Search results for: acceptor synthesis

Authors: J. Lyagaeva, D. Medvedev, A. Brouzgou, A. Demin, P. Tsiakaras

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The investigation of highly conductive and chemically stable electrolytes for solid oxide fuel cells (SOFC) is a necessity. The aim of the present work is to study the influence of acceptor dopant on the functional properties of textured BaCe0.5Zr0.3Ln0.2O3−δ (Ln = Yb, Y, Gd, Sm, Nd) ceramics. The X-Ray diffraction analysis, scanning electron microscopy, dilatometry and 4-probe dc method of conductivity measurements were used. It was found that the mean grain size of ceramics increases (from 1.4 to 3.2 μm), thermal expansion coefficient grows (from 7.6•10–6 to 10.7•10–6 К–1), but ionic conductivity decreases (from 14 to 3 mS cm–1 at 900°С), when ionic radii of impurity acceptor increases from 0.868 Å (Yb3+) to 0.983 Å (Nd3+).

Keywords: acceptor dopant, crystal structure, proton-conducting, SOFC

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Authors: Pasquale Porcu, Mireille Vonlanthen, Gerardo Zaragoza-Galán, Ernesto Rivera

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In this work, we report the synthesis of a novel series of dendritic molecules bearing donor-acceptor groups (pyrene-bodipy) with potential applications in energy transfer. Initially, first and second generation Fréchet type dendrons (Py2-G1OH and Py4-G2OH) were prepared from 1-pyrenylbutanol and 3,5-dihydroxybenzylic alcohol. These compounds were further linked to a bodipy unit via an esterification reaction in order to obtain the desired products (Bodipy-G1Py2) and Bodipy-G2Py4). These compounds were fully characterized by FTIR and 1H and 13C NMR spectroscopy and their molecular weights were determined by MALDITOF. The optical and photophysical properties of these molecules were evaluated by absorbance and fluorescence spectroscopy, in order to compare their behaviour with other analogue molecules.

Keywords: bodipy, dendritic molecules, optical properties, pyrene

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Authors: Mohamed Ayoub

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We perform computational investigation using density functional theory, B3LYP with aug-cc-pVTZ basis set followed by natural bond orbital analysis (NBO), which provides best single “natural Lewis structure” (NLS) representation of chosen wavefunction (Ψ) with natural resonance theory (NRT) to provide an analysis of molecular electron density in terms of resonance structures (RS) and weights (w). We selected for the study a wide range of gas phase dimers (B…HA), with hydrogen bond dissociation energies (ΔEB…H) that span more than two orders of magnitude. We demonstrate that charge transfer from a donor Lewis-type NBO (nB:) to an acceptor non-Lewis-type NBO (σHA*) is the primary cause for H-bonding not classical electrostatic (dipole-dipole or ionic). We provide a variety of structure, and spectroscopic descriptors to support the conclusion, such as IR frequency shift (ΔνHA), H-bond penetration distance (ΔRB..H), bond order (bB..H), charge-transfer (CTB→HA) and the corresponding donor-acceptor stabilization energy (ΔE(2)).

Keywords: natural bond orbital, hydrogen bonding, electron donor, electron acceptor

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Authors: Atul Kumar, Veeranjaneyulu Gannedi, Qazi Naveed Ahmed

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Oligosaccharides, which are essential to all cellular organisms, play vital roles in cell recognition, signaling, and are involved in a broad range of biological processes. The chemical synthesis of carbohydrates represents a powerful tool to provide homogeneous glycans. In carbohydrate synthesis, the major concern is the orthogonal protection of hydroxyl groups that can be unmasked independently. Classical protecting groups include benzyl ethers (Bn), which are normally cleaved through hydrogenolysis or by means of metal reduction, and acetate (Ac), benzoate (Bz) or pivaloate esters, which are removed using base promoted hydrolysis. In present work a series of α-Oxoester (COBz) protected saccharides, with divergent base sensitivity profiles against benzoyl (Bz) and acetyl (Ac), were designed and KHSO₅/CH₃COCl in methanol was identified as an easy, mild, selective and efficient deprotecting reagent for their removal in the perspective of carbohydrate synthesis. Timely monitoring of later reagent was advantageous in establishing both sequential as well as simultaneous deprotecting of COBz, Bz, and Ac. The salient feature of our work is its ease to generate different acceptors using designed monosaccharides. In summary, we demonstrated α-Oxoester (COBz) as a new protecting group for carbohydrates and the application of this group for the synthesis of Glycosylphosphatidylinositol (GPI) anchor are in progress.

