An asynchronous high‐speed synchrotron shutter

A high‐repetition‐rate mechanical shutter with asynchronous control and sub‐millisecond operation has been developed and tested for specialist X‐ray systems in the field of medical diagnostics and radiation therapy. Capacitor‐coupled linear voice coil actuators are utilized to achieve opening and closing speeds as fast as 700 µs for an aperture height of 4 mm. The design allows for asynchronous control, permitting slave operation of the shutter, a feature that is distinctly suitable for a number of applications including particle image velocimetry, where high‐frame‐rate operation must be accurately synchronized and triggered by the image acquisition sequence of the detector or timing device. The design and construction of the shutter also makes it ideal, with simple and limited modifications, for applications requiring larger apertures, in particular wide beams as found in many synchrotron beamlines.     

Photocondensation polymers: Polybenzopinacols. II. Photolytic coupling of aromatic diketones

Photolytic condensations of p,p′-dibenzoyldiphenyl sulfide, p,p′-dibenzoyldiphenyl ether, p,p′-dibenzoyldiphenylmethane, and p,p′-dibenzoyldiphenylethane with a 100-W long-wavelength ultraviolet lamp gave polypinacols having inherent viscosities ranging from 0.12 to 0.45. Treatment of the same monomers under similar conditions with a 450-W ultraviolet lamp produced polypinacols having inherent viscosities ranging from 0.04 to 0.37.     

Liquid deposition patterning of conducting polymer ink onto hard and soft flexible substrates via dip-pen nanolithography

Ink formulations and protocols that enable the deposition and patterning of a conducting polymer (PEDOT:PSS) in the nanodomain have been developed. Significantly, we demonstrated the ability to pattern onto soft substrates such as silicone gum and polyethylene terephthalate (PET), which are materials of interest for low cost, flexible electronics. The deposition process and dimensions of the polymer patterns are found to be critically dependent on a number of parameters, including the pen design, ink properties, time after inking the pen, dwell time of the pen on the surface, and the nature of material substrate. By assessing these different parameters, an improved understanding of the ability to control the dimensions of individual PEDOT:PSS structures down to 600 nm in width and 10-80 nm in height within patterned arrays was obtained. This applicability of DPN for simple and nonreactive liquid deposition patterning of conducting polymers can lead to the fabrication of organic nanoelectronics or biosensors and complement the efforts of existing printing techniques such as inkjet and extrusion printing by scaling down conductive components to submicrometer and nanoscale dimensions.     

Effect of flow on polymer-polymer miscibility

The effect of shear flow on the phase behaviour of partially miscible blends exhibiting a lower critical solution temperature behaviour has been investigated. Miscibility limits were detected, with and without the application of flow, as changes from optical clarity to turbidity using light scattering and as the appearance of double glass transition temperatures. Light scattering data were collected on a rheo-optical device that was designed to monitor phase changes in polymer blends undergoing shear flow between parallel glass plates in a temperature controlled environment. Glass transition temperatures of some quenched sheared blends were measured using a differential scanning calorimeter in order to confirm the conclusions from the light scattering data. It was found that shear induced demixing and shear induced mixing may be observed within the same blend depending on the magnitude of the applied flow. Miscibility gaps and closed miscibility loops may appear in the phase diagrams. At certain temperatures and shear rates unusual scattering patterns were observed and these were associated with a “ripple” morphology when directly viewed through the microscope.     

