Soluble Flavanthrone Derivatives: Synthesis,Characterization, and Application to Organic Light‐Emitting Diodes

Simple modification of benzo[h]benz[5,6]acridino[2,1,9,8‐klmna]acridine‐8,16‐dione, an old and almost‐forgotten vat dye, by reduction of its carbonyl groups and subsequent O‐alkylation, yields solution‐processable, electroactive, conjugated compounds of the periazaacene type, suitable for the use in organic electronics. Their electrochemically determined ionization potential and electron affinity of about 5.2 and ?3.2 eV, respectively, are essentially independent of the length of the alkoxyl substituent and in good agreement with DFT calculations. The crystal structure of 8,16‐dioctyloxybenzo[h]benz[5,6]acridino[2,1,9,8‐klmna]acridine ( FC‐8 ), the most promising compound, was solved. It crystallizes in space group P and forms π‐stacked columns held together in the 3D structure by dispersion forces, mainly between interdigitated alkyl chains. Molecules of FC‐8 have a strong tendency to self‐organize in monolayers deposited on a highly oriented pyrolytic graphite surface, as observed by STM. 8,16‐Dialkoxybenzo[h]benz[5,6]acridino[2,1,9,8‐klmna]acridines are highly luminescent, and all have photoluminescence quantum yields of about 80 %. They show efficient electroluminescence, and can be used as guest molecules with a 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl host in guest/host‐type organic light‐emitting diodes. The best fabricated diodes showed a luminance of about 1900 cd m^?12, a luminance efficiency of about 3 cd A^?1, and external quantum efficiencies exceeding 0.9 %.     

Sub‐Picosecond Singlet Exciton Fission in Cyano‐Substituted Diaryltetracenes

Thin films of 5,11‐dicyano‐6,12‐diphenyltetracene ( TcCN ) have been studied for their ability to undergo singlet exciton fission (SF). Functionalization of tetracene with cyano substituents yields a more stable chromophore with favorable energetics for exoergic SF (2E(T₁)?E(S₁)=?0.17 eV), where S₁ and T₁ are singlet and triplet excitons, respectively. As a result of tuning the triplet‐state energy, SF is faster in TcCN relative to the corresponding endoergic process in tetracene. SF proceeds with two time constants in the film samples (τ=0.8±0.2 ps and τ=23±3 ps), which is attributed to structural disorder within the film giving rise to one population with a favorable interchromophore geometry, which undergoes rapid SF, and a second population in which the initially formed singlet exciton must diffuse to a site at which this favorable geometry exists. A triplet yield analysis using transient absorption spectra indicates the formation of 1.6±0.3 triplets per initial excited state.     

Structural and electronic evolution of Cr2O3 on compression to 55 GPa

Synchrotron single-crystal x-ray diffraction experiments have been performed on corundum-type Cr₂O₃ up to a pressure of 55 GPa in Ne and He pressure transmitting media. Diffraction experiments were complemented by measurements of optical absorption spectra with single crystal samples up to 60 GPa. Results of the diffraction data analysis rule out the earlier reported monoclinic distortion at 15–30 GPa, but indicate evidence of two discontinuous transitions of electronic or magnetic nature, most likely associated with a change in magnetic ordering and charge transfer. The compression mechanism established from single crystal refinements indicates much smaller distortion of the Cr³⁺ coordination environment than was previously assumed.     

Multiplexed Immunosensing Platform Coupled to Hybridization Chain Reaction for Electrochemical Determination of MicroRNAs in Clinical Samples

There is an urgent need for development of rapid and inexpensive techniques for detection of microRNAs (miRNAs), which are potential biomarkers of various types of cancer. In this paper, we describe a multiplexed electrochemical platform for determination of three cancer‐relevant miRNAs: miR‐21, let‐7a and miR‐31. The strategy combines the use of magnetic beads (MBs) modified with a commercial antibody for the efficient capture of the heteroduplexes formed by hybridization of the target miRNA with DNA probe. Free non‐hybridized region of the DNA probe was thereafter hybridized with two biotin‐labeled auxiliary DNA probes in a process of hybridization chain reaction (HCR), resulting in a long hybrid bearing a large number of biotin molecules. Labeling of these multiple biotin units with streptavidin‐peroxidase conjugates allowed an amplification of the amperometric signal measured after capturing the modified MBs at a screen‐printed carbon electrode array of eight electrodes. The combined strategy demonstrated in a similar assay time significantly higher sensitivity than those previously described using modified MBs with the same capture antibody (without amplification by HCR) or a HCR strategy implemented on the surface of MBs, respectively. The methodology exhibits a good selectivity for discriminating single mismatches and was applied to the determination of the three target miRNAs in total RNA (RNA_t) extracted from various cancer cell lines and from cervical precancerous lesions.     

