Comparative characteristics of a tryptophan molecule in the gas phase and water

The L and D isomers of the tryptophan (Trp) molecule and the (Trp)⁺ cation in the gas phase and water are calculated at the DFT level to reveal the effect of water considered in the dielectric continuum approximation on the electronic characteristics of the molecule. The distribution of effective atomic charges and bond lengths enables the prediction of the most probable parts of the chemical bond cleavage during the fragmentation of the molecule under the ionizing particle flux. These data are supplemented with a calculation of fragmentation energies. Zwitterionic structures characterized by the appearance of considerable dipole moments and a change in their orientation with respect to the ground state are distinguished among the possible isomeric forms in water.     

Semiconducting covalent organic frameworks: a type of two-dimensional conducting polymers

In recent years,as a new class of two-dimensional polymer,covalent organic frameworks(COFs) have attracted intensive attention and developed rapidly.This review provides an overview of a type of COFs which can be utilized as organic semiconductors.Carefully choosing monomers as the building blocks will bestow different types of semiconducting character on COFs.We summarize the p-type,n-type and ambipolar semiconducting COFs and highlight the effects of π-functional building blocks on the photoconductive behaviors of the semiconducting COFs.     

Copolymer electrosynthesis of ethyl-3-thiophene acetate and 3-methylthiophene and characterization of the resulting copolymers by spectroscopic studies

Copolymers of ethyl-3-thiophene acetate (ETA) and 3-methylthiophene (MT) were synthesized electrochemically. Electrospray ionization mass spectra of the electrolyte containing 2×10^–3 M MT + 3×10^–2 M ETA after copolymerization showed cooligomers with different combination of ETA and MT units. Just one value of the glass transition temperature was observed by differential scanning calorimetry of the formation of homogeneous copolymers. Change of the copolymer composition led to change of thermal stability characterized by thermogravimetric analysis. The morphology of the copolymer film was studied by scanning electron microscopy, indicating a homogeneous and compact film. The electroactivity of the homopolymer/copolymer films was studied. Cyclic voltammograms of the polymer films revealed that poly(ethyl-3-thiophene acetate) possesses high electroactivity in non-aqueous solution, but its electroactivity was lost entirely after 50 cycles in 0.1 M N(Bu)₄PF₆/acetonitrile solution having 5 volume percentage of water; however, the copolymer of ETA and MT maintains its high electroactivity even in the aqueous solution. Similar results were also derived from impedance and photoelectrochemical measurements. Additionally, it was found that a bilayer of poly(3-methylthiophene) and copolymer was formed.     

Modifying transparent electrode with conjugated organic semiconductor hole transport material as interface for enhancing performance of organic solar cell

Indium tin oxide (ITO) is used as a substrate was covered with 4-[4-(4-methoxy-N-naphthalen-2-ylanilino) phenyl] benzoic acid (MNA) as a self-assembled monolayer (SAM). Poly(3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6) C₆₁ (PCBM) were mixed and used as a donor–acceptor in organic solar cell (OSC). The MNA (SAM) layer is used as an interface instead of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS) for hole injection. The HOMO-LUMO energy level of MNA-SAM molecule and the electronic charge distribution were calculated theoretically using Chemissian software. The HOMO-LUMO energy level of the MNA is calculated as E_HOMO = ?5.10 eV and E_LUMO = ?1.60 eV. The OSC modified with MNA showed an efficient performance in the absence of PEDOT: PSS as hole transport layer. The annealing of the ITO/SAM/P3HT: PCBM films at different temperatures are also investigated to study the effect of reducing defects. The interface structures of the organic semiconductor layer on ITO were characterized by Atomic Force Microcopy (AFM). In addition, Kelvin Probe Microscopy (KPM) is used to understand how the annealing changes the surface potential energy of the ITO/SAM substrate. Using the KPM method, which measures the surface potential energy of the films, the energy bands of the ITO were increased to maximum 5.09 eV. The ITO/SAM/P3HT: PCBM film's surface potential was determined to be 0.18 eV after being annealed at 80 °C. The surface potential of the modified films was discovered to be 0.33 V and 0.39 V when the annealing temperature was raised from 80 °C to 120 °C and 160 °C. The maximum device efficiency was demonstrated by the ITO/SAM/P3HT: PCBM film after an hour of annealing at 160 °C.     