Keywords: α-Oxoester, oligosaccharides, new protecting group, acceptor synthesis, glycosylation

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Authors: Akanksha Singh, Mahesh Kumar, Shailesh N. Sharma

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Semiconductor quantum dots (QDs) such as CdSe, CdS, InP, etc. have gained significant interest in the recent years due to its application in various fields such as LEDs, solar cells, lasers, biological markers, etc. The interesting feature of the QDs is their tunable band gap. The size of the QDs can be easily varied by varying the synthesis parameters which change the band gap. One of the limitations with II-VI semiconductor QDs is their biological application. The use of cadmium makes them unsuitable for biological applications. III-V QD such as InP overcomes this problem as they are structurally robust because of the covalent bonds which do not allow the ions to leak. Also, InP QDs has large Bohr radii which increase the window for the quantum confinement effect. The synthesis of InP QDs is difficult and time consuming. Authors have synthesized InP using a novel, quick synthesis method which utilizes trioctylphosphine as a source of phosphorus. In this work, authors have made InP composites with P3HT(Poly(3-hexylthiophene-2,5-diyl))polymer(organic-inorganic hybrid material) and gold nanoparticles(metal-semiconductor composites). InP-P3HT shows FRET phenomenon whereas InP-Au shows charge transfer mechanism. The synthesized InP QDs has an absorption band at 397 nm and PL peak position at 491 nm. The band gap of the InP QDs is 2.46 eV as compared to the bulk band gap of InP i.e. 1.35 eV. The average size of the QDs is around 3-4 nm. In order to protect the InP core, a shell of wide band gap material i.e. ZnS is coated on the top of InP core. InP-P3HT composites were made in order to study the charge transfer/energy transfer phenomenon between them. On adding aliquots of P3HT to InP QDs solution, the P3HT PL increases which can be attributed to the dominance of Förster energy transfer between InP QDs (donor) P3HT polymer (acceptor). There is a significant spectral overlap between the PL spectra of InP QDs and absorbance spectra of P3HT. But in the case of InP-Au nanocomposites, significant charge transfer was seen from InP QDs to Au NPs. When aliquots of Au NPs were added to InP QDs, a decrease in the PL of the InP QDs was observed. This is due to the charge transfer from the InP QDs to the Au NPs. In the case of metal semiconductor composites, the enhancement and quenching of QDs depend on the size of the QD and the distance between the QD and the metal NP. These two composites have different phenomenon between donor and acceptor and hence can be utilized for two different applications. The InP-P3HT composite can be utilized for LED devices due to enhancement in the PL emission (FRET). The InP-Au can be utilized efficiently for photovoltaic application owing to the successful charge transfer between InP-Au NPs.

Keywords: charge transfer, FRET, gold nanoparticles, InP quantum dots

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Authors: M. Nazim, S. Ameen, H. K. Seo, H. S. Shin

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Energy is the basis of life and strong attention has been growing for the cost-effective energy production. Recently, solution-processed small molecule organic solar cells (SMOSCs) have grown much attention due to the wages such as well-defined molecular structures, definite molecular weight, easy synthesis and easy purification techniques. In particular, the size of donor (D) and acceptor (A) unit is a crucial factor for the exciton-diffusion towards D-A interface and then charge-separation for the effective charge-transport to the electrodes. Furan-bridged materials are more electron-rich, high fluorescence, with better molecular-packing, and greater rigidity and greater solubility than their thiophene-counterparts In this work, a furan-bridged thiazolo[5,4-d]thiazole based organic small molecule (RFTzR) was formulated and applied for BHJ organic solar cells (OSCs). The introduction of furan spacer with two terminal alkyl units improved its absorption and solubility in the common organic solvents, significantly. RFTzR exhibited a HOMO and LUMO energy levels of -5.36 eV and -3.14 eV, respectively. The fabricated solar cell devices of RFTzR (donor) with PC60BM (acceptor) as photoactive materials showed high performance of 2.72% (RFTzR:PC60BM, 2:1, w/w) ratio with open-circuit voltage of 0.756 V and high photocurrent density of 10.13 mA/cm².

Keywords: chromophore, organic solar cells, photoactive materials, small molecule

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Authors: Hassan Bohra, Mingfeng Wang

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Conjugated porous polymers (CPPs) are amorphous, insoluble and highly robust organic semiconductors that have been largely synthesized by traditional transition-metal catalyzed reactions. The distinguishing feature of CPP materials is that they combine microporosity and high surface areas with extended conjugation, making them ideal for versatile applications such as separation, catalysis and energy storage. By applying a modular approach to synthesis, chemical and electronic properties of CPPs can be tailored for specific applications making these materials economical alternatives to inorganic semiconductors. Direct arylation - an environmentally benign alternative to traditional polymerization reactions – is one such reaction that extensively over the last decade for the synthesis of linear p-conjugated polymers. In this report, we present the synthesis and characterization of a new series of robust conjugated porous polymers synthesized by facile direct arylation polymerization of thiophene-flanked acceptor building blocks with multi-brominated aryls with different geometries. We observed that the porosities and morphologies of the polymers are determined by the chemical structure of the aryl bromide used. Moreover, good control of the optical bandgap in the range 2.53 - 1.3 eV could be obtained by using different building blocks. Structure-property relationships demonstrated in this study suggest that direct arylation polymerization is an attractive synthetic tool for the rational design of porous organic materials with tunable photo-physical properties for applications in photocatalysis, energy storage and conversion.

