Dielectric, piezoelectric and elastic properties of tetragonal BiScO3-PbTiO3 single crystal with single domain

Modified BiScO₃-PbTiO₃ (BSPT) tetragonal single crystals were grown using high temperature solution method. The dielectric, piezoelectric and elastic properties of single domain BSPT crystals, after poling along [001] crystallographic direction, have been determined experimentally using the resonance method. The results showed that the BSPT tetragonal crystals possess good piezoelectric properties, with electromechanical coupling factor about 88% and piezoelectric coefficient over 400 pC/N at room temperature. BSPT tetragonal crystals have high Curie temperature around 436 °C and high coercive field ∼28 kV/cm, also, the crystal exhibited a very good temperature stability of the properties till 380 °C. For comparison, the material constants of tetragonal Pb(Zn_1/3Nb_2/3)O₃-PbTiO₃ (PZNT) single crystals were measured and listed in this paper.     

PAMAM dendrimer interactions with supported lipid bilayers: a kinetic and mechanistic investigation

The interaction kinetics of polyamidoamine (PAMAM) dendrimers with supported lipid bilayers of 1,2-sn-glycero-dimyristoylphosphocholine prepared by the vesicle deposition has been probed by optical waveguide lightmode spectroscopy and atomic force microscopy (AFM). In particular, the influence of PAMAM dendrimer generation (G2, G4, and G6) and concentration (1 to 100 nM) on the levels of adsorption and lipid bilayer removal have been determined as a function of time; hence interaction kinetics and mechanisms have been further elucidated. Dendrimer interaction kinetics with the lipid bilayer are concentration dependent in a complex manner, with net bilayer removal at 1 and 100 nM and net adsorption at 10 nM; these effects are irrespective of dendrimer generation. The pseudo first order rate constant for bilayer removal (at 1 and 100 nM) follows the order G6 > G4 > G2. In contrast, the pseudo first order rate constant for adsorption at 10 nM follows the order G2 > G4 > G6. AFM has confirmed expansion of lipid bilayer defects, hole formation, and adsorption to the bilayer or bilayer defects, and their concentration and generation dependence. These findings have implications when designing dendrimers for specific biopharmaceutical activities, e.g., as drugs, drug delivery vehicles, transfection agents, or antimicrobials.     

Ultra-resolution imaging of a self-assembling biomolecular system using robust carbon nanotube AFM probes

Nanoscale structural features of a novel self-assembling DNA based nanostructure have been resolved. Image data is of sufficient resolution to allow molecular orientation and the effect of surface adsorption to be characterized. This has been achieved using AFM with probes employing carbon nanotubes attached via a thin film of plasma polymerized hexane. This presents the nanotube with a highly hydrophobic coating to which it can adsorb, increasing production success and probe robustness.     

Synthesis of diverse 2,3-dihydroindoles, 1,2,3,4-tetrahydroquinolines, and benzo-fused azepines by formal radical cyclization onto aromatic rings

2,3-Dihydroindoles, 1,2,3,4-tetrahydroquinolines, and 2,3,4,5-tetrahydrobenzo[b]azepines are available by a process that represents formal radical cyclization onto aromatic rings. Optically pure benzo-fused heterocycles are also accessible by this method. p-Iodophenols, especially those with the phenolic oxygen protected as a MOM-ether, can be coupled with amino alcohols to produce N-aryl amino alcohols, which can be converted into the corresponding alkyl iodides in which the nitrogen is protected as a carbamate. These compounds give cross-conjugated ketones after removal of the phenolic protecting group and oxidation with PhI(OAc)(2) in the presence of MeOH. The ketones undergo 5-, 6- or 7-exo-trigonal radical cyclization, and then exposure to acid, or sequential treatment with a Grignard reagent and then acid, effects rearomatization to produce the benzo-fused nitrogen heterocycles.     

Formal radical closure onto aromatic rings--a general route to carbocycles

A general method is described for indirectly effecting radical carbocyclization of an alkyl chain onto an aromatic ring. Birch reductive-alkylation of aromatic tert-butyl esters with alpha,omega-dibromides, chromium(vi)-mediated oxidation of the resulting 1,4-dienes and Finkelstein displacement of Br(-) with NaI gives cross-conjugated ketones that undergo radical cyclization. The products are easily aromatized to phenols by silylation, Saegusa oxidation and treatment with BiCl(3).H(2)O. A special feature of the route is that it allows attachment of a substituent to the original aromatic ring in place of the phenolic oxygen of the normal product.     

Synthesis of (-)-conocarpan by two routes based on radical cyclization and establishment of its absolute configuration

Two independent routes for the total synthesis of the bioactive neolignan (-)-conocarpan are described. The first (98% ee) is based on formal radical cyclization onto a benzene ring, and involves a 5-exo-trigonal closure onto a double bond restrained within a 6-membered ring. The second route (88% ee), which is shorter, is based on 5-exo-trigonal cyclization of an aryl radical onto a pendant terminal double bond. The two routes differ in their degree of stereoselectivity. The absolute configuration originally assigned to (+)-conocarpan had previously been called into question on the basis of empirical chiroptical rules; the present chemical work confirms the need for revision, and the assigned absolute configurations of several compounds correlated with (+)-conocarpan must also be changed.     

Synthesis of dihydrooxepin models related to the antitumor antibiotic MPC1001

4-Hydroxy-L-proline was converted into the tetrahydrooxepino[4,3-b]pyrrole ring system characteristic of the potent antitumor agent MPC1001. Key steps were regioselective formation of a vinylogous amide by use of Bredereck's reagent and acid-induced cyclization of an alcohol onto the carbon-carbon double bond of that amide by addition-elimination to generate the seven-membered oxacyclic subunit.     

Highly selective 4-amino-1,8-naphthalimide based fluorescent photoinduced electron transfer (PET) chemosensors for Zn(II) under physiological pH conditions

The design and synthesis of two novel fluorescent sensors based on the photoinduced electron transfer (PET) concept, and , for the detection of zinc under competitive media is described. These sensors are based on the 4-amino-1,8-naphthalimide fluorophore, which has an absorption band centred at 450 nm and emits in the green with lambda(max) approximately 550 nm. By functionalizing the chromophore with a simple benzyl or ethyl-aryl based iminodiacetate receptor at the 4-position, both high selectivity and sensitivity were achieved for the sensing of Zn(II) over other competitive transition and Group I and II metal ions. These sensors were also shown to be pH independent, with a pKa of 2.3 being determined for , which allows these to be used in highly competitive pH media. Upon sensing of Zn(II) the fluorescence emission spectrum is 'switched on' demonstrating the suppression of PET from the receptor to the fluorophore. For , the sensing of Zn(II) was achieved with Kd = 4 nM when measured in pH 7.4 buffered solution, in the presence of 1.1 mM of EGTA.     

Robustness of Tube Formula Based Confidence Bands

Abstract

Simultaneous confidence bands of a regression curve may be used to quantify the uncertainty of an estimate of the curve. The tube formula for volumes of tubular neighborhoods of a manifold provides a very powerful method for obtaining such bands at a prescribed level, when errors are Gaussian. This article studies robustness of the tube formula for non-Gaussian errors. The formula holds without modification for an error vector with a spherically symmetric distribution. Simulations are used for a variety of independent non-Gaussian error distributions. The results are acceptable for contaminated and heavy tailed error distributions. The formula can break down in some extreme cases for discrete and highly skewed errors. Computational issues involved in applying the tube formula are also discussed.