Shedding Light on Highly Emissive 1,4-Dihydropyrrolo[3,2-b]pyrrole Derivatives: Synthesis and Aggregate-Dependent Emission.

Three tetraaryl-1,4-dihydropyrrolo[3,2-b]pyrrole derivatives containing different number of long alkoxy chains (2, 4 and 6) were synthesized, characterized and applied in Organic Light Emitting Diodes (OLEDs). The compounds showed good emission properties with Photoluminescence Quantum Yields (PLQYs) higher than 80 % in solution and 50 % in solid state (thin film). The solvatochromism results revealed a pronounced vibronic emission in methylcyclohexane and toluene, characterized by two distinct sharp emission peaks and a small redshift in the following order: methylcyclohexane>toluene>dichloromethane>tetrahydrofuran>acetonitrile. Also, the compounds formed aggregates with redshifted emission, which can be attributed to excimer formation. This phenomenon was observed in solutions containing 90 % water and with the concentration variation in methylcyclohexane (MCH). Compounds with a greater number of peripheral chains showed the capacity to keep hexagonal columnar organization in films after fast cooling from liquid state. OLEDs fabricated with these compounds showed turn-on voltages lower than 4.0 V, with luminance higher than 1400 cd m-2 , electroluminescence spectra with Full Width at Half Maximum lower than 70 nm and maximum External Quantum Efficiency between 7.2 % and 4.3 %. Overall, this shows that the 1,4-dihydropyrrolo[3,2-b]pyrrole moiety is promising for applications where luminescence is paramount, as in organic light-emitting devices.

Methyl Ester Functionalized Phenalenyl Arene- and Bipyridine-Ruthenium-Based Complexes for Electroactive Langmuir-Blodgett Films.

We report the synthesis of a new phenalenyl ligand, functionalized with a methyl ester electron withdrawing group, named 9-hydroxy-1-oxo-1 H-phenalen-5-methyl carboxylate (L), and the generated complexes [Ru(bpy)2L]PF6 and [(η6-C6H6)Ru(L)Cl]. Compounds were characterized by spectroscopic and X-ray diffraction methods, and their electrochemical behavior was investigated via cyclic voltammetry and UV-vis spectroelectrochemistry. The one-electron oxidized compounds have an unpaired electron located in the phenalenyl ring, as supported by theoretical calculations (DFT) and EPR results. Langmuir-Blodgett (LB) films deposited by [Ru(bpy)2L]2+/3+ species mixed with stearic acid are electroactive, showing a quasi-reversible wave with E1/2Film1 = 0.74 V and E1/2Film2 = 0.81, which are promising systems that allow access to immobilized open-shell species in the film.

Cytotoxicity of η6-areneruthenium-based molecules to glioblastoma cells and their recognition by multidrug ABC transporters.

A new series of amphiphilic η6-areneruthenium(II) compounds containing phenylazo ligands (group I: compounds 1a, 1b, 2a and 2b) and phenyloxadiazole ligands (group II: compounds 3a, 3b, 4a and 4b) were synthesized and characterized for their anti-glioblastoma activity. The effects of the amphiphilic η6-areneruthenium(II) complexes on the viability of three human glioblastoma cell lines, U251, U87MG and T98G, were evaluated. The azo-derivative ruthenium complexes (group I) showed high cytotoxicity to all cell lines, whilst most oxadiazole-derivative complexes (group II) were less cytotoxic, except for compound 4a. The cationic complexes 2a, 2b and 4b were more cytotoxic than the neutral complexes. Compounds 2a and 2b caused a significant reduction in the percentage of cells in the G0/G1 phase, with concomitant increases in the G2/M phase and fragmented DNA in the T98G cell line. The η6-areneruthenium(II) compounds were also tested in cell lines that overexpress the multidrug ABC transporters P-gp, MRP1 and ABCG2. Compounds 2b and 4a were substrates for the P-gp protein, with resistance indexes of 8.6 and 1.9, respectively. Compound 2b was also a substrate for ABCG2 and MRP1 proteins, with lower resistance indexes (1.8 and 1.6, respectively). The contribution of multidrug ABC transporters to the cytotoxicity of compound 2b in T98G cells was evidenced, since verapamil (a characteristic inhibitor of MRP1) increased the cytotoxicity of compound 2b at concentrations up to 20 µmol L-1, whilst GF120918 and Ko143 (specific inhibitors of P-gp and ABCG2, respectively) had no significant effect. In addition, we showed that compound 2b interacts with glutathione (GSH), which could explain its cellular efflux by MRP1. Our results showed that the amphiphilic η6-areneruthenium(II) complexes are promising anti-glioblastoma compounds, especially compound 2b, which was cytotoxic for all three cell lines, although it is transported by the three main multidrug ABC transporters.