Keywords: direct arylation, conjugated porous polymers, triazine, photocatalysis

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Authors: Milica Carević, Katarina Banjanac, Marija ĆOrović, Ana Milivojević, Nevena Prlainović, Aleksandar Marinković, Dejan Bezbradica

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Nowadays, considering the growing awareness of functional food beneficial effects on human health, due attention is dedicated to the research in the field of obtaining new prominent products exhibiting improved physiological and physicochemical characteristics. Therefore, different approaches to valuable bioactive compounds synthesis have been proposed. β-Galactosidase, for example, although mainly utilized as hydrolytic enzyme, proved to be a promising tool for these purposes. Namely, under the particular conditions, such as high lactose concentration, elevated temperatures and low water activities, reaction of galactose moiety transfer to free hydroxyl group of the alternative acceptor (e.g. different sugars, alcohols or aromatic compounds) can generate a wide range of potentially interesting products. Up to now, galacto-oligosaccharides and lactulose have attracted the most attention due to their inherent prebiotic properties. The goal of this study was to obtain a novel product sorbitol galactoside, using the similar reaction mechanism, namely transgalactosylation reaction catalyzed by β-galactosidase from Aspergillus oryzae. By using sugar alcohol (sorbitol) as alternative acceptor, a diverse mixture of potential prebiotics is produced, enabling its more favorable functional features. Nevertheless, an introduction of alternative acceptor into the reaction mixture contributed to the complexity of reaction scheme, since several potential reaction pathways were introduced. Therefore, the thorough optimization using response surface method (RSM), in order to get an insight into different parameter (lactose concentration, sorbitol to lactose molar ratio, enzyme concentration, NaCl concentration and reaction time) influences, as well as their mutual interactions on product yield and productivity, was performed. In view of product yield maximization, the obtained model predicted optimal lactose concentration 500 mM, the molar ratio of sobitol to lactose 9, enzyme concentration 0.76 mg/ml, concentration of NaCl 0.8M, and the reaction time 7h. From the aspect of productivity, the optimum substrate molar ratio was found to be 1, while the values for other factors coincide. In order to additionally, improve enzyme efficiency and enable its reuse and potential continual application, immobilization of β-galactosidase onto tailored silica nanoparticles was performed. These non-porous fumed silica nanoparticles (FNS)were chosen on the basis of their biocompatibility and non-toxicity, as well as their advantageous mechanical and hydrodinamical properties. However, in order to achieve better compatibility between enzymes and the carrier, modifications of the silica surface using amino functional organosilane (3-aminopropyltrimethoxysilane, APTMS) were made. Obtained support with amino functional groups (AFNS) enabled high enzyme loadings and, more importantly, extremely high expressed activities, approximately 230 mg proteins/g and 2100 IU/g, respectively. Moreover, this immobilized preparation showed high affinity towards sorbitol galactoside synthesis. Therefore, the findings of this study could provided a valuable contribution to the efficient production of physiologically active galactosides in immobilized enzyme reactors.

Keywords: β-galactosidase, immobilization, silica nanoparticles, transgalactosylation

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Authors: Bandar Ali Al-Asbahi, Mohammad Hafizuddin Haji Jumali

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Forster energy transfer between poly (9,9'-di-n-octylfluorenyl-2,7-diyl) (PFO)/TiO2 nanoparticles (NPs) as a donor and Fluorol 7GA as an acceptor has been studied. The energy transfer parameters were calculated by using mathematical models. The dominant mechanism responsible for the energy transfer between the donor and acceptor molecules was Forster-type, as evidenced by large values of quenching rate constant, energy transfer rate constant and critical distance of energy transfer. Moreover, these composites which were used as an emissive layer in organic light emitting diodes, were investigated in terms of current density–voltage and electroluminescence spectra.

Keywords: energy transfer parameters, forster-type, electroluminescence, organic light emitting diodes

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Authors: M. Ravindiran, P. Shankar

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This paper deals with the comparison of two synthesis methods, namely, sol-gel, and combustion to prepare Fe doped ZnO nano material. Characterization results for structural, optical and magnetic properties were analyzed for the sol gel and combustion synthesis derived materials. Magnetic studies of the prepared compounds reveal that the combustion synthesis derived material has good magnetization of 50 emu/gm with a better hysteresis loop curve.

Keywords: DMS, combustion, ferromagnetic, synthesis methods

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Authors: Rabih Al-Kaysi

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When quasi-stable solutions of 9-methylanthracene (pi-electron donor, 0.0005 M) and 1,2,4,5-Tetracyanobenzene (pi-electron acceptor, 0.0005 M) in aqueous sodium dodecyl sulfate (SDS, 0.025 M) were gently mixed, uniform-shaped rectangular charge-transfer nanocrystals precipitated out. These red colored charge-transfer (CT) crystals were composed of a 1:1-mole ratio of acceptor/ donor and are highly insoluble in water/SDS solution. The rectangular crystals morphology is semi hollow with symmetrical twin pockets reminiscent of nanocapsules. For a typical crop of nanocapsules, the dimensions are 21 x 6 x 0.5 microns with an approximate hollow volume of 1.5 x 105 nm3. By varying the concentration of aqueous SDS, mixing duration and incubation temperature, we can control the size and volume of the nanocapsules. The initial number of CT seed nanoparticles, formed by mixing the D and A solutions, determined the number and dimensions of the obtained nanocapsules formed after several hours of incubation under still conditions. Prolonged mixing of the donor and acceptor solutions resulted in plenty of initial seeds hence smaller nanocapsules. Short mixing times yields less seed formation and larger micron-sized capsules. The addition of Doxorubicin in situ with the quasi-stable solutions while mixing leads to the formation of CT nanocapsules with Doxorubicin sealed inside. The Doxorubicin can be liberated from the nanocapsules by cracking them using ultrasonication. This method can be extended to other binary CT complex crystals as well.

