Near-Temperature-Independent Electron Transport Well beyond Expected Quantum Tunneling Range via Bacteriorhodopsin Multilayers.

A key conundrum of biomolecular electronics is efficient electron transport (ETp) through solid-state junctions up to 10 nm, often without temperature activation. Such behavior challenges known charge transport mechanisms, especially via nonconjugated molecules such as proteins. Single-step, coherent quantum-mechanical tunneling proposed for ETp across small protein, 2-3 nm wide junctions, but it is problematic for larger proteins. Here we exploit the ability of bacteriorhodopsin (bR), a well-studied, 4-5 nm long membrane protein, to assemble into well-defined single and multiple bilayers, from ∼9 to 60 nm thick, to investigate ETp limits as a function of junction width. To ensure sufficient signal/noise, we use large area (∼10-3 cm2) Au-protein-Si junctions. Photoemission spectra indicate a wide energy separation between electrode Fermi and the nearest protein-energy levels, as expected for a polymer of mostly saturated components. Junction currents decreased exponentially with increasing junction width, with uniquely low length-decay constants (0.05-0.5 nm-1). Remarkably, even for the widest junctions, currents are nearly temperature-independent, completely so below 160 K. While, among other things, the lack of temperature-dependence excludes, hopping as a plausible mechanism, coherent quantum-mechanical tunneling over 60 nm is physically implausible. The results may be understood if ETp is limited by injection into one of the contacts, followed by more efficient charge propagation across the protein. Still, the electrostatics of the protein films further limit the number of charge carriers injected into the protein film. How electron transport across dozens of nanometers of protein layers is more efficient than injection defines a riddle, requiring further study.

Retinal-Carotenoid Interactions in a Sodium-Ion-Pumping Rhodopsin: Implications on Oligomerization and Thermal Stability.

Microbial rhodopsin (also called retinal protein)-carotenoid conjugates represent a unique class of light-harvesting (LH) complexes, but their specific interactions and LH properties are not completely elucidated as only few rhodopsins are known to bind carotenoids. Here, we report a natural sodium-ion (Na+)-pumping Nonlabens (Donghaeana) dokdonensis rhodopsin (DDR2) binding with a carotenoid salinixanthin (Sal) to form a thermally stable rhodopsin-carotenoid complex. Different spectroscopic studies were employed to monitor the retinal-carotenoid interaction as well as the thermal stability of the protein, while size-exclusion chromatography (SEC) and homology modeling are performed to understand the protein oligomerization process. In analogy with that of another Na+-pumping protein Krokinobacter eikastus rhodopsin 2 (KR2), we propose that DDR2 (studied concentration range: 2 × 10-6 to 4 × 10-5 M) remains mainly as a pentamer at room temperature and neutral pH, while heating above 55 °C partially converted it into a thermally less stable oligomeric form of the protein. This process is affected by both the pH and concentration. At high concentrations (4 × 10-5 to 2 × 10-4 M), the protein adopts a pentamer form reflected in the excitonic circular dichroism (CD) spectrum. In the presence of Sal, the thermal stability of DDR2 is increased significantly, and the pigment is stable even at 85 °C. The results presented could have implications in designing stable rhodopsin-carotenoid antenna complexes.

Detailed Photophysical Studies of Poly(9,9-di-(2-ethylhexyl)-9-H-fluorene-2,7-vinylene) in Liquid Media and Thin Films.

For the present work, solvent (toluene, o-xylene, chloroform, chlorobenzene, and 1,2-dichloroethane) and concentration-dependent (∼10-6-10-3 g ml-1) photophysical properties of poly(9,9-di-(2-ethylhexyl)-9-H-fluorene-2,7-vinylene) (PEFV) were investigated in detail in liquid media as well as thin films. Also, temperature-dependent (3-60 oC) fluorescence emission measurements of PEFV were conducted in liquid media. The steady-state and time-resolved data indicate the existence of weak interchain interaction in liquid media at high concentration. However, both ground-state aggregation and interchain interaction are present for PEFV in thin film. The interchain interaction plays a dominant role on the fluorescence emission of PEFV in thin film on the red side of the spectra.

Organophotoredox-Catalyzed Direct C-H Amination of 2H-Indazoles with Amines.

A general and practical method for the direct C-H amination of 2H-indazoles with a series of amines including aliphatic primary amines, secondary amines, azoles, and sulfoximines via organophotoredox-catalyzed oxidative coupling has been disclosed at room temperature under ambient air conditions. Additionally, this protocol is used for free aminated 2H-indazole synthesis. A mechanistic study revealed that a single electron transfer (SET) pathway might be involved in this reaction.

Silicon Quantum Dot-Based Fluorescent Probe: Synthesis Characterization and Recognition of Thiocyanate in Human Blood.

