Tandem allylic oxidation-condensation/esterification catalyzed by silica gel: an expeditious approach towards antimalarial diaryldienones and enones from natural methoxylated phenylpropenes

A new one-pot strategy has been developed, wherein abundantly available methoxylated phenylpropenes are directly transformed into corresponding dienones (1,5-diarylpenta-2,4-dien-1-ones) and enones (chalcones and cinnamic esters) via allylic oxidation-condensation or allylic oxidation-esterification sequences. Preliminary antimalarial activity studies of the above synthesized diaryldienones and enones against Plasmodium falciparum (Pf3D7) have shown them to be promising lead candidates for developing newer and economical antimalarial agents. In particular, two enones (12b and 13b) were found to possess comparatively better activity (IC(50) = 4.0 and 3.4 μM, respectively) than licochalcone (IC(50) = 4.1 μM), a well known natural antimalarial compound.     

Gold(I)-catalyzed Claisen rearrangement of allenyl vinyl ethers; synthesis of substituted 1,3-dienes

Synthesis of substituted 1,3-dienes was achieved via gold(I)-catalyzed Claisen rearrangement of allenyl vinyl ethers. The N-heterocyclic carbene gold chloride catalyst (IPrAuCl) was superior in terms of activity and selectivity and afforded the 3,3-product in excellent yields. A proposed cation-π inter-action played a significant role in affecting the reaction rate.     

A terpyridyl-imidazole (tpy-HImzPh3) based bifunctional receptor for multichannel detection of Fe2+ and F- ions

The X-ray crystal structures of the tridentate ligand, 4'-[4-(4,5-diphenyl-1H-imidazol-2-yl)-phenyl]-[2,2':6',2']terpyridine (tpy-HImzPh(3)) and its bis-homoleptic iron(ii) complex of composition [Fe(tpy-HImzPh(3))(2)](2+) have been determined, showing that the ligand crystallized in a monoclinic form with the space group P2(1)/c while its Fe(II) complex crystallizes in an orthorhombic form with space group Fddd. Both the anion and cation binding properties of the receptor were thoroughly investigated in dimethylformamide-acetonitrile (1?:?9) solution using absorption, emission, and (1)H NMR spectral studies which revealed that the receptor acts as a sensor for both F(-) and Fe(2+). In the presence of excess F(-) ion, deprotonation of the imidazole N-H fragment of the receptor occurs, an event which is signaled by the development of a yellow color visible with the naked eye. The estimated value of the equilibrium constant of the receptor with F(-) is 1.9 × 10(4) M(-1). Deprotonation is also observed in the presence of hydroxide. The receptor also shows colorimetric and fluorimetric sensing ability towards Fe(2+) ions. The binding site for the metal ion in the system has been unambiguously established by single-crystal X-ray diffraction studies of the Fe(II) complex of the receptor. The influence of solvents on the absorption and fluorescence spectra of the receptor has been investigated in detail. Cyclic voltammetric (CV) and square wave voltammetric (SWV) measurements carried out in dimethylformamide-acetonitrile (2?:?3) provided evidence in favor of cation (Fe(2+)) and anion (F(-)) concentration dependent electrochemical responses, enabling the ligand to act as a suitable electrochemical sensor for F(-) and Fe(2+) ions.     

Sol–gel derived hybrid coatings as an environment friendly surface treatment for corrosion protection of metals and their alloys

Sol?Cgel derived organic inorganic hybrid coatings are effective corrosion protective systems for metals. They offer an excellent adhesion to metal as well as to the subsequent coat via strong covalent bond and a three dimensional network of ?CSi?CO?CSi?C linkages which helps to retard the penetration of corrosive medium through the coating. Unlike conventional surface protection methodology, silane based pre-treatment is an environment friendly technology with number of advantages like room temperature synthesis, chemical inertness, high oxidation and abrasion resistance, excellent thermal stability, very low health hazard etc. Further, the hybrid silane provides required flexibility and an increased compatibility with the subsequent coating in multicoat systems. The performance properties of hybrid systems depend on number of parameters like type of silane (mono or bis), degree of hydrolysis, type and dosage of inhibitive/barrier pigments (in case of pigmented system), application techniques, curing temperature and curing schedule, need to be optimized. A guideline formulation for maximum corrosion resistance with low environmental impact consist of a superprimer (a bis-silane with conventional resins, chrome free inhibitive pigments and additives) followed by epoxy or polyurethane top coat as per the exposure conditions.     