Keywords: charge-transfer, nanocapsules, nanocrystals, doxorubicin

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Authors: Nese Ozturk Korpe, Muhammed H. Karas

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Reaction synthesis, or combustion synthesis, is a processing technique in which the thermal activation energy of formation of a compound is sustained by its exothermic heat of reaction. The aim of the present study was to investigate the effect of high initial pressing pressures (420 MPa, 630 MPa, and 850 MPa) on porosity of Ti3Al which produced by volume combustion synthesis. Microstructure examinations were performed by optical microscope (OM) and scanning electron microscope (SEM). Phase analyses were performed with X-ray diffraction device (XRD). A significant decrease in porosity was obtained due to an increase in the initial pressing pressure.

Keywords: Titanium Aluminide, Volume Combustion Synthesis, Intermetallic, Porosity

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Authors: Mireille Vonlanthen, Pasquale Porcu, Ernesto Rivera

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Dendritic macromolecules are presenting unique physical and chemical properties. One of them is the faculty of transferring energy from a donor moiety introduced at the periphery to an acceptor moiety at the core, mimicking the antenna effect of the process of photosynthesis. The mechanism of energy transfer is based on the Förster resonance energy exchange and requires some overlap between the emission spectrum of the donor and the absorption spectrum of the acceptor. Since it requires a coupling of transition dipole but no overlap of the physical wavefunctions, the energy transfer by Förster mechanism can occur over quite long distances from 1 to a maximum of 10 nm. However, the efficiency of the transfer depends strongly on distance. The Förster radius is the distance at which 50% of the donor’s emission is deactivated by FRET. In this work, we synthesized and characterized a novel series of dendrimers bearing pyrene moieties at the periphery and a Ru (II) complex at the core. The optical and photophysical properties of these compounds were studied by absorption and fluorescence spectroscopy. Pyrene is a well-studied chromophore that has the particularity to present monomer as well as excimer fluorescence emission. The coordination compounds of Ru (II) are red emitters with low quantum yield and long excited lifetime. We observed an efficient singulet to singulet energy transfer in such constructs. Moreover, it is known that the energy of the MLCT emitting state of Ru (II) can be tuned to become almost isoenegetic with respect to the triplet state of pyrene, leading to an extended phosphorescence lifetime. Using dendrimers bearing pyrene moieties as ligands for Ru (II), we could combine the antenna effect of dendrimers as well as its protection effect to the quenching by dioxygen with lifetime increase due to triplet-triplet equilibrium.

Keywords: dendritic molecules, energy transfer, pyrene, ru-trisbipyridine complex

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Authors: Anitha Kandasamy, Thirumurugan Ramaiah

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Interestingly, organic materials exhibit large optical nonlinearity with quick responses and having the flexibility of molecular tailoring using computational modelling and favourable synthetic methodologies. Pyridine based organic compounds and carboxylic acid contained aromatic compounds play a crucial role in crystal engineering of NCS complexes that displays admirable optical nonlinearity with fast response and favourable physicochemical properties such as low dielectric constant, wide optical transparency and large laser damage threshold value requires for optoelectronics device applications. Based on these facts, it was projected to form an acentric molecule of π-conjugated system interaction with appropriately replaced electron donor and acceptor groups for achieving higher SHG activity in which quinoline-2-carboyxlic acid is chosen as an electron acceptor and capable of acting as an acid as well as a base molecule, while 2-amino-4-methylpyridine is used as an electron donor and previously employed in numerous proton transfer complexes for synthesis of NLO materials for optoelectronic applications. 2-amino-4-mehtylpyridinium quinoline-2-carboxylate molecular complex (2AQ) is having π-donor-acceptor groups in which 2-amino-4-methylpyridine donates one of its electron to quinoline -2-carboxylic acid thereby forming a protonated 2-amino-4-methyl pyridinium moiety and mono ionized quinoline-2-carboxylate moiety which are connected via N-H…O intermolecular interactions with non-centrosymmetric crystal packing arrangement at microscopic scale is accountable to the enhancement of macroscopic second order NLO activity. The 2AQ crystal was successfully grown by a slow evaporation solution growth technique and its structure was determined in orthorhombic crystal system with acentric, P212121, space group. Hirshfeld surface analysis reveals that O…H intermolecular interactions primarily contributed with 31.0 % to the structural stabilization of 2AQ. The molecular structure of title compound has been confirmed by 1H and 13C NMR spectral studies. The vibrational modes of functional groups present in 2AQ have been assigned by using FTIR and FT-Raman spectroscopy. The grown 2AQ crystal exhibits high optical transparency with lower cut-off wavelength (275 nm) within the region of 275-1500 nm. The laser study confirmed that 2AQ exhibits high SHG efficiency of 12.6 times greater than that of KDP. TGA-DTA analysis revealed that 2AQ crystal had a thermal stability of 223 °C. The low dielectric constant and low dielectric loss at higher frequencies confirmed good crystalline nature with fewer defects of grown 2AQ crystal. The grown crystal exhibits soft material and positive photoconduction behaviour. Mulliken atomic distribution and FMOs analysis suggested that the strong intermolecular hydrogen bonding which lead to the enhancement of NLO activity. These properties suggest that 2AQ crystal is a suitable material for optoelectronic and laser frequency conversion applications.