Crystal structure and mesogenic behaviour of a new fluorene derivative: 9,9‐dimethyl‐2,7‐bis(4‐pentylphenyl)‐9H‐fluorene

The title compound, C₃₇H₄₂, is a new mesogenic compound containing the fluorene moiety. It exhibits enantiotropic nematic liquid crystalline behaviour with melting at 125 °C and isotropization at 175 °C. The crystallographically independent unit contains two molecules oriented face‐to‐edge with respect to each other. The two molecules have nearly the same conformation of the bis‐phenyl fluorene moiety. The molecular packing in the crystal phase is nematic‐like.     

Electrochemical analysis of nucleic acids as potential cancer biomarkers

In recent years, a huge progress has been made regarding the development of electrochemical (EC) assays for detection of nucleic acids — DNA or RNA — as potential cancer biomarkers. Various ingenious strategies for determination of DNA methylation of gene promoters, circulating tumor DNAs, viral nucleic acids, or short noncoding microRNAs were presented, many of them showing remarkable sensitivities. However, a majority of these assays were not applied into clinical samples from patients, which is crucial should the electrochemistry compete with conventional, routinely used techniques. In this review, we critically evaluate strengths and weaknesses of EC assays that recognized this necessity and successfully determined endogenous DNA or RNA in patient samples with various forms of tumors.     

Multipoint laser Doppler vibrometry using holographic optical elements and a CMOS digital camera

A laser Doppler vibrometer (LDV) is described in which holographic optical elements are used to provide the interferometer reference and object illumination beams. A complementary metal-oxide semiconductor camera, incorporating a digital signal processor, is used to carry out real-time signal processing of the interferometer output to allow multipoint LDV to be implemented.     

Cationic copolymerization of tetrahydrofuran with ethylene oxide in the presence of diols: Composition,microstructure, and properties of copolymers

Cationic copolymerization of tetrahydrofuran (THF) with ethylene oxide (EO) in the presence of diols leads to dihydroxy terminated telechelic copolymers. In the present article the influence of copolymerization conditions on the copolymer structure was studied in view of conclusions derived from studies of copolymerization kinetics and mechanism. It was shown that according to established copolymerization mechanism, the number average molecular weights increase linearly with conversion up to M_n ≅ 2500, hydroxyl end groups are bound exclusively to EO units and copolymers are composed of [EO]–[THF]_y segments. Microstructure of copolymers may be to some extent regulated by changing reaction conditions. Some physical properties of copolymers also were studied. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3455–3463, 1999     

Polyethers containing stable ionic end-groups

Polyethers of low and medium molecular weight containing at both ends stable ionic groups (phosphonium ions) were obtained by living cationic polymerization of tetrahydrofuran initiated by difunctional initiator, trifluoromethanesulfonic anhydride, followed by termination with triphenylphosphine. It was shown, that products contain significant quantities of low molecular weight diphosphonium salt; a plausible explanation is presented. Alternative approach to the synthesis of diionically terminated polyethers was based on the conversion of hydroxyl end-groups of polyether diols, which can be obtained by cationic Activated Monomer (AM) polymerization of e.g. oxiranes, into phosphonium ion end-groups. Using this approach, poly(ethylene oxide)'s with M_n ranging from 300 to 3400, terminated at both ends with stable ionic groups, were prepared and characterized. Measurements of NMR relaxation times and viscosity measurements provide the evidence for the aggregation of ionic end-groups. The potential applications of inter- and intramolecular aggregation are discussed. It is shown, that intramolecular aggregation of ionic terminal groups in low molecular weight poly(ethylene oxide) leads to cyclic structures resembling crown ethers and showing comparable efficiency for complexing cations.