Controlled synthesis of nanocrystalline Li2MnSiO4 particles for high capacity cathode application in lithium-ion batteries

Monodispersed Li(2)MnSiO(4) nanoparticles are synthesized via a supercritical solvothermal method at 300 °C for 5 min reaction time. The as-synthesized nanoparticles are free from impurities and have 15-20 nm diameter. After coating with conductive polymer, a discharge capacity of 313 mA h g(-1) is obtained for the first time because of nearly 2Li(+) reaction.     

Structural Characterization of Backbone-Expanded Helices in Hybrid Peptides: (αγ)(n) and (αβ)(n) Sequences with Unconstrained β and γ Homologues of L-Val

Learning your αβγ's: The diversity of hydrogen-bonding patterns in backbone-expanded hybrid helices is shown by crystal-structure determination of several oligomeric peptides (see scheme; C=gray; H=white; O=red; N=blue). C(12) helices were observed in the αγ peptide series for n=2-8. In comparison, the αα peptide and αβ peptide sequences show C(10) and mixed C(14) /C(15) helices, respectively.     

Uniquely Clean Elements in Rings

It is well known that every uniquely clean ring is strongly clean. In this article, we investigate the question of when this result holds element-wise. We first construct an example showing that uniquely clean elements need not be strongly clean. However, in case every corner ring is clean the uniquely clean elements are strongly clean. Further, we classify the set of uniquely clean elements for various classes of rings, including semiperfect rings, unit-regular rings, and endomorphism rings of continuous modules.     

It takes more than an imine: the role of the central atom on the electron-accepting ability of benzotriazole and benzothiadiazole oligomers

We report on the comparison of the electronic and photophysical properties of a series of related donor-acceptor-donor oligomers incorporating the previously known 2H-benzo[d][1,2,3]triazole (BTz) moiety as the acceptor and the recently reported BTzTD acceptor, a hybrid of BTz and 2,1,3-benzothiadiazole (BTD). Although often implied in the polymer literature that BTz has good acceptor character, we show that this moiety is best described as a weak acceptor. We present electrochemical, computational, and photophysical evidence supporting our assertion that BTzTD is a strong electron acceptor while maintaining the alkylation ability of the BTz moiety. Our results show that the identity of the central atom (N or S) in the benzo-fused heterocyclic ring plays an important role in both the electron-accepting and the electron-donating ability of acceptor moieties with sulfur imparting a greater electron-accepting ability and nitrogen affording greater electron-donating character. We report on the X-ray crystal structure of a BTzTD trimer, which exhibits greater local aromatic character in the region of the triazole ring and contains an electron-deficient sulfur that imparts strong electron-accepting ability. Additionally, we examine the transient absorption spectra of BTzTD and BTz oligomers and report that the BTz core promotes efficient intersystem crossing to the triplet state, while the presence of the thiadiazole moiety in BTzTD leads to a negligible triplet yield. Additionally, while BTz does not function as a good acceptor, oligomers containing this moiety do function as excellent sensitizers for the generation of singlet oxygen.     

Efficient finite-edge diffraction using conservative from-region visibility

We present a fast algorithm to accelerate geometric sound propagation in complex 3D scenes. Our approach computes propagation paths from each source to the listener by taking into account specular reflections and higher-order edge diffractions around finite edges in the scene. We use the well known Biot–Tolstoy–Medwin (BTM) diffraction model along with efficient algorithms for region-based visibility to cull away primitives and significantly reduce the number of edge pairs that need to be processed. The performance of region-based visibility computation is improved by using a fast occluder selection algorithm that can combine small, connected triangles to form large occluders and perform conservative computations at object-space precision. We show that our approach is able to reduce the number of visible primitives considered for sound propagation by a factor of 2–4 for second order edge diffraction as compared to prior propagation algorithms. We demonstrate and analyze its performance on multiple benchmarks. To the best of our knowledge, this is the first algorithm that uses object-space visibility algorithms to improve the performance of finite-edge diffraction computation for geometric sound propagation.