Keywords: crystal growth, NLO activity, proton transfer complex, quantum chemical investigation

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Authors: Valentina A. Mikhailova, Serguei V. Feskov, Anatoly I. Ivanov

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In the last decade the nonequilibrium charge transfer have attracted considerable interest from the scientific community. Examples of such processes are the charge recombination in excited donor-acceptor complexes and the intramolecular electron transfer from the second excited electronic state. In these reactions the charge transfer proceeds predominantly in the nonequilibrium mode. In the excited donor-acceptor complexes the nuclear nonequilibrium is created by the pump pulse. The intramolecular electron transfer from the second excited electronic state is an example where the nuclear nonequilibrium is created by the forward electron transfer. The kinetics of these nonequilibrium reactions demonstrate a number of peculiar properties. Most important from them are: (i) the absence of the Marcus normal region in the free energy gap law for the charge recombination in excited donor-acceptor complexes, (ii) extremely low quantum yield of thermalized charge separated state in the ultrafast charge transfer from the second excited state, (iii) the nonexponential charge recombination dynamics in excited donor-acceptor complexes, (iv) the dependence of the charge transfer rate constant on the excitation pulse frequency. This report shows that most of these kinetic features can be well reproduced in the framework of stochastic point-transition multichannel model. The model involves an explicit description of the nonequilibrium excited state formation by the pump pulse and accounts for the reorganization of intramolecular high-frequency vibrational modes, for their relaxation as well as for the solvent relaxation. The model is able to quantitatively reproduce complex nonequilibrium charge transfer kinetics observed in modern experiments. The interpretation of the nonequilibrium effects from a unified point of view in the terms of the multichannel point transition stochastic model allows to see similarities and differences of electron transfer mechanism in various molecular donor-acceptor systems and formulates general regularities inherent in these phenomena. The nonequilibrium effects in photoinduced ultrafast charge transfer which have been studied for the last 10 years are analyzed. The methods of suppression of the ultrafast charge recombination, similarities and dissimilarities of electron transfer mechanism in different molecular donor-acceptor systems are discussed. The extremely low quantum yield of the thermalized charge separated state observed in the ultrafast charge transfer from the second excited state in the complex consisting of 1,2,4-trimethoxybenzene and tetracyanoethylene in acetonitrile solution directly demonstrates that its effectiveness can be close to unity. This experimental finding supports the idea that the nonequilibrium charge recombination in the excited donor-acceptor complexes can be also very effective so that the part of thermalized complexes is negligible. It is discussed the regularities inherent to the equilibrium and nonequilibrium reactions. Their fundamental differences are analyzed. Namely the opposite dependencies of the charge transfer rates on the dynamical properties of the solvent. The increase of the solvent viscosity results in decreasing the thermal rate and vice versa increasing the nonequilibrium rate. The dependencies of the rates on the solvent reorganization energy and the free energy gap also can considerably differ. This work was supported by the Russian Science Foundation (Grant No. 16-13-10122).

Keywords: Charge recombination, higher excited states, free energy gap law, nonequilibrium

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Authors: Deepshikha Verma, V. N. Rajasekharan Pillai

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The present study reports the synthesis of cyclic PNC-28 peptides with solid-phase peptide synthesis method. In the first step, we synthesize the linear PNC-28 Peptide and in the second step, we cyclize (N-to-C or head-to-tail cyclization) the linear PNC-28 peptide. The molecular formula of cyclic PNC-28 peptide is C64H88N12O16 and its m/z mass is ≈1233.64. Elemental analysis of cyclic PNC-28 is C, 59.99; H, 6.92; N, 13.12; O, 19.98. The characterization of LC-MS, CD, FT-IR, and 1HNMR has been done to confirm the successful synthesis and cyclization of linear PNC-28 peptides.

Keywords: CD, FTIR, 1HNMR, cyclic peptide

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Authors: J. Iqbal, Z. Zara

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Five new Acceptor-Donor-Acceptor (A-D-A) type small donor molecules (M1-M5) namely; dimethyl cyanoacetate terthiophene di(methylthiophene) dibenzosilole (DMCAO3TBS) (M1), dimelononitrile terthiophene di(methylthiophene) dibenzosilole (DMCNTBS) (M2), dimethyl rhodanine terthiophene di(methylthiophene) dibenzosilole (DMRTBS) (M3), dimelanonitrile terthiophene di(methylthiophene) methyl fluorene (DMCNTF) (M4) and dimethyl rhodanine terthiophene di(methylthiophene) methyl fluorine (DMRTF) (M5) were designed and theoretically explored their electronic, photophysical and geometrical properties via DFT best functional MPW1PW91/6-311G (d,p) level of theory with respect to reference molecules dioctyl cyanoacetate terthiophene di(octylthiophene) dioctylfluorene (DCAO3TF) (Ra) and dioctyl cyanoacetate terthiophene di(octylthiophene) octylcarbazole (DCAO3TCz) (Rb). Among the designed donor molecules (M1-M5), M2 and M4 represented lowest band gap value (2.480 eV and 2.47 eV) with distinctive broad absorption peak at 598 and 601 nm in chloroform due to the presence of stronger electron withdrawing acceptor molecule which pulls the λmax value towards red shift. Theoretically estimated reorganization energies of these molecules recommended excellent property of charge mobility. The designed donor molecules M1-M5, demonstrated lower λe value with reference to their λh, showing that these molecules could be ideal candidates for the transfer of electron with and M2, M4 are best among these as champion molecules with having lowest λe (0.006 D and 0.005 D respectively). Additionally, the Voc of M2 and M4 are 2.01 eV and 1.85 eV respectively with reference respect to PCBM. Thus, our present investigation suggested that our designed donor molecules (M1-M5) are suitable candidates for the solar cell and proposed for high and better performance for the small molecule based solar cell devices.

