An expeditious total synthetic route to naturally occurring tricarbocycIic ring ring-C-aromatic diter penoids: mechanisms of cyclialkylations

The critical role of the nature of aromatic ring substituents in the open chain substrates in the acid-catalyzed cyclialkylation reaction through 2-2(arylethyl)-l,3,3-trimethylcyclohexyl cation is exemplified with a large number of easily accessible mono- and disubstituted 2-(2-arylethyl)-l,3,3-trimethylcyclohexanols and a few 2-(2- arylethyl) -3,3-dimethyl-l-methylenecyclohexanes i n the distributions of the respective trans- and cis-podocarpatrienes. The cyclohexanol or the cyclohexylidene precursors having unactivated aromatic ring proceeds with high stereoselectivity leading to the respective trans- products, while the substrates with an electron donating substituent with respect to the site of electrophilic attack result in the corresponding cis- and the trans-product mixtures. Consistent mechanisms for these stereochemical results have been advanced. Based on these results simple syntheses of a few diterpenes have been realized

Synthesis of 1-p-methoxyphenyl- and 1-(p-methoxyphenyl)-4- methylbicyclo(2.2.1)heptan-7-one. The oxidation of 7-hydroxy-1-(p- methoxyphenyl)-4-methylbicyclo(2.2.1)heptane-7-carboxylic acid with lead tetraacetate

A simple synthetic route to 1-p-methoxyphenyl and 1-p-methoxyphenyl-4-methylbicyclo [2.2.1]heptan-7-one 6b,a has been developed through benzilic acid rearrangement of the bicyclo[2.2.1]octandiones 2b,a. The oxidation of 7-hydroxy-1-p-methoxyphenyl-4-methylbicyclo[2.2.1]heptan-7-carboxylic acid 3a with lead tetraacetate gives the carbolactone 7a which is also formed by the reaction of the ketone 6a with m-chloroperbenzoic acid

Acid-catalysed intra-molecular C-alkylation and alkylation-rearrangements through unsaturated diazomethyl ketones. A new varsatile approach to the synthesis of complex carbocylic systems

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Replicating Nanostructures on Silicon by Low Energy Ion Beams

We report on a nanoscale patterning method on Si substrates using self-assembled metal islands and low-energy ion-beam irradiation. The Si nanostructures produced on the Si substrate have a one-to-one correspondence with the self-assembled metal (Ag, Au, Pt) nanoislands initially grown on the substrate. The surface morphology and the structure of the irradiated surface were studied by high-resolution transmission electron microscopy (HRTEM). TEM images of ion-beam irradiated samples show the formation of sawtooth-like structures on Si. Removing metal islands and the ion-beam induced amorphous Si by etching, we obtain a crystalline nanostructure of Si. The smallest structures emit red light when exposed to a UV light. The size of the nanostructures on Si is governed by the size of the self-assembled metal nanoparticles grown on the substrate for this replica nanopatterning. The method can easily be extended for tuning the size of the Si nanostructures by the proper choice of the metal nanoparticles and the ion energy in ion-irradiation. It is suggested that off-normal irradiation can also be used for tuning the size of the nanostructures.Comment: 12 pages, 7 figures, regular paper submitted to Nanotechnolog

Primary brain T-cell lymphoma of the lymphoblastic type presenting as altered mental status

The authors present a case of a 56-year-old man with altered mental status. Magnetic resonance imaging (MRI) of the brain revealed non-enhancing abnormalities on T2 and FLAIR imaging in the brainstem, cerebellum, and cerebrum. Immunohistochemisty demonstrated precursor T-cell lymphoblastic lymphoma. After treatment with methotrexate, he improved clinically without focal sensorimotor deficits and with improving orientation. MRI showed almost complete resolution of brainstem and cerebral lesions. To the authors’ knowledge, there are only five previous reports of primary central nervous system T-cell lymphoblastic lymphoma. Since treatable, it deserves consideration in patients with altered mental status and imaging abnormalities that include diffuse, non-enhancing changes with increased signal on T2-weighted images

Endocrinologic, neurologic, and visual morbidity after treatment for craniopharyngioma

Craniopharyngiomas are locally aggressive tumors which typically are focused in the sellar and suprasellar region near a number of critical neural and vascular structures mediating endocrinologic, behavioral, and visual functions. The present study aims to summarize and compare the published literature regarding morbidity resulting from treatment of craniopharyngioma. We performed a comprehensive search of the published English language literature to identify studies publishing outcome data of patients undergoing surgery for craniopharyngioma. Comparisons of the rates of endocrine, vascular, neurological, and visual complications were performed using Pearson’s chi-squared test, and covariates of interest were fitted into a multivariate logistic regression model. In our data set, 540 patients underwent surgical resection of their tumor. 138 patients received biopsy alone followed by some form of radiotherapy. Mean overall follow-up for all patients in these studies was 54 ± 1.8 months. The overall rate of new endocrinopathy for all patients undergoing surgical resection of their mass was 37% (95% CI = 33–41). Patients receiving GTR had over 2.5 times the rate of developing at least one endocrinopathy compared to patients receiving STR alone or STR + XRT (52 vs. 19 vs. 20%, χ2P < 0.00001). On multivariate analysis, GTR conferred a significant increase in the risk of endocrinopathy compared to STR + XRT (OR = 3.45, 95% CI = 2.05–5.81, P < 0.00001), after controlling for study size and the presence of significant hypothalamic involvement. There was a statistical trend towards worse visual outcomes in patients receiving XRT after STR compared to GTR or STR alone (GTR = 3.5% vs. STR 2.1% vs. STR + XRT 6.4%, P = 0.11). Given the difficulty in obtaining class 1 data regarding the treatment of this tumor, this study can serve as an estimate of expected outcomes for these patients, and guide decision making until these data are available

Astrocytes: biology and pathology

Astrocytes are specialized glial cells that outnumber neurons by over fivefold. They contiguously tile the entire central nervous system (CNS) and exert many essential complex functions in the healthy CNS. Astrocytes respond to all forms of CNS insults through a process referred to as reactive astrogliosis, which has become a pathological hallmark of CNS structural lesions. Substantial progress has been made recently in determining functions and mechanisms of reactive astrogliosis and in identifying roles of astrocytes in CNS disorders and pathologies. A vast molecular arsenal at the disposal of reactive astrocytes is being defined. Transgenic mouse models are dissecting specific aspects of reactive astrocytosis and glial scar formation in vivo. Astrocyte involvement in specific clinicopathological entities is being defined. It is now clear that reactive astrogliosis is not a simple all-or-none phenomenon but is a finely gradated continuum of changes that occur in context-dependent manners regulated by specific signaling events. These changes range from reversible alterations in gene expression and cell hypertrophy with preservation of cellular domains and tissue structure, to long-lasting scar formation with rearrangement of tissue structure. Increasing evidence points towards the potential of reactive astrogliosis to play either primary or contributing roles in CNS disorders via loss of normal astrocyte functions or gain of abnormal effects. This article reviews (1) astrocyte functions in healthy CNS, (2) mechanisms and functions of reactive astrogliosis and glial scar formation, and (3) ways in which reactive astrocytes may cause or contribute to specific CNS disorders and lesions