Quantum chemical studies on corrosion inhibition for series of thio compounds on mild steel in hydrochloric acid

Quantum chemical calculations were performed on ten thio compounds using semi-empirical method PM3 within program package of Material Studio 5.5. The effect of molecular structure on the corrosion inhibition efficiency was investigated using the quantum chemical calculations. The electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels, (LUMO–HOMO) energy gap, dipole moment (λ) and fraction of electron transfer (ΔN) were calculated and discussed. A relationship between the corrosion inhibition efficiency and several quantum parameters was established with coefficient correlation (R²) of 0.8894.     

Light-Wavelength-Based Quantitative Control of Dihydrofolate Reductase Activity by Using a Photochromic Isostere of an Inhibitor

Photopharmacology has attracted research attention as a new tool for achieving optical control of biomolecules, following the methods of caged compounds and optogenetics. We have developed an efficient photopharmacological inhibitor—azoMTX—for Escherichia coli dihydrofolate reductase (eDHFR) by replacing some atoms of the original ligand, methotrexate, to achieve photoisomerization properties. This fine molecular design enabled quick structural conversion between the active “bent” Z isomer of azoMTX and the inactive “extended” E isomer, and this property afforded quantitative control over the enzyme activity, depending on the wavelength of irradiating light applied. Real-time photoreversible control over enzyme activity was also achieved.     

Star‐Shaped,Dendrimeric and Polymeric Triarylamines as Photoconductors and Hole Transport Materials for Electro‐Optical Applications

Recent developments in the synthesis and application of hole conducting oligomeric and polymeric triarylamines are reviewed. The materials are classified as Star‐shaped molecules, Spiros and dendrimers, Side‐chain polymers, and Main‐chain polymers and copolymers. This paper concentrates on the research results of our group on the synthesis of a variety of such compounds, their structure‐property relationship and their application in devices like organic light emitting diodes, solar cells and photorefractive systems. The thermal properties and electronic properties of these compounds were varied by changing the chemical structure and nature of substituents. In the case of low molecular weight star‐shaped molecules the glass transition temperature could be increased to above 140°C by suitable structural design. Similarly, for polymeric triarylamines the variation of glass transition temperature was achieved over a wide range from 92 to 237°C. This is especially necessary for the wide spectrum of applications of these materials as hole conductors in low‐T_g photorefractive composites to high‐T_g materials in OLEDs. Moreover, the electronic energy levels and the band gap in these compounds can be manipulated to optimize the hole injection or electron transfer or emission properties or even photocurrent generation to make them suitable for various applications. Especially, the concept of copolymerization with other functional monomers results in multifunctional copolymers with good hole injection and transport properties. The polymer networks involving triarylamine structures are not included in this Review, because this constitutes the subject‐matter of insoluble hole transport materials and will be published elsewhere.     

The synthesis of novel,visible-wavelength,oxidizable polymerization sensitizers based on the 8-halogeno-5,12-dihydroquinoxalino[2,3-b]quinoxaline skeleton

Novel dyes, based on the 8-halogeno-5,12-dihydroquinoxalino[2,3-b]quinoxaline skeleton, were synthesized and characterized using ¹H NMR spectroscopy and chemical ionization mass spectroscopy. Their electrochemical and spectral properties, such as absorption and emission spectra, quantum yield of fluorescence and quantum yield of singlet oxygen generation, were also measured. These dyes were used as oxidizable sensitizers for diphenyliodonium and N-alkoxypyridinium salts. Photoredox pairs, consisting of dyes and pyridinium or iodonium salts, were found to be effective visible-wavelength initiators of free radical or cationic polymerization, respectively. The ability of each dye to act as a photoinitiator strongly depended upon its chemical structure. The heavy atoms present in the chemical structure could lead to excited triplet states within the dye, thereby facilitating electron transfer from these states.     