Keywords: dibenzisilol, donor materials, hole mobility, organic solar cells

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Authors: D. S. Vardar, A. S. Kipcak, F. T. Senberber, E. M. Derun, S. Piskin, N. Tugrul

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Zinc borate is an important inorganic hydrate borate material, which can be use as a flame retardant agent and corrosion resistance material. This compound can loss its structural water content at higher than 290°C. Due to thermal stability; Zinc Borate can be used as flame reterdant at high temperature process of plastic and gum. In this study, the ultrasonic reaction of zinc borates were studied using hydrozincite (Zn5(CO3)2•(OH)6) and boric acid (H3BO3) raw materials. Before the synthesis raw materials were characterized by X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FT-IR). Ultrasonic method is a new application on the zinc borate synthesis. The synthesis parameters were set to 90°C reaction temperature and 55 minutes of reaction time, with 1:1, 1:2, 1:3, 1:4 and 1:5 molar ratio of starting materials (Zn5(CO3)2•(OH)6 : H3BO3). After the zinc borate synthesis, the products analyzed by XRD and FT-IR. As a result, optimum molar ratio of 1:5 (Zn5(CO3)2•(OH)6:H3BO3) is determined for the synthesis of zinc borates with ultrasonic method.

Keywords: borate, ultrasonic method, zinc borate, zinc borate synthesis

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Authors: Babak Azari, Afshin Pourahmad, Babak Sadeghi, Masuod Mokhtari

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In this work, Equisetnm arvense plant extract was used for preparing amorphous SiO₂. For preparing of SiO₂/zeolitic imidazolate framework-8 (ZIF-8) nanocomposite by solvothermal method, the synthesized SiO₂ was added to the synthesis mixture ZIF-8. The nanocomposite was characterized using a range of techniques. The photocatalytic activity of SiO₂/ZIF-8 was investigated systematically by degrading crystal violet as a cationic dye under Ultraviolet light irradiation. Among synthesized samples (SiO₂, ZIF-8 and SiO₂/ZIF-8), the SiO₂/ZIF-8 exhibited the highest photocatalytic activity and improved stability compared to pure SiO₂ and ZIF-8. As evidenced by Scanning Electron Microscopy and Transmission electron microscopy images, ZIF-8 particles without aggregation are located over SiO₂. The SiO₂ not only provides structured support for ZIF-8 but also prevents the aggregation of ZIF-8 Metal-organic framework in comparison to the isolated ZIF-8. The superior activity of this photocatalyst was attributed to the synergistic effects from SiO₂ owing to (I) an electron acceptor (from ZIF-8) and an electron donor (to O₂ molecules), (II) preventing recombination of electron-hole in ZIF-8, and (III) maximum interfacial contact ZIF-8 with the SiO₂ surface without aggregation or prevent the accumulation of ZIF-8. The results demonstrate that holes (h+) and •O₂- are primary reactive species involved in the photocatalytic oxidation process. Moreover, the SiO₂/ZIF-8 photocatalyst did not show any obvious loss of photocatalytic activity during five-cycle tests, which indicates that the heterostructured photocatalyst was highly stable and could be used repeatedly.

Keywords: nano, zeolit, potocatalist, nanocomposite

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Authors: M. Hoseinnezhad, K. Gharanjig

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Two organic dyes comprising carbazole as the electron donors and cyanoacetic acid moieties as the electron acceptors were synthesized. The organic dye was prepared by standard reaction from carbazole as the starting material. To this end, carbazole was reacted with bromobenzene and further oxidation and reacted with cyanoacetic acid. The obtained organic dye was purified and characterized using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (¹HNMR), carbon nuclear magnetic resonance (¹³CNMR) and elemental analysis. The influence of heteroatom on carbazole donors and cyno substitution on the acid acceptor is evidenced by spectral and electrochemical photovoltaic experiments. Finally, light fastness properties for organic dye were investigated.

Keywords: dye-sensitized solar cells, indoline dye, nanostructure, oxidation potential, solar energy

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Authors: M. Hosseinnejad, K. Gharanjig

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In the present study, metal free organic dyes were prepared and used as photo-sensitizers in dye-sensitized solar cells. Double rhodanine was utilized as the fundamental electron acceptor group to which electron donor aldehyde with varying substituents was attached to produce new organic dye. This dye was first purified and then characterized by analytical techniques. Spectrophotometric evaluations of the prepared dye in solution and on a nano anatase TiO₂ substrate were carried out in order to assess possible changes in the status of the dyes in different environments. The results show that the dye form j-type aggregates on the nano TiO₂. Additionally, oxidation potential measurements were also carried out. Finally, dye sensitized solar cell based on synthesized dye was fabricated in order to determine the photovoltaic behavior and conversion efficiency of individual dye.

