Monoamine oxidases catalyze the oxidative deamination of dietary amines and amine neurotransmitters, and assist in maintaining the homeostasis of the amine neurotransmitters in the brain. Dysfunctions of these enzymes can cause neurological and behavioral disorders including Parkinson's and Alzheimer's diseases. To understand their physiological roles, efficient assay methods for monoamine oxidases are essential. Reviewed in this Perspective are the recent progress in the development of fluorescent probes for monoamine oxidases and their applications to enzyme assays in cells and tissues. It is evident that still there is strong need for a fluorescent probe with desirable substrate selectivity and photophysical properties to challenge the much unsolved issues associated with the enzymes and the diseases.

The binding of TATA-binding protein (TBP) to the TATA-box containing promoter region is aided by many other transcriptional factors including TFIIA and TFIIB. The mechanistic insight into the assembly of RNA polymerase II preinitation complex (PIC) has been gained by either directly altering a function of target protein or perturbing molecular interactions using drugs, RNAi, or aptamers. Aptamers have been found particularly useful for studying a role of a subset of PIC on transcription for their ability to inhibit specific molecular interactions. One major hurdle to the wide use of aptamers as specific inhibitors arises from the difficulty with traditional assays to validate and determine specificity, affinity, and binding epitopes for aptamers against targets. Here, using a technique called the bio-layer interferometry (BLI) designed for a label-free, real-time, and multiplexed detection of molecular interactions, we studied the assembly of a subset of PIC, TBP binding to TATA DNA, and two distinct classes of aptamers against TPB in regard to their ability to inhibit TBP binding to TFIIA or TATA DNA. Using BLI, we measured not only equilibrium binding constants ($K_D$), which were overall in close agreement with those obtained by electrophoretic mobility shift assay, but also kinetic constants of binding ($k_{on}$ and $k_{off}$), differentiating aptamers of comparable KDs by their difference in binding kinetics. The assay developed in this study can readily be adopted for high throughput validation of candidate aptamers for specificity, affinity, and epitopes, providing both equilibrium and kinetic information for aptamer interaction with targets.

Several interesting features in trajectory were observed in the direct dynamics study of formaldehyde dissociation above radical dissociation limit. The hydrogen atom deliberately placed on the radical dissociation path can turn around at some distance from C without completion of dissociation and return to HCO moiety, colliding with it just as in a radical-radical recombination and producing a highly energized molecule. Excursion of a hydrogen atom to a distance of 6-8 bohrs and migration of a hydrogen atom back and forth between C and O are two of the most interesting features exhibited by the energized molecule. A series of excursions is seen to lead to a different kind of dissociation resembling roaming-like dissociation characterized by high vibrational excitation of $H_2$ fragment. It is suggested that excursion occurs due to involvement of two different force field systems that exhibit discontinuity in 6-8 bohrs from HCO moiety. We argue that roaming is a non-zero impact parameter version of the excursion.

Non-small cell lung cancer (NSCLC) is the most common type of lung cancer representing 85% of lung cancer patients. Despite several EGFR-targeted drugs have been developed in the treatment of NSCLC, the clinical efficacy of these EGFR-targeted therapies is being challenged by the occurrence of drug resistance. In this regard, Hsp90 represents great promise as a therapeutic target of cancerous diseases due to its role in modulating and stabilizing numerous oncogenic proteins. Accordingly, inhibition of single Hsp90 protein simultaneously disables multiple signaling networks so as to overcome drug resistance in cancer. In this study, we synthesized a series of 11 butein analogues and evaluated their biological activities against gefitinibresistant NSCLC cells (H1975). Our study indicated that analogue 1h inhibited the proliferation of H1975 cells, down-regulated the expression of Hsp90 client proteins, including EGFR, Met, Her2, Akt and Cdk4, and upregulated the expression of Hsp70. The result suggested that compound 1h disrupted Hsp90 chaperoning function and could serve a potential lead compound to overcome the drug resistance in cancer chemotherapy.

The electrochemical performance of Li-S cells was investigated in various ternary electrolyte solutions composed of 1,2-dimethoxyethane (DME), tetra(ethylene glycol) dimethyl ether (TGM), and 1,3-dioxolane (DOX). The discharge capacity values and cycle data obtained at each composition were statistically treated with the Minitab program to obtain mixture contour plots, from which the optimal composition of the ternary solvent systems was predicted. The discharge capacities and capacity retention were quite dependent on the electrolyte composition. It was estimated from the contour plots of the capacity at 1.0 C that the discharge capacity sharply increased with a decrease in the TGM content. High capacities greater than 900 mAh/g at 1.0 C were expected for the electrolyte composition with a volume ratio of DME/TGM/DOX = 1/0/1. In contrast, it was predicted from the mixture contour plot of the capacity retention that the cycle performance would significantly increase with an increase in the DME content.

The nickel oxide, the most widely used cathode material for the molten carbonate fuel cell (MCFC), has several disadvantages including NiO dissolution, poor mechanical strength, and corrosion phenomena during MCFC operation. The surface modification of NiO with lanthanum maintains the advantages, such as performance and stability, and suppresses the disadvantages of NiO cathode because the modification results in the formation of $LaNiO_3$ phase which has high conductivity, stability, and catalytic activity. As a result, La-modified NiO cathode shows low NiO dissolution, high degree of lithiation, and mechanical strength, and high cell performance and catalytic activity in comparison with the pristine NiO. These enhanced physico-chemical and electrochemical properties and the durability in marine environment allow MCFC to marine application as a auxiliary propulsion system.