Versatile photoluminescence from graphene and its derivatives

Graphene and its derivatives exhibit many interesting photoluminescence (PL) properties because of their unique electronic structures. In spite of the absence of the bandgap, graphene shows PL due to hot electrons. Graphene oxide (GO) fluorescence is different from that of a single organic fluorophore, for which the spectral properties and emission lifetime are independent of wavelength. Single-layered GO sheets are made of a large number of covalently connected independent fluorophores of varying sizes. These fluorophores are aromatic π-conjugated sp²-hybridized subsystems of carbon atoms surrounded by sp³ regions. The PL of GO is pH dependent because of the presence of many oxygen-containing groups in GO sheets. Reduced graphene oxide (rGO) PL is somewhat different from GO because the number and size of sp² fragments are increased in rGO due to the elimination of the functional groups containing oxygen via reduction. Nanosized graphene/GO possesses a strong quantum confinement effect and hence emits intense excitation wavelength-dependent PL. Moreover, graphene quantum dots show upconversion PL due to anti-Stokes transition. The diverse PL properties including the effect of reduction, pH, and solvent have been reported in many recent studies. Here, the versatile PL features of graphene derivatives are reviewed to elucidate the mechanism of PL.     

Synthesis and photoluminescent properties of four novel trinuclear europium complexes based on two tris-β-diketones ligands

Four novel trinuclear europium complexes with two tris-β-diketones ligands have been synthesized, and the chemical structures of ligands and complexes were characterized by FT-IR, UV-vis, ¹H NMR, ¹³C NMR, XRD, ESI-MS, and element analysis. The potoluminescent properties of trinuclear complexes in solid and THF solution were investigated. All trinuclear complexes exhibited strong relative luminescent intensity and long luminescent lifetime. Meanwhile, the results of lifetime decay curves indicated that only one chemical environment existed around the europium ion. The intrinsic luminescent quantum yields (Φ_LN) and experimental intensity parameters of trinuclear complexes were obtained based on the emission spectra and luminescent lifetime of ⁵D₀ excited state for europium ion. All trinuclear europium complexes exhibited relative high intrinsic luminescent yield and intensity parameters. Especially, due to the contribution of addition two europium lumophors in trinuclear europium complexes, the trinuclear complexes containing TTA exhibited much longer lifetime and higher intrinsic quantum yield than mononuclear europium complex Eu(TTA)₃phen.     

Recent advances in synthesis, physical properties and applications of conducting polymer nanotubes and nanofibers

This article summarizes and reviews the various preparation methods, physical properties, and potential applications of one-dimensional nanostructures of conjugated polyaniline (PANI), polypyrrole (PPY) and poly(3,4-ethylenedioxythiophene) (PEDOT). The synthesis approaches include hard physical template method, soft chemical template method, electrospinning, and lithography techniques. Particularly, the electronic transport (e.g., electrical conductivity, current-voltage (I-V) characteristics, magnetoresistance, and nanocontact resistance) and mechanical properties of individual nanowires/tubes, and specific heat capacity, magnetic susceptibility, and optical properties of the polymer nanostructures are presented with emphasis on size-dependent behaviors. Several potential applications and corresponding challenges of these nanofibers and nanotubes in chemical, optical and bio-sensors, nano-diodes, field effect transistors, field emission and electrochromic displays, super-capacitors and energy storage, actuators, drug delivery, neural interfaces, and protein purification are also discussed.     

Cycloaddition Reactions of Substituted Allenes with Triplet Excited Aromatic Thiones: Product Formation and Reaction Mechanism

The reactivity of substituted allenes H₂CCC(R)X towards three triplet aromatic thiones has been investigated. Product analysis reveal the formation of two (2+2)-cycloaddition products the thietanes 3, 4 (E + Z) and occasionally of one (4+2)-cycloaddition product, thiopyran derivative (Z)-5, generally in high overall yields. Steady state measurements show that electron donating substituents in the allenic system enhance the overall reaction rate. There is little effect of solvent polarity on the reaction rate. The correlation between the relative reaction rates and the first adiabatic ionization energy of the substituted allenes is in accordance with the formation of an exciplex between the excited thione and that π-bond of the allenic system which is conjugated with the substituent X. From this exciplex two isomeric allylic 1,4-biradicals (Z)-8 and (E)-8 are probably formed. After inter-system crossing, ring closure gives the thietanes 3 , (E)- 4 , (Z)- 4 and/or thiopyran derivative (Z)- 5 . The ratio in which 3 , (E)- 4 , (Z)- 4 and (Z)- 5 are formed is explained by considering electronic and steric factors in the proposed reaction mechanism. Experiments with an optically active allene (+)-PhC(H)CC(H)Me support the intermediacy of a non-chiral relatively stable allylic 1,4-biradical. At infinite allene concentration the quantum yield approaches 1, indicating no energy loss during the reaction. Thus no measurable disproportionation of the allylic biradicals (Z)- 8 and (E)- 8 occurs.     