Keywords: conversion efficiency, dye-sensitized solar cell, photovoltaic behavior, sensitizer

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Authors: Gurpreet Kaur, Manoj Kumar, Vandana Bhalla

Abstract:

Strong acceptor-weak acceptor system FN-TPy has been designed and synthesized which undergoes solvent dependent self-assembly in mixed aqueous media to generate through space intermolecular charge transfer assemblies. The as prepared entropically favoured assemblies of FN-TPy exhibit excellent photostability and photosensitizing properties in the assembled state to activate aerial oxygen for efficient generation of reactive oxygen species (ROS) through Type-I and Type-II pathways. The FN-TPy assemblies exhibit excellent potential for regulated oxidation of alcohols and aldehydes under mild reaction conditions (visible light irradiation, aqueous media, room temperature) using aerial oxygen as the ‘oxidant’. The present study demonstrates the potential of FN-TPy assemblies to catalyze controlled oxidation of benzyl alcohol to benzaldehyde and to corresponding benzoic acid.

Keywords: oxidations, photosensitizer, reactive oxygen species, supramolecular assemblies, through space charge transfer.

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Authors: N. Tugrul, E. Sariburun, F. T. Senberber, A. S. Kipcak, E. Moroydor Derun, S. Piskin

Abstract:

Boron-gypsum is a waste which occurs in the boric acid production process. In this study, the boron content of this waste is evaluated for the use in synthesis of magnesium borates and such evaluation of this kind of waste is useful more than storage or disposal. Magnesium borates, which are a sub-class of boron minerals, are useful additive materials for the industries due to their remarkable thermal and mechanical properties. Magnesium borates were obtained hydrothermally at different temperatures. Novelty of this study is the search of the solution density effects to magnesium borate synthesis process for the increasing the possibility of boron-gypsum usage as a raw material. After the synthesis process, products are subjected to XRD and FT-IR to identify and characterize their crystal structure, respectively.

Keywords: boron-gypsum, hydrothermal synthesis, magnesium borate, solution density

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Authors: Lishuang Ma

Abstract:

Charge transfer (CT) complex, also known as Electron donor-acceptor (EDA) complex, has received attentions increasingly in the field of synthetic chemistry community, due to the CT complex can absorb the visible light through the intermolecular charge transfer excited states, various of catalyst-free photochemical transformations under mild visible-light conditions. However, a number of fundamental questions are still ambiguous, such as the origin of visible light absorption, the photochemical and photophysical properties of the CT complex, as well as the detailed mechanism of the radical coupling pathways mediated by CT complex. Since these are critical factors for target-specific design and synthesis of more new-type CT complexes. To this end, theoretical investigations were performed in our group to answer these questions based on multiconfigurational perturbation theory. The photo-induced fluoroalkylation reactions are mediated by CT complexes, which are formed by the association of an acceptor of perfluoroalkyl halides RF−X (X = Br, I) and a suitable donor molecule such as β-naphtholate anion, were chosen as a paradigm example in this work. First, spectrum simulations were carried out by both CASPT2//CASSCF/PCM and TD-DFT/PCM methods. The computational results showed that the broadening spectra in visible light range (360-550nm) of the CT complexes originate from the 1(σπ*) excitation, accompanied by an intermolecular electron transfer, which was also found closely related to the aggregate states of the donor and acceptor. Moreover, from charge translocation analysis, the CT complex that showed larger charge transfer in the round state would exhibit smaller charge transfer in excited stated of 1(σπ*), causing blue shift relatively. Then, the excited-state potential energy surface (PES) was calculated at CASPT2//CASSCF(12,10)/ PCM level of theory to explore the photophysical properties of the CT complexes. The photo-induced C-X (X=I, Br) bond cleavage was found to occur in the triplet state, which is accessible through a fast intersystem crossing (ISC) process that is controlled by the strong spin-orbit coupling resulting from the heavy iodine and bromine atoms. Importantly, this rapid fragmentation process can compete and suppress the backward electron transfer (BET) event, facilitating the subsequent effective photochemical transformations. Finally, the reaction pathways of the radical coupling were also inspected, which showed that the radical chain propagation pathway could easy to accomplish with a small energy barrier no more than 3.0 kcal/mol, which is the key factor that promote the efficiency of the photochemical reactions induced by CT complexes. In conclusion, theoretical investigations were performed to explore the photophysical and photochemical properties of the CT complexes, as well as the mechanism of radical coupling reactions mediated by CT complex. The computational results and findings in this work can provide some critical insights into mechanism-based design for more new-type EDA complexes

Keywords: charge transfer complex, electron transfer, multiconfigurational perturbation theory, radical coupling

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Authors: Shuang Zhao, Shintaro Ito, Yoshihiro Ohba, Hiroshi Katagiri

Abstract:

We present the synthesis and single-crystal X-ray crystallography of a Cu(II) complex(bmn-bpy) of a pyridine-naphthoimidazole-based ligand containing two naphthoimidazoles as the chromophores and a vacant coordination site on Cu(II).