Allylamine-functionalized silicon quantum dots (ASQDs) of high photostability are synthesized by a robust inverse micelle method to use the material as a fluorescent probe for selective recognition of thiocyanate (a biomarker of a smoker and a nonsmoker). The synthesized ASQDs were characterized by absorption, emission, and Fourier transform infrared spectroscopy. Surface morphology is studied by transmission electron microscopy and dynamic light scattering. The synthesized material exhibits desirable fluorescence behavior with a high quantum yield. A selective and accurate (up to 10-10 M) method of sensing of thiocyanate anion is developed based on fluorescence amplification and quenching of ASQDs. The sensing mechanism is investigated and interpreted with a crystal clear mechanistic approach through the modified Stern-Volmer plot. The developed material and the method is applied to recognize the anion in the human blood sample for identification of the degree of smoking. The material deserves high potentiality in the field of bio-medical science.

Detail Photophysical Studies of Sulfonated Polyaniline in Aqueous Medium.

Sulfonated polyaniline (SPANI) has emerged as a promising polymer in the past few decades due to its solubility in water and relatively moderate conductivity. However, to date, literature data on the optical characterization of SPANI are very limited and preliminary in nature. In the present work, SPANI is synthesized by direct sulfonation of emeraldine salt form of polyaniline with chlorosulfonic acid in an inert solvent. Detail photophysical properties of SPANI are investigated in aqueous medium by using steady state (concentration, temperature, pH, and excitation wavelength dependence) and time-resolved spectroscopic techniques. The steady state fluorescence emission measurements are carried out carefully to avoid inner filter effect (especially secondary inner filter effect or reabsorption effect) as well as scattering. Two ground state conformations of SPANI are suggested to exist in aqueous medium. Excitation wavelength dependence of the fluorescence emission spectra is attributed to red-edge effect. All these observations are nicely corroborated by the fluorescence lifetime data of SPANI obtained from time-resolved measurements. All these new findings are extremely important in view of the potential applications of SPANI in polymer optoelectronics.

Ground state charge transfer complex formation of some metalloporphyrins with aromatic solvents: Further theoretical and experimental investigations.

In our earlier work (Chem. Phys. Letts. 592 (2014) 149-154), a new broad band was observed in the near infrared region (700-900nm) of the steady state absorption spectra of some metalloporphyrins (zinc tetraphenylporphyrin, zinc octaethylporphyrin and magnesium octaethylporphyrin) in aromatic solvents (chlorobenzene, 1,2-dichlorobenzene, benzonitrile, benzene and toluene) at high concentrations (~10-4molL-1). The band was ascribed to be due to ground state charge transfer complexation between solute and solvent molecules. In the present work, density functional theory calculations are carried out to study the possibility of such ground state charge transfer complex formation between zinc tetraphenylporphyrin and four aromatic solvents viz., benzene, toluene, chlorobenzene and benzonitrile with 1:1 and 2:1 solvent-solute stoichiometries. Also, we determined the association constants for the ground state charge transfer complex formation of zinc tetraphenylporphyrin and zinc octaethylporphyrin with two aromatic solvents (benzene and benzonitrile) by Benesi-Hildebrand method.

Visualization Based Data Mining for Comparison Between Two Solar Cell Libraries.

Material informatics may provide meaningful insights and powerful predictions for the development of new and efficient Metal Oxide (MO) based solar cells. The main objective of this paper is to establish the usefulness of data reduction and visualization methods for analyzing data sets emerging from multiple all-MOs solar cell libraries. For this purpose, two libraries, TiO2 |Co3 O4 and TiO2 |Co3 O4 |MoO3 , differing only by the presence of a MoO3 layer in the latter were analyzed with Principal Component Analysis and Self-Organizing Maps. Both analyses suggest that the addition of the MoO3 layer to the TiO2 |Co3 O4 library has affected the overall photovoltaic (PV) activity profile of the solar cells making the two libraries clearly distinguishable from one another. Furthermore, while MoO3 had an overall favorable effect on PV parameters, a sub-population of cells was identified which were either indifferent to its presence or even demonstrated a reduction in several parameters.

Putting DFT to the test: a first-principles study of electronic, magnetic, and optical properties of Co3O4.

First-principles density functional theory (DFT) and a many-body Green's function method have been employed to elucidate the electronic, magnetic, and photonic properties of a spinel compound, Co3O4. Co3O4 is an antiferromagnetic semiconductor composed of cobalt ions in the Co(2+) and Co(3+) oxidation states. Co3O4 is believed to be a strongly correlated material, where the on-site Coulomb interaction (U) on Co d orbitals is presumably important, although this view has recently been contested. The suggested optical band gap for this material ranges from 0.8 to 2.0 eV, depending on the type of experiments and theoretical treatment. Thus, the correlated nature of the Co d orbitals in Co3O4 and the extent of the band gap are still under debate, raising questions regarding the ability of DFT to correctly treat the electronic structure in this material. To resolve the above controversies, we have employed a range of theoretical methods, including pure DFT, DFT+U, and a range-separated exchange-correlation functional (HSE06) as well as many-body Green's function theory (i.e., the GW method). We compare the electronic structure and band gap of Co3O4 with available photoemission spectroscopy and optical band gap data and confirm a direct band gap of ca. 0.8 eV. Furthermore, we have also studied the optical properties of Co3O4 by calculating the imaginary part of the dielectric function (Im(ε)), facilitating direct comparison with the measured optical absorption spectra. Finally, we have calculated the nearest-neighbor interaction (J1) between Co(2+) ions to understand the complex magnetic structure of Co3O4.