Carbons as a route to synthetic metals

From its crystal structure graphite must be considered as a solid organic compound containing macroaromatic molecules and delocalised electrons. A hypothesis that intercalation crystal compounds of graphite are analogous in quantum chemistry with charge transfer compounds formed between smaller aromatic systems, and electron donor or electron acceptor molecules, has been abundantly verified experimentally. A great diversity of intercalation compounds of graphite has been prepared in polycrystalline compact or powdered form. All show much higher electrical conductivity than the parent graphite, with p or n carriers predominant according to the electron acceptor or electron donor character of the intercalate. Graphite exhibits extremely high anisotropy in its crystal structure and its physical properties. Much of this anisotropy persists in synthetic metals prepared from graphite by intercalation. This makes it essential to start with well oriented graphite in large pieces, to evaluate intrinsic electronic properties in the principal crystal directions with precision. Progressive advances are described in high temperature chemical engineering of graphite, whose final outcome has been the successful production of large pieces of well oriented material. Some of these novel procedures are also of interest, e.g. in the chemical engineering production of diamond from graphite. Using such well oriented materials, experimental study of intercalation (charge transfer) compounds has become much more precise. Some challenging problems have been revealed concerning the anisotropy of electronic properties. In general, conduction of electricity in the basal plane directions follows patterns familiar with other metals. But at right angles, unusual behaviour is apparent particularly at low temperatures.     

Synthesis,DNA Binding,and Antiproliferative Activity of Novel Acridine-Thiosemicarbazone Derivatives

In this work, the acridine nucleus was used as a lead-compound for structural modification by adding different substituted thiosemicarbazide moieties. Eight new (Z)-2-(acridin-9-ylmethylene)-N-phenylhydrazinecarbothioamide derivatives (3a–h) were synthesized, their antiproliferative activities were evaluated, and DNA binding properties were performed with calf thymus DNA (ctDNA) by electronic absorption and fluorescence spectroscopies. Both hyperchromic and hypochromic effects, as well as red or blue shifts were demonstrated by addition of ctDNA to the derivatives. The calculated binding constants ranged from 1.74 × 10⁴ to 1.0 × 10⁶ M⁻¹ and quenching constants from −0.2 × 10⁴ to 2.18 × 10⁴ M⁻¹ indicating high affinity to ctDNA base pairs. The most efficient compound in binding to ctDNA in vitro was (Z)-2-(acridin-9-ylmethylene)-N-(4-chlorophenyl) hydrazinecarbothioamide (3f), while the most active compound in antiproliferative assay was (Z)-2-(acridin-9-ylmethylene)-N-phenylhydrazinecarbothioamide (3a). There was no correlation between DNA-binding and in vitro antiproliferative activity, but the results suggest that DNA binding can be involved in the biological activity mechanism. This study may guide the choice of the size and shape of the intercalating part of the ligand and the strategic selection of substituents that increase DNA-binding or antiproliferative properties.     

Towards tuning of surface properties by atomic and molecular adsorption on boron-terminated cubic boron nitride (111) surface: A first-principles study

We present a theoretical investigation for the adsorptions of triangular nitrogen trimer radical (N₃) at both the hollow (H3) and fourfold coordinated top (T4) sites on boron-terminated (111) (B(111)) surface of cubic boron nitride (c-BN) in terms of structure, adsorption energy, band structure and work function. For the first time, we explore the H3 and T4 adsorption mechanisms. Moreover, we study the subsequent co-adsorption of N₃, boron and hydrogen atoms on the same adsorption site on the B(111) surface, which will form either pyramid quantum cluster or nearly planar adsorbate. We find that the surface band structure varies substantially depending on the types of terminated surface formed (changing from metallic to semi-conducting), and consequently, the surface work function changes. These results indicate the electronic characteristics of the B(111) surface can be tuned readily using chemical co-adsorption, suggesting its potential for chemical sensing applications.     

