Deposition of DNA-functionalized gold nanospheres into nanoporous surfaces

We report the deposition of DNA-conjugated gold nanospheres into arrays of surface nanopores obtained from hexagonally ordered thin polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer films on silicon. The deposition occurs spontaneously from aqueous solution and is driven by either electrostatic interactions or specific DNA hybridization events between the DNA nanospheres and the surface nanopores. To mitigate this spontaneous deposition, we have chemically modified the nanopores with either positively charged aminosilanes or oligonucleotide probe sequences. The deposition of DNA nanospheres into the surface nanopores was characterized by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). We have observed preferential immobilization of individual DNA nanospheres within the nanopores, based on the size matching between the two entities. The inclusion density and selectivity of DNA nanosphere deposition into the surface nanopores was found to depend predominantly on the methods through which the nanoporous surfaces were prepared and chemically functionalized.     

Fe(0)-mediated synthesis of tri- and tetra-substituted olefins from carbonyls: an environmentally friendly alternative to Cr(II)

Fe(0) was investigated as a cost-effective, environmentally friendly alternative to Cr(II) for the olefination of carbonyls by activated polyhalides. In many instances, Fe(0) was equivalent or superior to Cr(II). Notably, Fe(0), but not Cr(II), proved compatible with a wide range of functionality, inter alia, unprotected phenol, aryl nitro, carboxylic acid, and alkyl nitrile. A surprising reversal of stereoselectivity for aldehydes versus ketones was observed using both metals. The resultant alpha-halo-alpha,beta-unsaturated or alpha,beta-unsaturated carboxylic acids, esters, and nitriles are common structural elements in numerous compounds of interest as well as key intermediates in the preparation of other functionality.     

Reactions of 2‐amino‐4h‐1‐benzopyran‐4‐one with 4‐oxo‐4h‐1‐benzopyran‐3‐carbaldehydes

The title aldehyde 1 reacts smoothly with the enamine moiety of 2 ‐aminochromone 2 to produce hitherto unreported 3‐(2‐hydroxybenzoyl)‐5H‐1‐benzopyrano[2,3‐b]pyridin‐5‐one (azaxanthone) 5 . This reaction has been extended for the synthesis of bisazaxanthone 9.     

Reciprocal Ontological Models Show Indeterminism Comparable to Quantum Theory

We show that within the class of ontological models due to Harrigan and Spekkens, those satisfying preparation-measurement reciprocity must allow indeterminism comparable to that in quantum theory. Our result implies that one can design quantum random number generator, for which it is impossible, even in principle, to construct a reciprocal deterministic model.     

Spin dynamics and spin noise in the presence of randomly varying spin-orbit interaction in a semiconductor quantum wire

Using ensemble Monte Carlo simulation, we have studied hot carrier spin dynamics and spin noise in a multi-subband GaAs quantum wire in the presence of a randomly varying Rashba spin-orbit interaction. The random variation reduces the carrier ensemble's spin dephasing time due to the D'yakonov-Perel' mechanism, but otherwise makes no qualitative difference to the temporal spin relaxation characteristics. However, it makes a qualitative difference to the spatial spin relaxation characteristics which change from monotonic and smooth to non-monotonic and chaotic because of a complex interplay between carriers in different subbands. As far as spin fluctuation and spin noise are concerned, the random variation has no major effect except that the low-frequency noise power spectral density increases slightly when the magnitude of the Rashba spin-orbit interaction field is varied randomly while holding the direction constant.     

Emulsion of aqueous-based nonspherical droplets in aqueous solutions by single-chain surfactants: templated assembly by nonamphiphilic lyotropic liquid crystals in water

Single-chain surfactants usually emulsify and stabilize oily substances into droplets in an aqueous solution. Here, we report a coassembly system, in which single types of anionic or non-ionic surfactants emulsify a class of water-soluble nonamphiphilic organic salts with fused aromatic rings in aqueous solutions. The nonamphiphilic organic salts are in turn promoted to form droplets of water-based liquid crystals (chromonic liquid crystals) encapsulated by single-chain surfactants. The droplets, stabilized against coalescence by encapsulated in a layer (or layers) of single chain surfactants, are of both nonspherical tactoid (elongated ellipsoid with pointy ends) and spherical shapes. The tactoids have an average long axis of ～9 μm and a short axis of ～3.5 μm with the liquid crystal aligning parallel to the droplet surface. The spherical droplets are 5-10 μm in diameter and have the liquid crystal aligning perpendicular to the droplet surface and a point defect in the center. Cationic and zwitterionic surfactants studied in this work did not promote the organic salt to form droplets. These results illustrate the complex interplay of self-association and thermodynamic incompatibility of molecules in water, which can cause new assembly behavior, including potential formation of vesicles or other assemblies, from surfactants that usually form only micelles. These unprecedented tactoidal shaped droplets also provide potential for the fabrication of new soft organic microcapsules.     