Proteins as functional interlayer in organic field-effect transistor

The paper summarizes and discusses the recent advances of proteins as functional interlayers in organic field-effect transistors (OFETs). Specific focus is given on the proteins integrated into the device structure, either to act as dielectric materials or to perform as the functional interlayer between the dielectric and the organic semiconductor (OSC). The main emphasis is give to the location and the specific effect of protein layers in the structure of OFETs. Besides, the possibility of amyloid serving as useful building blocks for OFET is discussed.     

Study of the factors affecting the photoelectrode characteristics of a perylene/phthalocyanine bilayer working in the water phase

Some types of phthalocyanines (MPc (M = H(2), Cu, or Zn), a p-type semiconductor) were used in combination with 3,4,9,10-perylenetetracarboxyl-bisbenzimidazole (PTCBI, an n-type semiconductor), with which those photoelectrode characteristics in the water phase were investigated in terms of kinetics. Each film of the PTCBI/MPc bilayer functioned as a photoanode, where the photoinduced oxidation of thiol occurs at the MPc/water interface along with the hole conduction through the MPc layer. The holes originate on account of the photophysical events in the p/n interior, involving the charge separation of excitons at the p/n interface. The typical photoelectrochemical characteristic in the PTCBI/MPc photoanodes involved a transient photocurrent occurring in the initial stage under illumination (under potentiostatic conditions): thereafter, it attained a steady state. Moreover, both the initial spiky photocurrents and the steady-state photocurrents exhibited saturation at higher concentrations. An analysis with photoelectrode kinetics was performed by assuming an adsorption step prior to a rate-limiting charge transfer step, where equations were applied to photocurrents based on the Langmuir adsorption equilibrium. The kinetic analyses evidently showed that the photoanodic reactions are kinetically dominated by the charge transfer between MPc and thiol, where the overall kinetics for thiol oxidation decreases in the following order: H(2)Pc > ZnPc > CuPc; that is, it appeared that H(2)Pc acts as the more efficient photofunctional interface capable of oxidation in the water phase when PTCBI was concurrently employed as an electron conductor. Considering that the photocurrent generated is proportional to the surface concentration of thiol (Gamma) at the MPc as well as the intrinsic oxidation rate (cf., ZnPc > H(2)Pc approximately CuPc), the higher efficiency in the output at the H(2)Pc surface was attributed to an exceptionally high Gamma (i.e., from the kinetic analyses, the Gamma value at the H(2)Pc surface was also inferred to be 2-3 times higher than that at the other MPcs). Through the present kinetic analysis, it also revealed that the activity for thiol oxidation taking place at Pc ring is comparable to that at the conventional active catalysts (i.e., polycarboxyphthalocyaninato Co(ii) and Fe(iii)) where a central metal is an active site.     

Photoresponsive n-channel organic field-effect transistors based on a tri-component active layer

Photoresponsive OFETs were fabricated based on a tri-component active layer (NDI2OD-DTYM2, spiropyran and polystyrene). The results demonstrated that these OFETs displayed photoresponsive feature to alternate UV and vis light due to the photoisomerization of spiropyran between the closed-ring state and ionic open-ring state.     

HPLC analysis of organic acids using a novel stationary phase

In the present work, a high performance liquid chromatographic method with UV detection for the separation of six organic acids including, tartaric, malic, acetic, lactic, citric and succinic is described.The separation was performed on a novel stationary phase TEKNOKROMA, Tr-010065 Mediterranea sea₁₈ (15 cm × 0.4 cm, i.d. 3 μm) and using water with a 0.1% (v/v) of formic acid as mobile phase. The advantages of this packing over a conventional octadecylsilane (ODS2) column are reported.The method was validated with respect to linearity, limits of detection and repeatabilities within day and between days and satisfactory results were obtained.The proposed method was applied for the determination of these compounds in commercially available white wines. The samples were injected directly without previous treatment. LC-MS was used as a confirmatory technique.     