Synthesis, Spectral, Morphology, Thermal Degradation Kinetics and Antibacterial Studies of Terpolymer Metal Complexes

Terpolymer metal complexes involving transition metal ions such as Cu(II), Mn(II) and Zn(II) were prepared using a terpolymer ligand derived from anthranilic acid–phenyl hydrazine–formaldehyde (APHF). The terpolymer ligand and its metal complexes were intended to spectral characterizations viz. FTIR, electronic, ESR, ¹H NMR and ¹³C NMR to elucidate the structural confirmations. The number, weight, and size average molecular weights of the terpolymer ligand were determined by gel permeation chromatography (GPC). The empirical formula of the repeating unit for both the terpolymer ligand and its metal complexes was clearly justified by elemental analysis. The thermal stability of the ligand and its metal complexes was established by thermogravimetric analysis (TGA). On basis of the TGA data, the kinetic and thermodynamic parameters such as activation energy (E _a), order of reaction (n), entropy change (ΔS), apparent entropy (S*), frequency factor (Z) and free energy change (ΔF) were calculated using Freeman–Carroll and Sharp–Wentworth methods. Further the degradation mechanism for the thermal decomposition was also identified from Phadnis–Desphande method. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis were used to establish the surface morphology and nature of the terpolymer ligand and its metal complexes. In addition, the terpolymer ligand and its metal complexes were screened against the growth of few bacteria and their inhibitions were measured and reported.     

High mobility single crystal diamond detectors for dosimetry: Application to radiotherapy

Diamond exhibits properties of interest for applications in the medical field. It is a very attractive material for detector fabrication due to its intrinsic properties and particularly its soft-tissue equivalence (Z = 6 compared to Z = 7.42 for human tissue), mechanical robustness and radiation hardness. Detectors fabricated from natural diamonds are used in several hospitals as dosimetric tools for the dose measurement received by the patient during radiotherapy and for beam calibration. Natural diamond based devices are expensive and long delivery times are common. The use of synthetic single crystal diamond is a promising issue for point dosimeter. Here we report on the growth of synthetic diamond using the CVD technique to fabricate free standing single crystals. Samples were characterized from their optical and electronic properties (Raman, TOF) and mounted as solid ionisation chambers with blocking contacts, for the evaluation of their dosimetric properties. Clinical tests were conducted in a medical facility at the Institute Gustave Roussy (IGR) in France specialised in the medical treatment of tumours. The results obtained demonstrate that our single crystal diamond detectors comply with the required specifications for radiotherapy applications.     

Spectral properties of chalcone containing triphenylamino structural unit in solution and in polymer matrices

