Diterpenes with new isoryanodane derived skeletons from Persea indica

A phytochemical study of the aerial parts of Persea indica has permitted the isolation of two diterpenes with novel skeletons derived from isoryanodane, which have named perseaindicol and secoperseanol. A third compound, also with a new carbon framework, proved to be identical with cinncassiol E, whose structure has been now corrected.     

Radical intermediates in the photorearrangement of 3-hydroxyindolic nitrones

A number of 3-hydroxy substituted indolic nitrones were found to quantitatively photorearrange to (2-benzoylamino)phenyl ketones upon UV-A irradiation. EPR-Spin Trapping experiments suggest that the process, which is believed to proceed via the formation of an oxaziridine, follows a homolytic pathway. Although DFT calculations do not allow to totally exclude alternative routes involving singlet intermediates, they do provide support to the proposed homolytic mechanism, which would be driven by a 1,5-hydrogen transfer subsequent to the oxaziridine ring opening. When this hydrogen transfer was made impossible by methylation of the 3-OH group, a benzoxazine was isolated as the sole reaction product.     

Site‐Specific Chemical Surface Functionalization and Electronic Patterning of Graphene by Electrooxidative Lithography

The combination of different properties being manipulated on nanomaterials is one of the challenges in nanotechnology research. In particular, the possibility to tailor the electronic and chemical properties offers promising possibilities for the design of functional nanostructures. Herein, we report an approach that permits control of these properties on the basis of electrooxidative lithography to structure reduced graphene oxide functionalized with a self‐assembled monolayer of n‐octadecyltrichlorosilane. The electrochemical oxidation process first induces the formation of polar acid groups on the monolayer, which can be used to covalently bind nanoparticles and molecules and, secondly, also allows the reoxidation of the underlying reduced graphene oxide. As such, the chemical signature as well as the electronic properties of the substrate can be tailored on the micro‐ and nanometer scale. Details on the oxidation of the monolayer as well as thorough characterization of the electronic properties will be presented. Finally, the approach is used to demonstrate the fabrication of a sensitive glucose sensor device.     

A pure aqueous route to mesoporous silica thin films via dip-coating of prefabricated hybrid micelles

Journal of Sol-Gel Science and Technology - Mesoporous thin films were prepared by dip-coating with a purely aqueous method, as a substitute for the alcohol-based evaporation-induced self-assembly...     

Polymerization of free secondary amine bearing monomers by RAFT polymerization and other controlled radical techniques

This work describes the polymerization of the free secondary amine bearing monomer 2,2,6,6‐tetramethylpiperidin‐4‐yl methacrylate (TMPMA) by means of different controlled radical polymerization techniques (ATRP, RAFT, NMP). In particular, reversible addition‐fragmentation chain transfer (RAFT) polymerization enabled a good control at high conversions and a polydispersity index below 1.3, thereby enabling the preparation of well‐defined polymers. Remarkably, the polymerization of the secondary amine bearing methacrylate monomer was not hindered by the presence of the free amine that commonly induces degradation of the RAFT reagent. Subsequent oxidation of the polymer yielded the polyradical poly(2,2,6,6‐tetramethylpiperidinyloxy‐4‐yl methacrylate), which represents a valuable material used in catalysis as well as for modern batteries. The obtained polymers having a molar mass (M_n) of 10,000–20,000 g/mol were used to fabricate well‐defined, radical‐bearing polymer films by inkjet‐ printing. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Finding common RNA pseudoknot structures in polynomial time

This paper presents the first polynomial time algorithm for finding common RNA substructures that include pseudoknots and similar structures. While a more general problem is known to be NP-hard, this algorithm exploits special features of RNA structures to match RNA bonds correctly in polynomial time. Although the theoretical upper bound on the algorithm?s time and space usage is high, the data-driven nature of its computation enables it to avoid computing unnecessary cases, dramatically reducing the actual running time. The algorithm works well in practice, and has been tested on sample RNA structures that include pseudoknots and pseudoknot-like tertiary structures.     

Cancer genetic counseling in public health care hospitals: the experience of three Brazilian services

In Brazil, genetic counseling is usually available in university-affiliated medical genetics services located in tertiary centers that provide cancer diagnosis and treatment. The present study aims to describe the structure and characteristics of three cancer genetic services in Brazilian public health care hospitals and discuss alternatives for the identification and prevention of hereditary cancer syndromes in developing countries. The three services presented here are similar in their structure, routine procedures for cancer risk estimation and criteria for the indication of genetic testing. They all demand that genetic counseling be an essential part of the cancer risk evaluation process, before and after cancer predisposition testing. However, when high-risk patients are identified, all services describe difficulties in the access and continuity of genetic and medical services to the patient and his/her at-risk relatives. The services differ in the type of population served, reflecting distinct referral guidelines. This study emphasizes the importance of the creation of new cancer genetic services in other Brazilian regions and the necessity for establishing a collaborative network to facilitate the diagnosis and research of cancer genetic syndromes.