New observations on scratch deformations of soda lime silica glass

In spite of the wealth of literature, the role of the scratching speed in affecting the material removal mechanism in soda lime silica (SLS) glass is yet to be comprehensively understood. Here we report the surface and sub‐surface deformation mechanisms of SLS glass scratched under three different normal loads of 5, 10 and 15 N at various speeds in the range of 100–1000 μm/s with a diamond indenter of ~ 200 μm tip radius. The results show that at any given applied normal load, the width, depth, wear volume of the scratch grooves and wear rate of the SLS glass decreased with an inverse power law dependence on the applied scratching speed. The surface damage also reduced with the increase in scratching speed. A new, simple model was developed to explain these observations. The significant contributions of the time of contact, the tensile stress behind the indenter and the shear stress active just underneath the indenter in governing the material removal mechanisms of the SLS glass were discussed.     

Novel synthesis of 3-pyrrole substituted β-lactams via microwave-induced bismuth nitrate-catalyzed reaction

Highly stereoselective synthesis of 3-pyrrole substituted β-lactams is accomplished. The first step involves the synthesis of 3-phthalimido substituted β-lactams following Staudinger cycloaddition reaction of acid chloride equivalent with imines. Synthesis of 3-amino β-lactams is achieved via the deprotection of phthalimido group with ethylenediamine. These 3-amino β-lactams are converted to a new series of N-substituted pyrroles at room temperature as well as using microwave-induced bismuth nitrate-catalyzed reaction with an excellent yield. Exclusive formation of trans pyrrole-substituted β-lactams is observed with N-chrysenyl system. The method is equally efficient for the synthesis of racemic as well as optically pure 3-pyrrole substituted β-lactams.     

peri-Dimethylamino substituent effects on proton transfer at carbon in α-naphthylacetate esters: a model for mandelate racemase

The rate constants for exchange of hydrogen for deuterium at the α-CH(2) positions of 8-(N,N-dimethylaminonaphthalen-1-yl)acetic acid tert-butyl ester 1 and naphthalen-1-ylacetic acid tert-butyl ester 2 have been determined in potassium deuteroxide solutions in 1 : 1 D(2)O : CD(3)CN, in order to quantify the effect of the neighbouring peri-dimethylamino substituent on α-deprotonation. Intramolecular general base catalysis by the (weakly basic) neighbouring group was not detected. Second-order rate constants, k(DO), for the deuterium exchange reactions of esters 1 and 2 have been determined as 1.35 × 10(-4) M(-1) s(-1) and 3.95 × 10(-3) M(-1) s(-1), respectively. The unexpected 29-fold decrease in the k(DO) value upon the introduction of a peri-dimethylamino group is attributed to an unfavourable steric and/or electronic substituent effect on intermolecular deprotonation by deuteroxide ion. From the experimental k(DO) values, carbon acid pK(a) values of 26.8 and 23.1 have been calculated for esters 1 and 2.     

Can functionalized cucurbituril bind actinyl cations efficiently? A density functional theory based investigation

The feasibility of using cucurbituril host molecule as a probable actinyl cation binders candidate is investigated through density functional theory based calculations. Various possible binding sites of the cucurbit[5]uril host molecule to uranyl are analyzed and based on the binding energy evaluations, μ(5)-binding is predicted to be favored. For this coordination, the structure, vibrational spectra, and binding energies are evaluated for the binding of three actinyls in hexa-valent and penta-valent oxidation states with functionalized cucurbiturils. Functionalizing cucurbituril with methyl and cyclohexyl groups increases the binding affinities of actinyls, whereas fluorination decreases the binding affinities as compared to the native host molecule. Surprisingly hydroxylation of the host molecule does not distinguish the oxidation state of the three actinyls.