Novel chalcones (3-phenyl-1-phenylprop-2-en-1-ones) substituted on one end (position 3) with electron donating diphenylaminophenyl substituent and on the other end (position 1) with thiophenes with variable electronic effects (CH-1-CH-5) were prepared. The spectral properties of these molecules in solvents such as chloroform, cyclohexane, acetonitrile, methanol and incorporated into polymer matrices of polystyrene (PS), poly(methyl methacrylate) (PMMA) and poly(vinyl chloride) (PVC) were compared with those of 3-[4-(N,N-dimethylamino)-phenyl]-1-phenylprop-2-en-1-one (CH-1m) and 3-[4-(N,N-dimethylamino)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one (CH-2m). The longest wavelength absorption band of model chalcones CH-1m and CH-2m was in the range of 400-420 nm and did not appear to be influenced by the medium. The fluorescence increased with the addition of acetonitrile, while it was effectively quenched in methanol. The strong electron-attracting nitro group quenched the fluorescence of CH-2m in nearly all solvents. In contrast, the fluorescence became more intense when the molecule was incorporated in a polymer matrix. The longest wavelength absorption band of novel chalcones was observed in the range of 410-450 nm in all media. The fluorescence of chalcones was red-shifted to the range of 530-575 nm and was most intense in chloroform. The quantum yield of fluorecence was the highest in chloroform for the chalcone with a methyl-thiophene (0.49) and low for the chalcone with a fluorenyl-thiophene group (0.07). The fluorescence of all chalcones (CH-1-CH-5) was effectively quenched in polar acetonitrile and methanol, and was less intense relative to chloroform when incorporated into a polymer matrix and more intense relative to other solvents. The lifetime of fluorescence was in the range of 1-4 ns. The Stokes shift was in the range of 4000-5000 cm⁻¹ in chloroform, and lower in all other media. The spectral behavior of model chalcones CH-1m and CH-2m and novel chalcones with diphenylamino substituents was similar, producing observable fluorescence in several polymer matrices. The effect of the solvent on the fluorescence is discussed in terms of negative and positive solvatokinetic effects.     

Structural and electronic effects induced by carboxylic acid substitution in isomeric 2,2′-bithiophenes and oligothiophenes: A computational study

The structural and electronic properties of carboxylic acid-substituted 2,2′-bithiophenes have been examined using quantum mechanical methods based on density functional theory. Calculations at the B3PW91/6-31+G(d,p) level were performed on 2,2′-bithiophene-4,4′-dicarboxylic acid, 2,2′-bithiophene-3,4′-dicarboxylic acid and 2,2′-bithiophene-3,3′-dicarboxylic acid, different arrangements being additionally considered for the carboxylic acid substituents of each isomer. The energy gap calculated for 2,2′-bithiophene-3,4′-dicarboxylic acid was about 0.15 eV smaller than that predicted for unsubstituted 2,2′-bithiophene. Additional calculations were performed on oligothiophenes containing n carboxylic acid substituted thiophene rings, n ranging from 2 to 7. The results, which allowed to estimate the band gap for the corresponding poly(thiophene carboxylic acid)s, indicated that the introduction of carboxylic acid substituents at polythiophene produces a very small increase in the ε_g gap.     

Photopharmacological Applications for Cherenkov Radiation Generated by Clinically Used Radionuclides

Translational photopharmacological applications are limited through irradiation by light showing wavelengths within the bio-optical window. To achieve sufficient tissue penetration, using wavelengths >500 nm is mandatory. Nevertheless, the majority of photopharmacological compounds respond to irradiation with more energetic UV light, which shows only a minor depth of tissue penetration in the µm range. Thus, we became interested in UV light containing Cherenkov radiation (CR) induced as a by-product by clinically employed radionuclides labeling specific tissues. Therefore, CR may be applicable in novel photopharmacological approaches. To provide evidence for the hypothesis, we verified the clinically established radionuclides ⁶⁸Ga and ⁹⁰Y but not ¹⁸F in clinically used activities to be capable of generating CR in aqueous solutions. We then investigated whether the generated CR was able to photoactivate the caged kinase inhibitor cagedAZD5438 as a photoresponsive model system. Herein, 21% uncaging of the model system cagedAZD5438 occurred by incubation with ⁹⁰Y, along with a non-specific compound decomposition for ⁶⁸Ga and partly for ⁹⁰Y. The findings suggest that the combination of a clinically employed radionuclide with an optimized photoresponsive agent could be beneficial for highly focused photopharmacological therapies.     