Subcritical water extraction of organic matter from sedimentary rocks

Subcritical water extraction of organic matter containing sedimentary rocks at 300 °C and 1500 psi produces extracts comparable to conventional solvent extraction. Subcritical water extraction of previously solvent extracted samples confirms that high molecular weight organic matter (kerogen) degradation is not occurring and that only low molecular weight organic matter (free compounds) are being accessed in analogy to solvent extraction procedures. The sedimentary rocks chosen for extraction span the classic geochemical organic matter types. A type I organic matter-containing sedimentary rock produces n-alkanes and isoprenoidal hydrocarbons at 300 °C and 1500 psi that indicate an algal source for the organic matter. Extraction of a rock containing type II organic matter at the same temperature and pressure produces aliphatic hydrocarbons but also aromatic compounds reflecting the increased contributions from terrestrial organic matter in this sample. A type III organic matter-containing sample produces a range of non-polar and polar compounds including polycyclic aromatic hydrocarbons and oxygenated aromatic compounds at 300 °C and 1500 psi reflecting a dominantly terrestrial origin for the organic materials. Although extraction at 300 °C and 1500 psi produces extracts that are comparable to solvent extraction, lower temperature steps display differences related to organic solubility. The type I organic matter produces no products below 300 °C and 1500 psi, reflecting its dominantly aliphatic character, while type II and type III organic matter contribute some polar components to the lower temperature steps, reflecting the chemical heterogeneity of their organic inventory. The separation of polar and non-polar organic compounds by using different temperatures provides the potential for selective extraction that may obviate the need for subsequent preparative chromatography steps. Our results indicate that subcritical water extraction can act as a suitable replacement for conventional solvent extraction of sedimentary rocks, but can also be used for any organic matter containing mineral matrix, including soils and recent sediments, and has the added benefit of tailored extraction for analytes of specific polarities.     

Efficient deep-red organic light-emitting diodes based on blending MEH-PPV with a small molecule compound

Efficient deep-red organic light-emitting diodes(OLEDs) were investigated based on the blend of poly[2- methoxy-5-(2’-ethyl-hexyloxy)-l,4-phenylene vinylene](MEH-PPV) with 4,7-bis(5-(7-(9H-carbazol-9-yl)-9,9-dioctyl-9H-fluoren -2-yl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole(compound 1).By optimizing the blend ratio,the turn-on voltage of the devices was significantly reduced from 4.9 V to 2.4 V.A highest external quantum efficiency of 2.56%was achieved at a blend ratio of 95:5(wt) for compound 1:MEH-PPV.The CIE coordinate was measured to be(0.70,0.30),with the luminescence peak at around 680 nm.Based on experimental observations the improvement mechanism is described.     

Degradation of organic dyes in water by electrical discharges

The degradation of several organic compounds in aqueous solution: methyl yellow (C₁₄H₁₅N₃), methyl red (C₁₅H₁₅N₃O₂), methyl orange (C₁₄H₁₄N₃NaO₃S), phenol red (C₁₉H₁₄O₅S) and methylene blue (C₁₆H₁₈ClN₃S), was investigated in a pulsed corona discharge. High voltage pulses of 17 kV amplitude, 24 ns rise time and approximately 200 ns duration (full width at half maximum––FWHM) were applied to an array of six hollow needles. When oxygen was bubbled into the solution through the needle, current pulses of 90 A amplitude were obtained and the average power dissipated in the discharge was 19 W at 100 Hz pulse repetition rate. UV-visible spectra of the aqueous solutions show a significant reduction of the absorbance in the visible range, up to 90%, after plasma treatment, suggesting fragmentation of the compounds. Several aliphatic compounds were identified as oxidation products of methyl yellow, methyl red and methyl orange. For methylene blue and phenol red aromatic reaction products were detected as well.     