Polar Order and Symmetry Breaking at the Boundary between Bent-Core and Rodlike Molecular Forms: When 4-Cyanoresorcinol Meets the Carbosilane End Group.

Two isomeric achiral bent-core liquid crystals involving a 4-cyanoresorcinol core and containing a carbosilane unit as nanosegregating segment were synthesized and were shown to form ferroelectric liquid-crystalline phases. Inversion of the direction of one of the COO groups in these molecules leads to a distinct distribution of the electrostatic potential along the surface of the molecule and to a strong change of the molecular dipole moments. Thus, a distinct degree of segregation of the carbosilane units and consequent modification of the phase structure and coherence length of polar order result. For the compound with larger dipole moment (CN1) segregation of the carbosilane units is suppressed, and this compound forms paraelectric SmA and SmC phases; polar order is only achieved after transition to a new LC phase, namely, the ferroelectric leaning phase (SmCLs PS ) with the unique feature that tilt direction and polar direction coincide. The isomeric compound CN2 with a smaller dipole moment forms separate layers of the carbosilane groups and shows a randomized polar SmA phase (SmAPAR ) and ferroelectric polydomain SmCs PS phases with orthogonal combination of tilt and polar direction and much higher polarizations. Thus, surprisingly, the compound with the smaller molecular dipole moment shows increased polar order in the LC phases. Besides ferroelectricity, mirror-symmetry breaking with formation of a conglomerate of macroscopic chiral domains was observed in one of the SmC phases of CN1. These investigations contribute to the general understanding of the development of polar order and chirality in soft matter.

Leaning-type polar smectic-C phase in a freely suspended bent-core liquid crystal film.

A rich variety of responsive behavior occurs in complex structured fluids due to their lower symmetries. On the other hand, fluid disorder tends to increase the symmetry of liquid crystal mesophases. Here, we report direct evidence for the existence of a mesophase with CS symmetry. The observations are based on optical studies of director inversion walls in freely suspended films in electric fields under obliquely incident light. This phase is distinguished by the polarization lying in the molecular tilt plane in freely suspended films. Such a low-symmetry polar fluid phase has been long predicted to occur in bent-core liquid crystals. The stability of this phase is attributed to the bent shape of the mesogens and dominating dispersion interactions.

A label-free electrochemical immunosensor based on an ionic organic molecule and chitosan-stabilized gold nanoparticles for the detection of cardiac troponin T.

A label-free electrochemical immunosensor based on an ionic organic molecule ((E)-4-[(4-decyloxyphenyl)diazenyl]-1-methylpyridinium iodide) and chitosan-stabilized gold nanoparticles (CTS-AuNPs) was developed for the detection of cardiac troponin T (cTnT). The new ionic organic molecule was strategically employed as a redox probe, and CTS-AuNPs were applied as a "green" platform for the immobilization of the monoclonal anti-cTnT antibody, for the construction of the immunosensor. The characterization of the proposed immunosensor was carried out by employing cyclic and square-wave voltammetry and electron microscopy. The film of ionic organic molecules acts as a redox probe and from its electrochemical response the presence of cTnT antigens, which interact specifically with the anti-cTnT antibody immobilized on the surface of the immunosensor, can be detected. This interaction results in a decrease in the analytical signal, which is proportional to the amount of cTnT antigens present in the sample analyzed. Under optimized conditions, using square-wave voltammetry (a frequency of 100 Hz, an amplitude of 100 mV and an increment of 8 mV) and an incubation time of 10 min, the proposed immunosensor showed linearity in the range of 0.20 to 1.00 ng mL(-1) cTnT, with a calculated limit of detection of 0.10 ng mL(-1). The proposed immunosensor shows some advantages when compared to other sensors reported in the literature, especially with regard to the detection limit and the time of incubation. A study of the interday precision (n = 8) showed a coefficient of variation of 3.33%. The potential interference of some compounds (glucose, ascorbic acid, albumin, uric acid, creatine, and creatinine) on the response of the immunosensor was evaluated and the inhibition of the immunosensor response was found to be less than 8.0%. The immunosensor was successfully used for the determination of cTnT in samples of simulated blood serum with a relative error of <13.0%. Furthermore, the proposed methodology provides a working range that allows the detection of cTnT antigens at levels below the cutoff value used for the diagnosis of acute myocardial infarction and was also found to be faster than the conventional methods.

