Enantioselective total syntheses of manzamine a and related alkaloids

As a prelude to undertaking the total syntheses of the complex manzamine alkaloids, a series of model studies were conducted to establish the scope and limitations of intramolecular [4 + 2] cycloadditions of N-acylated vinylogous ureas with the trienic substrates 17a,b, 28a,b, and 34. These experiments clearly demonstrated that the geometry of the internal double bond and the presence of an electron-withdrawing group on the diene moiety were essential for the facile and stereoselective formation of the desired cycloadducts. The enantioselective syntheses of the manzamine alkaloids ircinol A (75), ircinal A (5), and manzamine A (1) were then completed by employing a convergent strategy that featured a novel domino Stille/Diels-Alder reaction to construct the tricyclic ABC ring core embodied in these alkaloids. Thus, the readily accessible chiral dihydropyrrole 58 was first converted in a single chemical operation into the key tricyclic intermediate 60. Two ring-closing metathesis reactions were then used to form the 13- and 8-membered rings leading to Z-72 and 74, the latter of which was quickly elaborated into ircinal A (5) via ircinol A (75). The synthetic 5 thus obtained was converted into manzamine A (1) following literature precedent. This concise synthesis of ircinal A required a total of 24 operations from commercially available starting materials with the longest linear sequence being 21 steps.     

Protective Effects of Thymoquinone,an Active Compound of Nigella sativa,on Rats with Benzo(a)pyrene-Induced Lung Injury through Regulation of Oxidative Stress and Inflammation

Benzopyrene [B(a)P] is a well-recognized environmental carcinogen, which promotes oxidative stress, inflammation, and other metabolic complications. In the current study, the therapeutic effects of thymoquinone (TQ) against B(a)P-induced lung injury in experimental rats were examined. B(a)P used at 50 mg/kg b.w. induced lung injury that was investigated via the evaluation of lipid profile, inflammatory markers, nitric oxide (NO), and malondialdehyde (MDA) levels. B(a)P also led to a decrease in superoxide dismutase (SOD) (34.3 vs. 58.5 U/mg protein), glutathione peroxidase (GPx) (42.4 vs. 72.8 U/mg protein), catalase (CAT) (21.2 vs. 30.5 U/mg protein), and total antioxidant capacity compared to normal animals. Treatment with TQ, used at 50 mg/kg b.w., led to a significant reduction in triglycerides (TG) (196.2 vs. 233.7 mg/dL), total cholesterol (TC) (107.2 vs. 129.3 mg/dL), and inflammatory markers and increased the antioxidant enzyme level in comparison with the group that was administered B(a)P only (p < 0.05). B(a)P administration led to the thickening of lung epithelium, increased inflammatory cell infiltration, damaged lung tissue architecture, and led to accumulation of collagen fibres as studied through haematoxylin and eosin (H&E), Sirius red, and Masson’s trichrome staining. Moreover, the recognition of apoptotic nuclei and expression pattern of NF-κB were evaluated through the TUNEL assay and immunohistochemistry, respectively. The histopathological changes were found to be considerably low in the TQ-treated animal group. The TUNEL-positive cells increased significantly in the B(a)P-induced group, whereas the TQ-treated group showed a decreased apoptosis rate. Significantly high cytoplasmic expression of NF-κB in the B(a)P-induced group was seen, and this expression was prominently reduced in the TQ-treated group. Our results suggest that TQ can be used in the protection against benzopyrene-caused lung injury.     

Noble Metal Nanocrystal‐Incorporated Fullerene‐Like Polyoxometalate Based Microspheres

Monodisperse fullerene‐like polyoxometalate‐based microspheres are synthesized using a single‐phase approach which is quick, easier to control surfactant to polyoxometalate (POM) molar ratios and result in better control over the size‐distribution range. Noble‐metal nanocrystals are successfully incorporated in the surfactant encapsulated complex multilayered spherical assemblies without any change in their layered morphology. Combining the merits of fullerene‐like POMs and monodisperse noble metal nanocrystals, these monodisperse hybrid spheres show interesting composition‐ and size‐dependent photochemical properties.     

Polysilicon thin-film transistors with channel length and widthcomparable to or smaller than the grain size of the thin film

Poly-Si thin-film transistors (TFTs) with channel dimensions (width W, and length L) comparable to or smaller than the grain size of the poly-Si film were fabricated and characterized. The grain size of the poly-Si film was enhanced by Si ion implantation followed by a low-temperature anneal and was typically 1 to 3 μm in diameter. A remarkable improvement was observed in the device characteristics as the channel dimensions decreased to W=L =2 μm. On the other hand, TFTs with submicrometer channel dimensions were characterized by an extremely abrupt switching in their I_D versus V_GS characteristics. The improvement was attributed to a reduction in the effect of the grain boundaries and to the effect of the device's floating body     

Opportunities and challenges in using WPAN and WLAN technologies in medical environments [Accepted from Open Call]

The present view of medical environments, where isolated networks are used for IT and medical applications, is changing toward an integrated heterogeneous network scenario that can support a wide range of applications. WPAN and WLAN technologies play a fundamental role in enabling such integrated environment that is expected to support both medical and nonmedical applications. The ultimate goal is to exploit WPAN and WLAN technologies, as well as other wireless networks, such as 3G cellular systems and satellite networks, to support highly efficient medical care delivery, anytime and anywhere. However, the life-critical nature of some medical applications imposes additional challenges that have not been considered in nonmedical scenarios. This article discusses some future scenarios where WLAN and WPAN technologies can be used to provide an integrated and ubiquitous network in medical environments, and identifies the main issues to be addressed in order to meet the QoS requirements of different medical applications when operating in integrated environment     

Direct photon production from pions and protons at 200 GeV/c

Direct photon production has been studied by an experiment performed with the NA3 spectrometer at CERN, using incident negative and positive beams at 200 GeV/c interacting with an isoscalar Carbon target. Two different triggers have been used; one of them requires the photon conversion. The experiment is sensitive to direct photons produced with 3.0≦P _T ≦6 GeV/c and center-of-mass rapidity ?0.4≦y ^*≦1.2. Inclusive cross sections are given for incident π^± and protons, and compared with second order QCD predictions; finally an estimation of the gluon structure function of the nucleon is given.     

Furan-containing conjugated polymers for organic solar cells

Development of organic semiconductors is one of the most intriguing and productive topics in material science and engineering. Many efforts have been made on the synthesis of aromatic building blocks such as benzene, thiophene and pyrrole due to the facile preparation accompanied by the intrinsic environmental stability and relatively efficient properties of the resulting polymers. In the past, furan has been less explored in this field because of its high oxidation potential. Recently, furan has attracted obsession due to its weaker aromaticity, the greater solubilities of furan-containing π-conjugated polymers relative to other benzenoid systems and the accessibility of furan-based starting materials from renewable resources. This review elaborates the advancements of organic photovoltaic polymers containing furan building blocks. The uniqueness and advantages of furan-containing building blocks in semiconducting materials are also discussed.