Using organic nanoparticle fluorescence to determine nitrite in water

Organic fluorescence nanoparticles (1-aminopyrene nanoparticles) were prepared under ultrasonic radiation and used to determine nitrite. Such nanoparticles have a broad, continuous excitation spectrum, but they are also photochemically stable and water-soluble. Nitrite determination was based upon nitrite quenching the fluorescence of the nanoparticles due to a simple diazotization reaction; a simple and specific method. Under optimal conditions, the linear range of the calibration curve was 20–1400 ng ml^–1, with a correlation coefficient of 0.9987 for nitrite. The detection limit was 3 ng ml^–1. The method was applied to various water samples from several sources. Quantitative nitrite recoveries and satisfactory results were achieved.     

Structural phase transitions in organized organic thin films built of alkali stearates

Temperature-dependent structure modification of organised organic thin films (OOTF) built of sodium (NaSt) and lithium (LiSt) stearates was investigated by DSC and vibrational spectroscopy. Structural phases found for the bulk specimens of substances by DSC measurements, correspond to those previously known [1]. The pre-transitional structural changes observed for thin films in the first crystalline phase were investigated by using temperature dependent FTIR spectroscopy. Changes in orientation of stearate long axis and alkyl chain conformation in NaSt and LiSt thin films with temperature are reported. It was found that film heating from 20 up to 110°C leads to decrease of the tilt of alkyl radicals with respect to the surface for NaSt films. With temperature increasing, in the IR absorption spectra of NaSt and LiSt films, the frequency of methylene symmetric C-H stretching IR band change from 2849 to 2851 cm⁻¹ upon the temperature variation in the range 70–90°C and at 100°C, respectively. This indicates the onset of partial melting of the chains at this temperatures which are lower as compared to those of bulk specimens. It is suggested that this may be caused by a peculiar structural organisation of the films near the substrate surface.     

Calculated physical properties of a water molecule in an ice-Like cluster

Some properties of a H₂O molecule surrounded by the four nearest neighbours arranged as in the ice I geometry have been calculated within a SCF scheme in terms of an extended STO's basis. The effect of the outer molecules is treated as a coulombic perturbation. The different possible geometric configurations of the perturbators have been taken into account. Comparisons are made with the experimental changes of some physical properties of water in passing from vapor to condensed phase.

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Zusammenfassung Es werden einige Eigenschaften des Wassermoleküls, das von seinen vier nächsten Nachbarn in Eis-I-Geometrie umgeben ist, mit Hilfe eines SCF-Schemas mit erweiterter STO-Basis berechnet. Dabei wird der Effekt der äußeren Moleküle als Coulombstörung behandelt. Die verschiedenen möglichen geometrischen Konfigurationen der Störmoleküle sind in Betracht gezogen worden. Die Rechenergebnisse werden mit den experimentellen Änderungen einiger physikalischer Eigenschaften des Wassers beim Übergang von der Gasphase zur kondensierten Phase verglichen.

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Work performed with the C.N.R. financial aid.     

Thermal transitions in the bilayer assembly of dimyristoylphosphatidylglycerol sodium salt dispersion in water: a new phase transition through an intermediate state