Troponin T immunosensor based on liquid crystal and silsesquioxane-supported gold nanoparticles.

A nanostructured immunosensor based on the liquid crystal (E)-1-decyl-4-[(4-decyloxyphenyl)diazenyl]pyridinium bromide (Br-Py) and gold nanoparticles supported by the water-soluble hybrid material 3-n-propyl-4-picolinium silsesquioxane chloride (AuNP-Si4Pic(+)Cl(-)) was built for the detection of troponin T (cTnT), a cardiac marker for acute myocardial infarction (AMI). The functionalized nanostructured surface was used to bind anti-cTnT monoclonal antibodies through electrostatic interaction. The immunosensor (ab-cTnT/AuNP-Si4Pic(+)Cl(-)/Br-Py/GCE) surface was characterized by microscopy techniques. The electrochemical behavior of the immunosensor was studied by cyclic voltammetry and electrochemical impedance spectroscopy. A calibration curve was obtained by square-wave voltammetry. The immnunosensor provided a limit of detection of 0.076 ng mL(-1) and a linear range between 0.1 and 0.9 ng mL(-1) (appropriate for AMI diagnosis).

Liquid crystal and gold nanoparticles applied to electrochemical immunosensor for cardiac biomarker.

A label-free electrochemical immunosensor based on the ionic liquid crystal (E)-1-decyl-4-[(4-decyloxyphenyl)diazenyl]pyridinium bromide (Br-Py) coated on a glassy carbon electrode (GCE) for the quantitative detection of myoglobin (Mb), a cardiac marker for acute myocardial infarction, is reported herein for the first time. The monoclonal anti-myoglobin antibody (ab-Mb) was covalently immobilized using glyoxal on a film of polyethyleneimine-coated gold nanoparticles (AuNP-PEI). The proposed method for Mb detection is based on voltammetric suppression of the Br-Py signal when the immunosensor was incubated with Mb antigen. The electrochemical performance of the Mb immunosensor was studied by electrochemical impedance spectroscopy, and cyclic and square-wave voltammetry. Under the optimal conditions, the proposed immunosensor shows a good linear relationship between the electrochemical inhibition response and the concentration of Mb over the range of 9.96-72.8 ng mL(-1) with a detection limit of 6.29 ng mL(-1). The results obtained indicate that the proposed immunosensor provides good sensitivity and simple operation for detecting acute myocardial infarction with Mb as a biomarker.

Ab initio, density functional theory, and continuum solvation model prediction of the product ratio in the S(N)2 reaction of NO2(-) with CH3CH2Cl and CH3CH2Br in DMSO solution.

The reaction pathways for the interaction of the nitrite ion with ethyl chloride and ethyl bromide in DMSO solution were investigated at the ab initio level of theory, and the solvent effect was included through the polarizable continuum model. The performance of BLYP, GLYP, XLYP, OLYP, PBE0, B3PW91, B3LYP, and X3LYP density functionals has been tested. For the ethyl bromide case, our best ab initio calculations at the CCSD(T)/aug-cc-pVTZ level predicts product ratio of 73% and 27% for nitroethane and ethyl nitrite, respectively, which can be compared with the experimental values of 67% and 33%. This translates to an error in the relative DeltaG* of only 0.17 kcal mol(-1). No functional is accurate (deviation <0.5 kcal mol(-1)) for predicting relative DeltaG*. The hybrid X3LYP functional presents the best performance with deviation 0.82 kcal mol(-1). The present problem should be included in the test set used for the evaluation of new functionals.

Absolute solvation free energy of Li+ and Na+ ions in dimethyl sulfoxide solution: a theoretical ab initio and cluster-continuum model study.

The solvation of the lithium and sodium ions in dimethyl sulfoxide solution was theoretically investigated using ab initio calculations coupled with the hybrid cluster-continuum model, a quasichemical theory of solvation. We have investigated clusters of ions with up to five dimethyl sulfoxide (DMSO) molecules, and the bulk solvent was described by a dielectric continuum model. Our results show that the lithium and sodium ions have four and five DMSO molecules into the first coordination shell, and the calculated solvation free energies are -135.5 and -108.6 kcal mol(-1), respectively. These data suggest a solvation free energy value of -273.2 kcal mol(-1) for the proton in dimethyl sulfoxide solution, a value that is more negative than the present uncertain experimental value. This and previous studies on the solvation of ions in water solution indicate that the tetraphenylarsonium tetraphenylborate assumption is flawed and the absolute value of the free energy of transfer of ions from water to DMSO solution is higher than the present experimental values.