Light‐activated ruthenium polypyridyl anticancer prodrugs often suffer from poor water solubility, poor selectivity, and/or ill‐defined intracellular targets. Coordination of the d ‐ or l ‐glucose thioether ligand 3 (2‐(2‐(2‐(methylthio)ethoxy)ethoxy)ethyl‐β‐glucopyranoside) to the highly lipophilic ruthenium complex [Ru(tpy)(dppn)(H2O)]2+ ([ 1 ]2+; dppn=benzo[i]dipyrido‐[3,2‐a:2′,3′‐c]phenazine, tpy=2,2′:6′,2′′‐terpyridine) solved all these problems at once. The two enantiomers of [Ru(tpy)(dppn)( 3) ][PF6]2, [d ‐ 2 ][PF6]2 and [l ‐ 2 ][PF6]2, were soluble in water, which allowed the influence of the chirality of the glucose moiety on uptake, toxicity, and intracellular localization of the prodrug to be probed without changing any other physicochemical properties. Both compounds showed mild, but different, cytotoxicity in A549 (human lung carcinoma) and MCF‐7 (human breast adenocarcinoma) cancer cells in the dark, whereas following low doses of visible light irradiation (3.1 J cm?2 at λ = 454 nm), a similar, but high cytotoxicity (EC50 < 1 μm ), was observed. Irrespective of the chirality, both slightly emissive Ru complexes were found in the mitochondria, and two modes of action may contribute to light‐induced cell death: 1) the glucose thioether ligand is photosubstituted by water, thus [ 1 ]2+, which interacts with DNA at an exceptionally high 400:1 base pair/Ru ratio, is released; 2) both [ 1 ]2+ and [ 2 ]2+ produce massive amounts of singlet oxygen, which leads to very efficient photodynamic DNA cleavage. 相似文献
Three thiadiazoloquinoxaline‐containing long pyrene‐fused N‐heteroacenes with 8, 13, and 18 rings were designed and synthesized. They show high electron affinities (EAs) of approximately 4.1 eV, which were derived from the onset of the reduction peaks in cyclic voltammetry. Crystal structure analysis revealed in‐plane extension through close contacts between thiadiazole units as well as layered packing, enabling in‐plane and interlayer electron transport. Organic field‐effect transistor devices provided electron mobilities, which suggest a potential way to enhance the charge transport in long N‐heteroacenes. 相似文献
A novel cross‐linkable electron‐transport material has been designed and synthesized for use in the fabrication of solution‐processed OLEDs. The material exhibits a low LUMO level of ?3.51 eV, a high electron mobility of 1.5×10?5 cm2 V?1 s?1, and excellent stability. An average 9.3 % shrinkage in film thickness was observed for the film after thermal curing. A maximum external quantum efficiency (EQE) of 15.6 % (35.0 cd A?1) was achieved for blue‐phosphorescent OLEDs by spin‐coating and 13.8 % (31.0 cd A?1) for an ink‐jet‐printed device, both of which are better than the EQE of a control device prepared by vacuum‐deposition (see figure). 相似文献
Exciton migration! Spectroscopic analyses and extensive molecular dynamics studies revealed a well‐defined 41 helix in which the perylene molecules (see figure) form four “helter‐skelter‐like” overlapping pathways along which excitons and electrons can rapidly migrate.
Gas‐Phase Equilibria of Quaternary Bismuth Selenium Oxidechlorides The existence of new compounds Bi4O4SeCl2, Bi10O12SeCl4, and Bi22O28SeCl8 in the pseudoternary area Bi2O3/Bi2Se3/BiCl3 has been established by solid state and chemical vapour transport reactions. Furthermore, heterogeneous equilibria between solid state and vapour phase have been studied by mass‐spectrometric measurements. The novel gas‐molecule BiSeCl has been detected. The results of ab initio calculations for structure and refining of thermochemistry of this molecule are given: (Bi–Se) = 2,44 Å; (Bi–Cl) = 2,49 Å; (Se–Bi–Cl) = 106,0°; Thermodynamics: δH°B,298 (BiSeClg) = 6,0 kcal/mol; S°298 (BiSeClg) = 75,8 cal/mol K; Cp (BiSeClg) = 13,583 + 0,64 · 10–3 · T – 0,41 · 105 · T–2 – 0,35 · 10–6 · T2 cal/mol K. Finally, the composition of the gaseous phase has been calculated and estimations about chemical vapour transport were carried out by thermodynamic modelling. 相似文献
A series of self‐complementary ureido pyrimidinedione (UPy) derivatives modified with different aurophilic anchoring groups were synthesized. Their electron transport properties through the quadruple hydrogen bonds in apolar solvent were probed employing the scanning tunneling microscopy break junction (STMBJ) technique. The molecule terminated with a thiol shows the optimal electron transport properties, with a statistical conductance value that approaches 10?3 G0. The 1H NMR spectra and control experiments verify the formation of quadruple hydrogen bonds, which can be effectively modulated by the polarity of the solvent environment. These findings provide a new design strategy for supramolecular circuit elements in molecular electronics. 相似文献
The present review focuses on the recent progress made in thin film orientation of semi‐conducting polymers with particular emphasis on methods using epitaxy and shear forces. The main results reported in this review deal with regioregular poly(3‐alkylthiophene)s and poly(dialkylfluorenes). Correlations existing between processing conditions, macromolecular parameters and the resulting structures formed in thin films are underlined. It is shown that epitaxial orientation of semi‐conducting polymers can generate a large palette of semi‐crystalline and nanostructured morphologies by a subtle choice of the orienting substrates and growth conditions.