The thermal properties of the dispersion of sodium salt of dimyristoylphosphatidylglycerol (NaDMPG) in water have been investigated as functions of incubation temperature and aging time by DSC, XRD, sodium ion activity, pH, zeta-potential, and IR measurements. The DSC charts for NaDMPG dispersions incubated below 30 degrees C showed an endothermic peak at 31.7 degrees C with a small shoulder peak at Tm (gel-liquid crystal transition temperature: 23.5 degrees C). The temperature of 31.7 degrees C coincides with the T* temperature at which a high-order transition in the NaDMPG bilayer assembly has been found to occur in our previous studies. However, no peak was observed for the dispersions incubated above 32 degrees C. These results indicate that thermal properties of NaDMPG bilayers definitely differ below and above the T* temperature. The dispersion which had been once incubated at 40 degrees C for 24 h never showed the endothermic peak at T* even after the further aging at 3 degrees C for 12-day. Namely, the NaDMPG bilayer assembly exhibits an intensive thermohysteresis. The XRD charts for the NaDMPG dispersions incubated at 25 degrees C showed a sharp X-ray diffraction pattern corresponding to the repeat distance of d = 4.75 nm regardless of their aging time, while the dispersions incubated at 40 degrees C had no diffraction peak until 9-day elapsed. After 10-day aging at 40 degrees C, however, a diffraction peak corresponding to d = 5.55 nm clearly appeared. In the DSC measurements for the dispersion incubated at 40 degrees C, a few endothermic peaks began to appear between Tm and T* after approximately 7-day aging. Then, they shifted toward higher temperatures and finally converged into a single peak at 40-42 degrees C after 14-day aging. These XRD and DSC peaks observed after a long period of aging time above T* suggest that conformations of the hydrophilic groups and the hydrocarbon chains in the NaDMPG bilayers take a more tight and closer arrangement very slowly via an intermediate state above T*, and a new gel phase of the bilayers is consequently formed, the transition temperature (T(I) temperature) of which is 40-42 degrees C. A molecular interpretation for such transition processes in the bilayer assembly of NaDMPG dispersions has been proposed on the basis of pH, sodium ion activity, zeta-potential, IR data, etc.     

Photoinduced redox reactions between colloidal manganese dioxide and some organic compounds of environmental importance

Numerous organic compounds of environmental importance, i.e., phenol, citric, tartaric, and oxalic acids, proved to promote or accelerate reductive dissolution of colloidal manganese dioxide upon irradiation. This is accounted for the formation of surface-located charge-transfer complexes between the MnO₂ particulates and the organic electron donors. From the dependences of the rate of the photoassisted and thermal dissolution on the concentration of the organic compounds, the equilibrium constants for the formation of these complexes have been determined in the case of phenol, resorcinol, citrate, and tartaric acid. The quantum yields for these photoinduced reactions (at λ _ir = 365 nm), however, do not show any correlation with the values of the corresponding equilibrium constants, although adsorption is prerequisite for the efficient reductive dissolution of MnO₂. The changes in pH markedly affect the rate of this process, indicating that protonation of both the electron donors and the surface of the MnO₂ particulates may play significant roles in these systems. The results of experiments carried out in manganese dioxide excess suggest that total mineralization of organic electron donors is strongly hindered by the disadvantageous adsorption properties of the primary redox products. Dedicated to Professor Janos H. Fendler on the occasion of his 70th birthday.     

Synthesis of conjugated organic dyes containing alkyl substituted thiophene for solar cell

Three organic dyes, JK-41, JK-42, and JK-43 containing bis-dimethylfluoreneaniline and alkyl substituted thiophene unit are designed and synthesized. Under standard global AM 1.5 solar condition, the JK-41 sensitized cell gave a short circuit photocurrent density (J_sc) of 15.23 mA cm⁻², open circuit voltage (V_oc) of 0.67 V, and a fill factor of 0.67, corresponding to an overall conversion efficiency η of 7.69%. Molecular-orbital calculations of the three dyes suggest that the electron distribution moves from the aniline derivative to the cyanoacrylic acid moiety. We found that the power conversion efficiency was shown to be quite sensitive to the structural variations of alkyl substituted thiophene moiety.     

Fabrication of organic phase biosensors based on multilayered polyphenol oxidase protected by an alginate coating

We describe herein, the creation of an organic phase enzyme electrode (OPEE) via avidin–biotin interactions built over an electrogenerated polymer. Multilayered polyphenol oxidase (PPO) assemblies were transferred into an organic solvent (chloroform) for the catechol detection at −0.2 V. In conjunction with an alginate gel, as a hydrophilic additive, the biosensor performance was widely enhanced. The effects of biotinylated polypyrrole film and alginate gel on the diffusion process through the biosensor coating are studied by rotating disk electrode experiments carried out in chloroform with hydroquinone as electroactive permeant.