Purkinje imaging system to measure anterior segment scattering in the human eye

We present an instrument based on Purkinje imaging that permits the objective measurement of the amount of scattering associated with the eye's anterior segment, avoiding the contribution from the retina. The experimental system records the fourth Purkinje image, and adequate processing is used to compute a parameter that quantifies the scattering. The method was first tested in an artificial eye and later in normal young eyes wearing customized contact lenses that induced different amounts of scatter. We were able to detect scattering increments, which indicates that this technique may be used as an objective tool to quantify the level of scattering in the anterior segment of the living human eye. The future use of this technique in clinical environments might help to estimate the level of corneal haze in eyes undergoing refractive surgery or/and scattering within the lens during cataract development.     

Strong Electronic Communication in Linearly Elongated Rylenes Featuring Tunable Bridges

A modified synthetic pathway towards perylene-perylene dimers and a facile purification method to obtain the regioisomerically pure syn- and anti-isomers are reported. In addition, a novel perylene-naphthalene heterodimer with 30 conjugated π-electron pairs was designed and synthesized on the basis of a previously described precursor and the resulting regioisomers were separated from each other. Thereby, the opto-electronic properties of the linearly elongated chromophores could be investigated regarding the differences in length of their aromatic system and the configuration of the isomers. Further tuning of their energy gaps was realized via protonation and methylation of the dibenzimidazole-bridging unit. Extraordinary red-shifts of the absorption maxima of 62 nm for the methylated and 92 nm for the protonated perylene-perylene anti-isomer could be achieved. Moreover, the maxima for the syn-isomer could be shifted bathochromically by 87 and 113 nm, respectively.     

The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

The benzyl radical ( 1 ) is a key intermediate in the combustion and tropospheric oxidation of toluene. Because of its relevance, the reaction of 1 with molecular oxygen was investigated by matrix‐isolation IR and EPR spectroscopy as well as computational methods. The primary reaction product of 1 and O₂ is the benzylperoxyl radical ( 2 ), which exists in several conformers that can easily interconvert even at cryogenic temperatures. Photolysis of radical 2 at 365 nm results in a formal [1,3]‐H migration and subsequent cleavage of the O?O bond to produce a hydrogen‐bonded complex between the hydroxyl radical and benzaldehyde ( 4 ). Prolonged photolysis produces the benzoyl radical ( 5 ) and water, which finally yield the phenyl radical ( 7 ), CO, and H₂O. Thus, via a sequence of exothermic reactions 1 is transformed into radicals of even higher reactivity, such as OH and 7 . Our results have implications for the development of models for the highly complicated process of combustion of aromatic compounds.     

Mono‐ and Bis(pyrrolo)tetrathiafulvalene Derivatives Tethered to C60: Synthesis,Photophysical Studies,and Self‐Assembled Monolayers

A series of mono‐ (MPTTF) and bis(pyrrolo)tetrathiafulvalene (BPTTF) derivatives tethered to one or two C₆₀ moieties was synthesized and characterized. The synthetic strategy for these dumbbell‐shaped compounds was based on a 1,3‐dipolar cycloaddition reaction between aldehyde‐functionalized MPTTF/BPTTF derivatives, two different tailor‐made amino acids, and C₆₀. Electronic communication between the MPTTF/BPTTF units and the C₆₀ moieties was studied by a variety of techniques including cyclic voltammetry and absorption spectroscopy. These solution‐based studies indicated no observable electronic communication between the MPTTF/BPTTF units and the C₆₀ moieties. In addition, femtosecond and nanosecond transient absorption spectroscopy revealed, rather surprisingly, that no charge transfer from the MPTTF/BPTTF units to the C₆₀ moieties takes place on excitation of the fullerene moiety. Finally, it was shown that the MPTTF–C₆₀ and C₆₀–BPTTF‐C₆₀ dyad and triad molecules formed self‐assembled monolayers on a Au(111) surface by anchoring to C₆₀.     

