Parallel synthesis of 1,3-dihydro-1,4-benzodiazepine-2-ones employing catch and release

An efficient solid-phase method has been developed for the parallel synthesis of 1,3-dihydro-1,4-benzodiazepine-2-one derivatives. A key step in this procedure involves catching crude 2-aminobenzoimine products 4 on an amino acid Wang resin 10. Mild acidic conditions then promote a ring closure and in the same step cleavage from the resin to give pure benzodiazepine products 12. The 2-aminobenzoimines 4 can be synthesized from either 2-aminobenzonitriles 1 and Grignard reagents 2 or from iodoanilines 5 and nitriles 7 allowing a range of diversification. Further diversification can be introduced to the benzodiazepine products by N-alkylation promoted by a resin bound base and alkylating agents 13.     

平面波在任意磁化方向旋磁媒质中传播时的极化特性

在铁氧体基片平面电路和发射天线中必须研究平面波在任意磁化方向旋磁媒质中的传播。这时平面波的特征波为ＴＥ波,其磁通密度、磁场、电通密度、电场的极化是不相同的,磁场的极化方向为左、右椭圆极化。     

Photopatterned polymer brushes promoting cell adhesion gradients

The ability to spatially control cellular adhesion in a continuous manner on a biocompatible substrate is an important factor in designing new biomaterials for use in wound healing and tissue engineering applications. In this work, a novel method of engineering cell-adhesive RGD-ligand density gradients to control specific cell adhesion across a substrate is presented. Polymer brushes exhibiting spatially defined gradients in chain density are created and subsequently functionalized with RGD to create ligand density gradients capable of inducing cell adhesion on an otherwise weakly adhesive substrate. Cell studies indicate that these ligand-functionalized surfaces are noncytotoxic, with cellular adhesion increasing with RGD-ligand density across the gradient brush surface.     

Anti-biofouling properties of comblike block copolymers with amphiphilic side chains

Surfaces of novel block copolymers with amphiphilic side chains were studied for their ability to influence the adhesion of marine organisms. The surface-active polymer, obtained by grafting fluorinated molecules with hydrophobic and hydrophilic blocks to a block copolymer precursor, showed interesting bioadhesion properties. Two different algal species, one of which adhered strongly to hydrophobic surfaces, and the other, to hydrophilic surfaces, showed notably weak adhesion to the amphiphilic surfaces. Both organisms are known to secrete adhesive macromolecules, with apparently different wetting characteristics, to attach to underwater surfaces. The ability of the amphiphilic surface to undergo an environment-dependent transformation in surface chemistry when in contact with the extracellular polymeric substances is a possible reason for its antifouling nature. Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) was used, in a new approach based on angle-resolved X-ray photoelectron spectroscopy (XPS), to determine the variation in chemical composition within the top few nanometers of the surface and also to study the surface segregation of the amphiphilic block. A mathematical model to extract depth-profile information from the normalized NEXAFS partial electron yield is developed.     

Mono-layer of Ni(100-x)Fe(x) nanoparticles fabricated on a polyimide film under different curing atmospheres

A mono-layer of nano-sized metal particles was prepared on the surface of a polyimide film by simply depositing a thin film of Ni80Fe20 on top of the polyamic acid that was spin coated onto a Si wafer. During thermal imidization of the polyamic acid film, Fe was selectively etched by reacting with the carbonyl group of the polyamic acid to leave behind uniformly distributed Ni-rich metallic particles. The average diameter of the particles was 4 nm and the particles were confined into a single layer on top of the polymer film. Moreover, it was also shown that the morphology of the nanoparticles can be substantially altered by curing the precursor film in a hydrogen atmosphere, without significantly damaging the polymer film. Thus produced nanoparticles lay exposed on top of the electrically insulating and chemically stable polymer film so that it is possible that the nanoparticles can be directly used for fabricating a nonvolatile flash memory device or as a template for building functional nano-structures.     

Biomodification of coal to remove mercury

A biological process for removal of mercury from coal is under investigation. Iron and sulfur oxidizing bacteria have previously been used for desulfurization of coal and for mineral mining. We have shown that removal of mercury from coal is also possible via the same principles. Two pure cultures, Leptospirillum ferrooxidans and Acidithiobacillus ferrooxidans and four environmental consortium samples obtained from an acid mine drainage site were studied for mercury removal from coal. Four different coal samples were included in the study and the preliminary results have shown that up to 20% of the mercury can be removed in batch cultures compared to control. Additional parameters such as media composition and inoculum size were also studied. This is the first report demonstrating successful leaching of mercury from coal using biological treatment.     

Biomolecular imaging based on far-red fluorescent protein with a high two-photon excitation action cross section

Received October 14, 2005; revised January 7, 2006; accepted January 9, 2006; posted January 12, 2006 (Doc. ID 65391) The two-photon excitation action cross section of Hc-Red fluorescent proteins (Hc-RFPs) is measured and found to be of the same order as that of enhanced green fluorescent proteins. With a 618 nm emission wavelength in the far-red region and with an excitation wavelength around 1200 nm, Hc-RPF-based two-photon fluorescence microscopy (2PFM) can offer deep penetration capability inside live samples and is ideal for in vivo gene expression study and biomolecular imaging in live objects. In vivo 2PFM of the developing heart deep inside a transgenic zebrafish embryo tagged by Hc-RFP is also successfully demonstrated.     

Low-loss subwavelength plastic fiber for terahertz waveguiding

We report a simple subwavelength-diameter plastic wire, similar to an optical fiber, for guiding a terahertz wave with a low attenuation constant. With a large wavelength-to-fiber-core ratio, the fractional power delivered inside the lossy core is reduced, thus lowering the effective fiber attenuation constant. In our experiment we adopt a polyethylene fiber with a 200 microm diameter for guiding terahertz waves in the frequency range near 0.3 THz in which the attenuation constant is reduced to of the order of or less than 0.01 cm(-1). Direct free-space coupling efficiency as high as 20% can be achieved by use of an off-axis parabolic mirror. Furthermore, all the plastic wires are readily available, with no need for complex or expensive fabrication.     

Copper(I)-catalyzed regio- and chemoselective single and double addition of nucleophilic silicon to propargylic chlorides and phosphates

Copper(I)-catalyzed propargylic substitution of linear precursors with (Me(2)PhSi)(2)Zn predominantly yields the γ isomer independent of the propargylic leaving group. The thus formed allenylic silane reacts regioselectively with another equivalent of (Me(2)PhSi)(2)Zn, yielding a bifunctional building block with allylic and vinylic silicon groups. The reaction rates of both steps are well-balanced for chloride (γ:α ≥ 99:1) where the propargylic displacement occurs quantitatively prior to the addition step. Substitutions of α-branched propargylic phosphates are also reported.     

Asymmetric cyclization reactions of allenoates with imines or α,β-unsaturated ketones catalyzed by organocatalysts derived from cinchona alkaloids

Lewis base-catalyzed cyclization reactions of allenoates with electron-deficient olefins and imines have been demonstrated by the preparation of biologically active natural products and pharmaceutically interesting substances and have emerged as powerful synthetic tools in the rapid construction of cyclic molecular complexity. In contrast to phosphine-containing Lewis bases, nitrogen-containing Lewis base amines display markedly different reaction profiles; however, this area is not well-developed. Herein we summarize the recent progress in this emerging field and outline the challenges ahead.