A new enabling technology for convenient laboratory scale continuous flow processing at low temperatures

A new machine for conducting continuous flow processes at low temperatures on a laboratory scale is reported. The use of this cryogenic flow reactor has been demonstrated by the preparation of a variety of (hetero)aromatic boronic acids and esters via lithium halogen exchange chemistry. Furthermore, scale-up of the reaction conditions not only demonstrates the application of this device for the preparation of useful building blocks but also combines the ability to process n-butyllithium directly through pump heads attached to the unit.     

Controlling the properties of self-assembled monolayers by substrate curvature

Properties of self-assembled monolayers (SAMs) can be tailored by the curvature of the underlying surface. This is so because on a curved support the density of SAM headgroups is always smaller than that of the surface-attachment sites. This density difference increases with increasing curvature and is most pronounced for SAMs formed on nanoscopic particles. This Perspective describes systems in which nanoscale curvature causes pronounced changes in the pK(a) of acid-presenting SAMs or in the electrochemical potential of redox-active molecules (including supramolecular "switches") attached to nanoparticles. It is suggested that in nanoparticles having regions of different curvature these geometrical differences can translate into site-selective charging; such "patchy" particles could be used as building blocks of pH-sensitive assemblies.     

One-Pot Functionalization of Graphene with Porphyrin through Cycloaddition Reactions

Two types of graphene‐based hybrid materials, graphene‐TPP (TPP=tetraphenylporphyrin) and graphene‐PdTPP (PdTPP=palladium tetraphenylporphyrin), were prepared directly from pristine graphene through one‐pot cycloaddition reactions. The hybrid materials were characterized by thermogravimetric analysis (TGA), by TEM, by UV/Vis, FTIR, Raman, and luminescence spectroscopy, and by fluorescence/phosphorescence lifetime measurements. The presence of the covalent linkages between graphene and porphyrin was confirmed by FTIR and Raman spectroscopy and further supported by control experiments. The presence of TPP (or PdTPP) in the hybrid material was demonstrated by UV/Vis spectroscopy, with TGA results indicating that the graphene‐TPP and graphene‐PdTPP hybrid materials contained approximately 18 % TPP and 20 % PdTPP. The quenching of fluorescence (or phosphorescence) and reduced lifetimes suggest excited state energy/electron transfer between graphene and the covalently attached TPP (or PdTPP) molecules.     

Application of circular dichroism spectroscopy in the study of mixed-valence asymmetric ruthenium polypyridyl complexes

Circular dichroism (CD) spectroelectrochemistry is used to determine the extent of singly occupied molecular orbital delocalization in mixed-valence multinuclear complexes, specifically the mixed-valence Ru(II)Ru(III) states of the four diastereoisomers of [(Ru(bpy)(2))(2)(bpt)](3+) [1; bpy = 2,2'-bipyridyl and bpt = 3,5-bis(pyrid-2'-yl)-1,2,4-triazolato anion]. The complex was found to be stable to thermal racemization in the three oxidation states, but photoracemization in the Ru(II)Ru(II) state was observed.     

How good must single photon sources and detectors be for efficient linear optical quantum computation?

We present a scheme for linear optical quantum computation that is highly robust to imperfect single photon sources and inefficient detectors. In particular we show that if the product of the detector efficiency with the source efficiency is greater than 2/3, then efficient linear optical quantum computation is possible. This high threshold is achieved within the cluster state paradigm for quantum computation.