Direct synthesis of aqueous quantum dots through 4,4'-bipyridine-based twin ligand strategy

We report a new class of derivatized 4,4'-bipyridinium ligands for use in synthesizing highly fluorescent, extremely stable, water-soluble CdSe and CdTe quantum dots (QDs) for bioconjugation. We employed an evaporation-condensation technique, also known as solvated metal atom dispersion (SMAD), followed by a digestive ripening procedure. This method has been used to synthesize both metal nanoparticles and semiconductors in the gram scale with several stabilizing ligands in various solvents. The SMAD technique comprised evaporation condensation and stabilization of CdSe or CdTe in tetrahydrofuran. The as-prepared product was then digestively ripened in both water and dimethyl formamide, leading to narrowing of the particle size distributions. The ligands were synthesized by nucleophilic substitution (S(N)2) reactions using 4,4'-bipyridine as a nucleophile. Confocal microscopy images revealed the orange color of the nanocrystalline QDs with diameters of ~5 nm. The size has been confirmed by using transmission electron microscopy. As a part of our strategy, 85% of the 4,4'-bipyridinium salt was synthesized as propionic acid derivative and used to both stabilize the QDs in water and label basic amino acids and different biomarkers utilizing the carboxylic acid functional group. Fifteen percent of the 4,4'-bipyridinium salt was synthesized as N-propyl maleimide and used as a second ligand to label any protein containing the amino acid cysteine by means of a 1,4-Michael addition.     

Preparation of 3-azetidinols with non-bulky 1-alkyl substituents

Cyclization of either the tetrahydropyranyl or trimethylsilyl ether of 1-(alkylamino)-3-chloro-2-propanols 1 followed by cleavage of the azetidinyl ether provides a general method for the preparation of 1-alkyl-3-azetidinols. Unhindered amines provide a more facile preparation of derivatives of 1 , or its ethers, than do hindered amines, while hindered derivatives of 1 undergo more facile ring closure.     

Engineered Biocatalytic Synthesis of β-N-Substituted-α-Amino Acids

Non-canonical amino acids (ncAAs) are useful synthons for the development of new medicines, materials, and probes for bioactivity. Recently, enzyme engineering has been leveraged to produce a suite of highly active enzymes for the synthesis of β-substituted amino acids. However, there are few examples of biocatalytic N-substitution reactions to make α,β-diamino acids. In this study, we used directed evolution to engineer the β-subunit of tryptophan synthase, TrpB, for improved activity with diverse amine nucleophiles. Mechanistic analysis shows that high yields are hindered by product re-entry into the catalytic cycle and subsequent decomposition. Additional equivalents of l -serine can inhibit product reentry through kinetic competition, facilitating preparative scale synthesis. We show β-substitution with a dozen aryl amine nucleophiles, including demonstration on a gram scale. These transformations yield an underexplored class of amino acids that can serve as unique building blocks for chemical biology and medicinal chemistry.     

Not So Innocent After All: Interfacial Chemistry Determines Charge-Transport Efficiency in Single-Molecule Junctions

Most studies in molecular electronics focus on altering the molecular wire backbone to tune the electrical properties of the whole junction. However, it is often overlooked that the chemical structure of the groups anchoring the molecule to the metallic electrodes influences the electronic structure of the whole system and, therefore, its conductance. We synthesised electron-accepting dithienophosphole oxide derivatives and fabricated their single-molecule junctions. We found that the anchor group has a dramatic effect on charge-transport efficiency: in our case, electron-deficient 4-pyridyl contacts suppress conductance, while electron-rich 4-thioanisole termini promote efficient transport. Our calculations show that this is due to minute changes in charge distribution, probed at the electrode interface. Our findings provide a framework for efficient molecular junction design, especially valuable for compounds with strong electron withdrawing/donating backbones.     

Influence of Cyclodextrins on the Kinetics of Oxidation of Amino Acids and BSA by Hydrazyl Radicals

The kinetics of oxidation of amino acids (Arg, His, Lys, Phe, Thr and Tyr), a dipeptide (Gly-His), and BSA (bovine serum albumin) by two persistent water soluble free radicals of the hydrazyl type has been studied.The rate decreases in the order Arg>Lys>Tyr>Thr>HisBSAPheGly-His with bothfree radicals. Addition to the reaction mixture of - and -cyclodextrin decreases the oxidation rate, probably due to amino acidencapsulation in the cyclodextrin cavity. -Cyclodextrin protects more efficiently against oxidation than -cyclodextrin.