Phase Transition of [2,2]‐Paracyclophane – An End to an Apparently Endless Story

In this contribution, the solid‐state low‐temperature phase structure of [2,2]‐paracyclophane is unambiguously characterised by single‐crystal X‐ray analysis. Additionally, a heat capacity measurement was undertaken, which proves the existence of a λ‐type phase transition at 45 K, a transition that is connected with the formation of a secondary C_p/T feature at 60 K. The low‐temperature phase (<45 K) crystallises in the lower symmetry space group P$\bar 4$ n2, whereas the high‐temperature phase (>60 K) crystallises in space group P4₂/mnm. This proves what has been postulated both by experimental and theoretical chemists but has repeatedly been dismissed as speculation many times.     

Observation of Unusual Molecular Diffusion Behaviour below the Lower Critical Solution Temperature of Water/2‐Butoxyethanol Mixtures by using Fluorescence Correlation Spectroscopy

The effect of solute affinity on solute diffusion in binary liquids well below the lower critical solution temperature (LCST) was studied by using fluorescence correlation spectroscopy. We measured the hydrodynamic radii of a hydrophobic and an amphiphilic fluorescent dye under systematic variation of the relative molar fractions of water/2‐butoxyethanol and, for comparison, of water/methanol mixtures, which do not show phase separation. We found that the apparent hydrodynamic radius of the hydrophobic dye almost doubled in water/2‐butoxyethanol, whereas it remained largely unchanged for the amphiphilic dye and in water/methanol mixtures. Our results indicate that the translational diffusion of solutes is influenced by transient local solution structures, even at temperatures well below the LCST. We conclude that, even far below LCST, different solutes can experience different environments in binary liquid mixtures depending on both the solute and solvent properties, all of which impact their reactivity.     

Symmetry-Breaking Charge-Transfer Chromophore Interactions Supported by Carbon Nanodots

Carbon dots (CDs) and their derivatives are useful platforms for studying electron-donor/acceptor interactions and dynamics therein. Herein, we couple amorphous CDs with phthalocyanines (Pcs) that act as electron donors with a large extended π-surface and intense absorption across the visible range of the solar spectrum. Investigations of the intercomponent interactions by means of steady-state and pump-probe transient absorption spectroscopy reveal symmetry-breaking charge transfer/separation and recombination dynamics within pairs of phthalocyanines. The CDs facilitate the electronic interactions between the phthalocyanines. Thus, our findings suggest that CDs could be used to support electronic couplings in multichromophoric systems and further increase their applicability in organic electronics, photonics, and artificial photosynthesis.     

Non-Oxido-Vanadium(IV) Metalloradical Complexes with Bidentate 1,2-Dithienylethene Ligands: Observation of Reversible Cyclization of the Ligand Scaffold in Solution

Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)₂Cl₂] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P) . This blue complex has two bidentate en-diolato ligands which chelate the V^IV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P) . Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution.     

The Persistent Radical Effect in Organic Synthesis

Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if the radicals have different lifetimes and if they are generated at equal rates, cross‐coupling will become the dominant process. This high cross‐selectivity is based on a kinetic phenomenon called the persistent radical effect (PRE). In this Review, an explanation of the PRE supported by simulations of simple model systems is provided. Radical stabilities are discussed within the context of their lifetimes, and various examples of PRE‐mediated radical–radical couplings in synthesis are summarized. It is shown that the PRE is not restricted to the coupling of a persistent with a transient radical. If one coupling partner is longer‐lived than the other transient radical, the PRE operates and high cross‐selectivity is achieved. This important point expands the scope of PRE‐mediated radical chemistry. The Review is divided into two parts, namely 1) the coupling of persistent or longer‐lived organic radicals and 2) “radical–metal crossover reactions”; here, metal‐centered radical species and more generally longer‐lived transition‐metal complexes that are able to react with radicals are discussed—a field that has flourished recently.