by further introducing optoelectronics. In this paper, a tribotronic phototransistor (TPT) is proposed by coupling a field‐effect phototransistor and a triboelectric nanogenerator (TENG), in which the contact‐induced inner gate voltage by the mobile frictional layer is used for modulating the photodetection characteristics of the TPT. Based on the TPT, alternatively, a coupled energy‐harvester (CEH) is fabricated for simultaneously scavenging solar and wind energies, in which the output voltage on the external resistance from the wind driven TENG is used as the gate voltage of the TPT for enhancing the solar energy conversion. As the wind speed increases, the photovoltaic characteristics of the CEH including the short‐circuit current, open‐circuit voltage, and maximal output power have been greatly enhanced. This work has greatly expanded the functionality of tribotronics in photodetection and energy harvesting, and provided a potential solution for highly efficient harvesting and utilizing multitype energy.     

Approximation of Invariant Measures for Regime-switching Diffusions

In this paper, we are concerned with long-time behavior of Euler-Maruyama schemes associated with regime-switching diffusion processes. The key contributions of this paper lie in that existence and uniqueness of numerical invariant measures are addressed (i) for regime-switching diffusion processes with finite state spaces by the Perron-Frobenius theorem if the “averaging condition” holds, and, for the case of reversible Markov chain, via the principal eigenvalue approach provided that the principal eigenvalue is positive; (ii) for regime-switching diffusion processes with countable state spaces by means of a finite partition method and an M-Matrix theory. We also reveal that numerical invariant measures converge in the Wasserstein metric to the underlying ones. Several examples are constructed to demonstrate our theory.     

图的k部划分的一个注记

设k≥2是一个整数。本文证明了任意有m条边的图都存在一个顶点的划分V_1,V_2…,V_k,使得e(V_1,V_2…,V_k)≥k-1/k m+k-1/2k((2m+1/4)~1/2-1/2)-(k-2)~2/8k,且max{e(V_i):1≤i≤k}≤m/k~2+(k-1)/2k~2((2m+1/4)~1/2-1/2+3/8-7k-4/8k~2.我们的结果改进了[Fan G.,Hou J.,Zeng Q.,A bound for judicious k-partitions of graphs,Discrete Appl.Math.,2014,179:86—99]的主要结论.     

基于PSO算法的RoboCup2D机器人研究

对机器人体系结构、动作学习及行为的组织方式进行了研究,以演化计算为基本方法,以RoboCup2D为平台,设计了基于PSO算法的足球机器人的体系结构,解决感知、动作、和规划问题;在训练环境下,形成感知规则,优化感知相关参数,得到对信息高效快速的感知方法,并根据指定的粒度、功能、参数,对RoboCup2D机器人的原子动作进行了组合优化,得到一组带参数和执行效果描述的粒子动作;最后在赛场环境和任务驱动下,搜索粒子动作并进行组织规划,得到完成特定任务的机器人行为;RoboCup2D仿真实验表明,演化计算方法不仅能利用原子动作进行组合优化,得到适应于不同条件的粒子动作,而且能通过其在线搜索粒子动作,动态组成机器人行为;基于演化计算的足球机器人能更好地完成跑位、截球、带球、传球等任务,具有更强的适应性。     

Improved reconstruction for MR spectroscopic imaging

Sensitivity limitations of in vivo magnetic resonance spectroscopic imaging (MRSI) require that the extent of spatial-frequency (k-space) sampling be limited, thereby reducing spatial resolution and increasing the effects of Gibbs ringing that is associated with the use of Fourier transform reconstruction. Additional problems occur in the spectral dimension, where quantitation of individual spectral components is made more difficult by the typically low signal-to-noise ratios, variable lineshapes, and baseline distortions, particularly in areas of significant magnetic field inhomogeneity. Given the potential of in vivo MRSI measurements for a number of clinical and biomedical research applications, there is considerable interest in improving the quality of the metabolite image reconstructions. In this report, a reconstruction method is described that makes use of parametric modeling and MRI-derived tissue distribution functions to enhance the MRSI spatial reconstruction. Additional preprocessing steps are also proposed to avoid difficulties associated with image regions containing spectra of inadequate quality, which are commonly present in the in vivo MRSI data     

Antibacterial thymol derivatives isolated from Centipeda minima

Two new monoterpenoids, 8,10-dihydroxy-9(2)-methylbutyryloxythymol (1) and 10-hydroxy-8,9-dioxyisopropylidene-thymol (2), together with five known thymol derivatives: 8,9,10-trihydroxythymol (3), thymol-beta-glucopyranoside (4), 9-hydroxythymol (5), 8,10-dihydroxy-9-isobutyryloxythymol (6), and 8-hydroxy-9,10-diisobutyryloxythymol (7), were isolated from Centipeda minima. Their structures were identified by means of spectroscopic analyses. Interestingly, compound 2 is not an extraction artifact according to a close HPLC examination of material after extraction by analytical MeOH at ambient temperature. The antibacterial activities of compounds 1-7 were evaluated against eight microbial strains by the agar dilution method.     

Optimisation of Hydrocortisone Production by Curvularia lunata

A new method for breeding the hydrocortisone overproducing strain Curvularia lunata by screening ketoconazole-resistance mutant was developed. A hydrocortisone overproducing mutant C. lunata KA-91 with ketoconazole-resistance marker was obtained from protoplasts treated with ultraviolet radiation. The hydrocortisone conversion rate of C. lunata KA-91 was increased by 42.1% compared to the original strain CL-114 at the substrate 17α-hydroxypregn-4-en-3, 20-dione-21-acetate addition concentration of 1.0 g/L. The by-products produced by KA-91 were fewer than those of the original strain. It was assumed that the higher cytochrome P450 content of ketoconazole-resistance mutant resulted in the increase of 11β-hydroxylation capacity. The culture conditions for biotransformation of 17α-hydroxypregn-4-en-3, 20-dione-21-acetate to hydrocortisone were optimized by response surface methodology. Plackett–Burman design was applied to elucidate the key factors affecting the hydrocortisone production, and the results indicated that glucose, initial pH, and glucose to total nitrogen sources ratio (ω) had significant effects on hydrocortisone production. Box–Behnken design was employed to search for the optimal parameters of those three key factors. According to the model, the trial checking at the optimal conditions showed a high hydrocortisone conversion rate of 82.67%.     

Tuning of redox properties of iron and iron oxides via encapsulation within carbon nanotubes

We report the tuning of the redox properties of iron and iron oxide nanoparticles by encapsulation within carbon nanotubes (CNTs) with varying inner diameters. Raman spectroscopy was employed to investigate the interaction of the encapsulated nanoparticles with the CNTs. A red shift of the Fe-O mode is observed in the nanoparticles deposited on the outer CNT surfaces with respect to bulk Fe2O3. However, this mode is found to be stepwise blue-shifted with decreasing inner diameter in the CNT-encapsulated Fe2O3 nanoparticles, suggesting an enhanced interaction of Fe2O3 with the inner CNT surface as its curvature increases. The autoreduction of the encapsulated Fe2O3 is significantly facilitated inside CNTs with respect to the outside nanoparticles. Interestingly, it becomes more facile with decreasing CNT channel diameter as evidenced by temperature programmed reaction, in situ XRD, and Raman spectroscopy. The oxidation of encapsulated metallic Fe nanoparticles on the other hand is retarded in comparison to that of the outside Fe particles as shown by in situ XRD and gravimetrical measurements with an online microbalance. We attribute this tunable redox behavior of transition metal nanoparticles inside CNTs to a particular electronic interaction of the encapsulates with the interior CNT surface, which stabilizes the metallic state of Fe.