Photoswitchable Azo- and Diazocine-Functionalized Derivatives of the VEGFR-2 Inhibitor Axitinib

In this study, we aimed at the application of the concept of photopharmacology to the approved vascular endothelial growth factor receptor (VEGFR)-2 kinase inhibitor axitinib. In a previous study, we found out that the photoisomerization of axitinib’s stilbene-like double bond is unidirectional in aqueous solution due to a competing irreversible [2+2]-cycloaddition. Therefore, we next set out to azologize axitinib by means of incorporating azobenzenes as well as diazocine moieties as photoresponsive elements. Conceptually, diazocines (bridged azobenzenes) show favorable photoswitching properties compared to standard azobenzenes because the thermodynamically stable Z-isomer usually is bioinactive, and back isomerization from the bioactive E-isomer occurs thermally. Here, we report on the development of different sulfur–diazocines and carbon–diazocines attached to the axitinib pharmacophore that allow switching the VEGFR-2 activity reversibly. For the best sulfur–diazocine, we could verify in a VEGFR-2 kinase assay that the Z-isomer is biologically inactive (IC₅₀ >> 10,000 nM), while significant VEGFR-2 inhibition can be observed after irradiation with blue light (405 nm), resulting in an IC₅₀ value of 214 nM. In summary, we could successfully develop reversibly photoswitchable kinase inhibitors that exhibit more than 40-fold differences in biological activities upon irradiation. Moreover, we demonstrate the potential advantage of diazocine photoswitches over standard azobenzenes.     

Modulation of silica layer properties by varying the granulometric state of tetraethyl orthosilicate precursor aerosols during combustion chemical vapor deposition (CCVD)

Abstract

For the purpose of silica surface layer modulation, a pneumatic-controlled two-substance atomizer with inertia-based coarse droplet separation was operated at different system pressures for tetraethyl orthosilicate precursor aerosol supply during combustion chemical vapor deposition. A comprehensive testing study was performed to characterize the atomizer’s performance characteristics, initial precursor aerosols at the atomizer’s outlet, transformed aerosols before combustion, combustion aerosols and formed layers. Laser diffraction spectrometry, differential electrical mobility analyses and condensation particle counting were used for aerosol characterization with regard to particle size and particle production quantities. Layers were characterized by scanning electron microscopy, atomic force microscopy, spectral ellipsometry, water contact angle measurements and light transmission concerning geometric properties (thickness, surface structure and roughness) and physical behaviors (i.e., optical behaviors, hydrophobicity). Results show a quasi-linear relationship of the ejection mass flow of the pneumatic-controlled atomizer and geometric layer properties which again show a direct relationship to the physical properties. No correlation was found between the aerosols before combustion and the combustion aerosols since the majority of combustion aerosol particles are synthesized solely from the gas phase based on evaporated precursor material.

Copyright © 2020 American Association for Aerosol Research     

Synthesis, absorption and fluorescence of hydrazone colorants based on pyrrolinone esters

Ten azo dyes were prepared by diazotization of a series of electronically different para substituted anilines and subsequent azo coupling of these diazonium salts with ethyl 4,5-dihydro-5-oxo-2-aryl(1H)pyrrole-3-carboxylate as a the coupling component. All of the dyes were confirmed as keto-hydrazone tautomers and were found as a mixtures of E- and Z-isomers with respect to the exocyclic CN bond by ¹H-NMR spectroscopy. The absorption spectra are all similar irrespective of substituent and solvent. By comparison the fluorescence is strongly dependent on the electronic character of the substituents. All compounds fluoresce in a low temperature solvent glass and in the solid state and only the 4-cyanophenyl and 4-nitrophenyl derivatives show fluorescence in solution at room temperature. The spectroscopic behavior is explained in terms of competition between E/Z isomerization and fluorescence after excitation.     

Evaluation of the aniline chemical oxidation process using multiple simultaneous electrochemical responses

In this paper we show the simultaneous evaluation of the electrochemical impedance, the open circuit potential and the mass variation of the polyaniline deposited on a metal substrate during chemical oxidation of aniline. We detected that the final properties of the polymer could be practically defined after the inflection point of the potential profile. Considering a series connection of R and C, impedance Z was decomposed into the resistive and capacitive components. The resistivity and permittivity show a slight change after the inflection point in the potential profile. Impedance data and mass changes during synthesis also contributed to a better definition of the induction period. We described the system as whole, which relates to an electronic transport and to an electronic charge storage process. Although very simple, this model helps us to interpret and correlate different techniques to explain the results. In addition, we demonstrated that the in situ evaluation of the parameters described above offers new insights on the chemical synthesis mechanism of polyaniline.