This review article focuses on the structures and properties of novel hybrid nanocarbon materials, which are created by incorporating atoms and molecules into the hollow spaces of carbon nanotubes (CNTs); thus they are called nanopeapods. After dealing with synthesis procedures, we discuss the structures and electronic properties of the hybrid materials based on high‐resolution transmission electron microscopy (HRTEM), electron energy‐loss spectroscopy (EELS), X‐ray and electron diffraction, scanning tunneling microscopy (STM), and field‐effect transistor transport measurements. Utilization of the low‐dimensional nanosized spaces of CNTs to produce novel low‐dimensional nanocluster, nanowire, and nanotube materials is also discussed. 相似文献
Various mixed liquid crystals containing crown ether‐cholesteryl liquid crystal, benzo‐15‐crown‐5‐COO‐C27H45 (B15C5‐COOCh), with various common cholesteric liquid crystals, e.g., cholesteryl chloride, cholesteryl benzoate and cholesteryl palmitate, were prepared and studied using polarizing microscopy and differential scanning calorimetry. Investigating the concentration effect of B15C5‐COOCh in mixed liquid crystals revealed that the addition of B15C5‐COOCh resulted in wider phase transition temperature ranges of these cholesteryl liquid crystals. The stability of these B15C5‐COOCh/cholesteryl mixed liquid crystals was studied using comprehensive graphic molecular modeling computer programs (Insight II and Discover) to calculate their molecular energy and stability energy. The effect of salts, e.g. Na+, Co3+, Y3+ and La3+, on the transition temperature range of the mixed liquid crystals was also investigated. The crown ether cholesteric liquid crystal B15C5‐COOCh was applied both as a surfactant and an ion transport carrier to transport metal ions through liquid membranes. Cholesteryl benzo‐15‐crown‐5 exhibited distinctive characteristics of a surfactant and the critical micellar concentration (CMC) of the surfactant was investigated by the pyrene fluorescence probe method. Cholesteryl benzo‐15‐crown‐5 was successfully applied as a good ion transport carrier (Ionophore) to transport various metal ions, e.g. Li+, Na+, La3+, Fe3+ and Co3+, through organic liquid membranes. The transport ability of the cholesteryl benzo‐15‐crown‐5 surfactant for these metal ions was in the order: Co3+ ≥ Li+ > Fe3+ > Na+ > La3+. 相似文献
A triphosphaazatriangulene (H3L) was synthesized through an intramolecular triple phospha‐Friedel–Crafts reaction. The H3L triangulene contains three phosphinate groups and an extended π‐conjugated framework, which enables the stimuli‐responsive reversible transformation of [Cu(HL)(DMSO)?(MeOH)]n, a 3D‐MOF that exhibits reversible sorption characteristics, into (H3L?0.5 [Cu2(OH)4?6 H2O] ?4 H2O), a 1D‐columnar assembled proton‐conducting material. The hydrophilic nature of the latter resulted in a proton conductivity of 5.5×10?3 S cm?1 at 95 % relative humidity and 60 °C. 相似文献
An excellent hole-transport material,1,3-diphenyl-5-(9-phenanthryl)-2-pyrazoline(DPPhP)for OLEDs was studied.This compound not only offers hlgh glass transition temperature(Tg=96℃),good film forming ability,and high HOMO energy level,but also displays excellent hole-transport property.The electrlumlnescent device with a simple structure of ITO/DPPhP(60nm)/AIQ(60mm)/LiF(0.8nm)/Al shows an external quantom efficiency as high as 1.6? 相似文献
Increasing the length of N‐heteroacenes or their analogues is highly desirable because such materials could have great potential applications in organic electronics. In this report, the large π‐conjugated N‐heteroquinone 6,10,17,21‐tetra‐((triisopropylsilyl)ethynyl)‐5,7,9,11,16,18,20,22‐octaazanonacene‐8,19‐dione (OANQ) has been synthesized and characterized. The as‐prepared OANQ shows high stability under ambient conditions and has a particularly low LUMO level, which leads to it being a promising candidate for air‐stable n‐type field‐effect transistors (FETs). In fact, FET devices based on OANQ single crystals have been fabricated and an electron mobility of up to 0.2 cm2 V?1 s?1 under ambient conditions is reported. More importantly, no obvious degradation was observed even after one month. Theoretical calculations based on the single crystal are consistent with the measured mobility. 相似文献
The experimental investigation of intermolecular charge transport in π‐conjugated materials is challenging. Herein, we describe the investigation of charge transport through intermolecular and intramolecular paths in single‐molecule and single‐stacking thiophene junctions by the mechanically controllable break junction (MCBJ) technique. We found that the ability for intermolecular charge transport through different single‐stacking junctions was approximately independent of the molecular structure, which contrasts with the strong length dependence of conductance in single‐molecule junctions with the same building blocks, and the dominant charge‐transport path of molecules with two anchors transited from an intramolecular to an intermolecular path when the degree of conjugation increased. An increase in conjugation further led to higher binding probability owing to the variation in binding energies, as supported by DFT calculations. 相似文献