Keywords: synthesis, Cu(II) complex, single-crystal X-ray crystallography

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Authors: S. A. Gayvoronsky, T. A. Ezangina

Abstract:

The robust control system objects with interval-undermined parameters is considers in this paper. Initial information about the system is its characteristic polynomial with interval coefficients. On the basis of coefficient estimations of quality indices and criterion of the maximum stability degree, the methods of synthesis of a robust regulator parametric is developed. The example of the robust stabilization system synthesis of the rope tension is given in this article.

Keywords: interval polynomial, controller synthesis, analysis of quality factors, maximum degree of stability, robust degree of stability, robust oscillation, system accuracy

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Authors: Maria da Gloria Guara-Tavares

Abstract:

This article reports a synthesis of the research in Brazilian Sign Language conducted from 2000 to 2017. The objective of the synthesis was to identify the most researched areas and the most used methodologies. Articles published in three Brazilian journals of Translation Studies, unpublished dissertations and theses were included in the analysis. Abstracts and the method sections of the papers were scrutinized. Sixty studies were analyzed, and overall results indicate that the research in Brazilian Sign Language has been fragmented in several areas such as linguistic aspects, facial expressions, subtitling, identity issues, bilingualism, and interpretation strategies. Concerning research methods, the synthesis reveals that most research is qualitative in nature. Moreover, results show that the cognitive aspects of Brazilian Sign Language seem to be poorly explored. Implications for a future research agenda are also discussed.

Keywords: Brazilian sign language, qualitative methods, research agenda, synthesis

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Authors: Javed Iqbal

Abstract:

The growing need for energy by the human society and depletion of conventional energy sources demands a renewable, safe, infinite, low-cost and omnipresent energy source. One of the most suitable ways to solve the foreseeable world’s energy crisis is to use the power of the sun. Photovoltaic devices are especially of wide interest as they can convert solar energy to electricity. Recently the best performing solar cells are silicon-based cells. However, silicon cells are expensive, rigid in structure and have a large timeline for the payback of cost and electricity. Organic photovoltaic cells are cheap, flexible and can be manufactured in a continuous process. Therefore, organic photovoltaic cells are an extremely favorable replacement. Organic photovoltaic cells utilize sunlight as energy and convert it into electricity through the use of conductive polymers/ small molecules to separate electrons and electron holes. A major challenge for these new organic photovoltaic cells is the efficiency, which is low compared with the traditional silicon solar cells. To overcome this challenge, usually two straightforward strategies have been considered: (1) reducing the band-gap of molecular donors to broaden the absorption range, which results in higher short circuit current density (JSC) of devices, and (2) lowering the highest occupied molecular orbital (HOMO) energy of molecular donors so as to increase the open-circuit voltage (VOC) of applications devices.8 Keeping in mind the cost of chemicals it is hard to try many materials on test basis. The best way is to find the suitable material in the bulk. For this purpose, we use computational approach to design molecules based on our organic chemistry knowledge and determine their physical and electronic properties. In this study, we did DFT calculations with different options to get high open circuit voltage and after getting suitable data from calculation we finally did synthesis of a novel D–π–A–π–D type low band-gap small molecular donor material (ZOPTAN-TPA). The Aarylene vinylene based bis(arylhalide) unit containing a cyanostilbene unit acts as a low-band- gap electron-accepting block, and is coupled with triphenylamine as electron-donating blocks groups. The motivation for choosing triphenylamine (TPA) as capped donor was attributed to its important role in stabilizing the separated hole from an exciton and thus improving the hole-transporting properties of the hole carrier.3 A π-bridge (thiophene) is inserted between the donor and acceptor unit to reduce the steric hindrance between the donor and acceptor units and to improve the planarity of the molecule. The ZOPTAN-TPA molecule features a low HOMO level of 5.2 eV and an optical energy gap of 2.1 eV. Champion OSCs based on a solution-processed and non-annealed active-material blend of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and ZOPTAN-TPA in a mass ratio of 2:1 exhibits a power conversion efficiency of 1.9 % and a high open-circuit voltage of over 1.0 V.

Keywords: high open circuit voltage, donor, triphenylamine, organic solar cells

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Authors: Hossein Anaraki-Ardakani

Abstract:

A green and efficient one-pot synthesis of benzylamino coumarin derivatives by a three-component condensation of 4-hydroxycoumarin, cyclic secondary amine, and aromatic aldehyde in the presence of ZrO2 nanoparticles (NPs) as a heterogeneous catalyst in water at room temperature has been reported.

Keywords: 3-benzyl substituted coumarin derivative, ZrO2 nanoparticles (NPs), green synthesis, multicomponent reaction

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Authors: Zubi Sadiq, Ghazala Yaqub, Almas Hamid

Abstract:

We wish to report herein a very stimulating variation in Fischer indole reaction by adopting solvent and catalyst free conditions. A concise synthesis of dinitro tetrahydrocarbazole derivative 3 was introduced without the use of any accelerating agent at ambient temperature with fairly good yield. Product was fully corroborated by UV, FTIR, 1H NMR, 13C NMR, MS, and CHN analysis.

Keywords: fischer indole reaction, neutral medium, solvent free synthesis, tetrahydrocarbazole

Procedia PDF Downloads 356