Metal-carbon nanoreactors (MCNRs) were prepared from a pristine carbon cage (CC) using a simple and efficient template method with nano silica ball (NSB), pyrolysis fuel oil (PFO) and transition metals, such as palladium and gold. Metal nanoparticles were embedded in approximately 25 and 170 nm sized, highly ordered carbon cages. The newly developed Pd, Au and Au-Pd doped carbon nanoreactors were characterized by microanalysis, $N_2$ adsorption-desorption isotherm, powder X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), transmission electron microscopy and inductively coupled plasma (ICP) analysis. The ordered MCNRs have exhibited dynamic hydrogen adsorption capability compared to the carbon cage.

Membrane disruption by an antimicrobial peptide (AMP) was investigated by measuring the $^2H$ solid-state nuclear magnetic resonance spectra of 1-palmitoyl-$d_{31}$-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC_$d_{31}$) in mixtures of POPC_$d_{31}$/cholesterol and either magainin 2 or aurein 3.3 deposited on thin cover-glass plates. The line shapes of the experimental $^2H$ solid-state nuclear magnetic resonance (SSNMR) spectra were best simulated by assuming the coexistence of a mosaic spread of bilayers containing pore structures and a fasttumbling isotropic phase or a hexagonal phase. Within a few days of incubation in a hydration chamber, an isotropic phase and a pore structure were induced by magainin 2, while in case of aurein 3.3 only an isotopic phase was induced in the presence of a bilayer phase. After an incubation period of over 100 days, alignment of the bilayers increased and the amount of the pore structure decreased in case of magainin 2. In contrast with magainin 2, aurein 3.3 induced a hexagonal phase at the peptide-to-lipid ratio of 1/20 and, interestingly, cholesterol was not found in the hexagonal phase induced by aurein 3.3. The experimental results indicate that magainin 2 is more effective in disrupting lipid bilayers containing cholesterol than aurein 3.3.

Molecular structures of the various conformational stereoisomers of 2,8,14,20-cyanophenyl pyrogallol[4]arenes 1 were optimized using the mPW1PW91 (hybrid Hartree-Fock density functional) calculation method. The total electronic and Gibbs free energies and the normal vibrational frequencies of the different structures from three major conformations (CHAIR, TABLE, and 1,2-Alternate) of the four stereoisomers [1(rccc), 1(rcct), 1(rctt), and 1(rtct)] were analyzed. The mPW1PW91/6-31G(d,p) calculations suggested that $1(rcct)_{1,2-A}$, 1(rctt)CHAIR, and $1(rtct)_{CHAIR}$ were the more stable conformations of the respective stereoisomers. Hydrogen bonding is the primary factor for the relative stabilities of the various conformational isomers, and maximizing the ${\pi}-{\pi}$ interaction between the cyanophenyl rings is the secondary factor. The calculated IR spectra of the more stable conformers [$1(rctt)_{CHAIR}$, $1(rcct)_{1,2-A}$, $1(rtct)_{CHAIR}$] were compared with the experimental IR spectrum of $1(rtct)_{CHAIR}$.

The kinetic studies on the reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-pyridines have been carried out in dimethyl sulfoxide. The free energy correlations with X in the nucleophiles are biphasic concave upwards with a break point at X = H, while those for substituent Z variations in the leaving groups are linear. The negative sign of ${\rho}_{XZ}$ implies that the reaction proceeds through a concerted mechanism for both the strongly and weakly basic pyridines. The biphasic concave upward free energy relationships with X are rationalized by a change in the nucleophilic attacking direction from frontside with the strongly basic pyridines to backside with the weakly basic pyridines.

Expanded polytetrafluoroethylene (ePTFE) grafts have been used as vascular access for many patients suffering from end stage renal disease. However, the vascular graft can cause significant clinical problems such as stenosis or thrombosis. For this reason, many studies have been performed to make drug eluting graft, but initial burst is major problem in almost drug eluting systems. Therefore we used biodegradable polymer to reduce initial burst and make sustained drug delivery. The ePTFE grafts were dipped into a paclitaxel-dissolved solution and then PLGA-dissolved solution was passed through the lumen of ePTFE. We analyzed whether the dose of paclitaxel is enough and the loading amount of PLGA on ePTFE graft increases according to the coating solution's concentration. Scanning electron microscope (SEM) images of various concentration of PLGA showed that the porous surface of graft was more packed with PLGA by tetrahydrofuran solution dissolved PLGA. In addition, in vitro release profiles of Ptx-PLGA graft demonstrated that early burst was gradually decreased as increasing the concentration of PLGA. These results suggest that PLGA coating of Ptx loaded graft can retard drug release, it is useful tool to control drug release of medical devices.

A novel and convenient route for the synthesis of a series of thalidomide derivatives is described. Compound 2 was cyclized with different amines under alkaline condition to obtain 4-nitro substituted phthalimidines 3a-d. Hydroxylactams 4a-d were produced via bromination and hydroxylation. Different acyl chlorides were reacted with hydroxylactams to provide the desired esters 5a-d. All compounds were evaluated by MTT assay for their inhibitory activities against HCT-116, MG-63, MCF-7, HUVEC and HMVEC cell lines in vitro. Most of them showed no obvious cytotoxic effect on normal human cells, compounds 4a-d, $5a_2$, $5a_4$, $5a_5$, $5b_2$, $5c_2$ and $5d_2$ exhibited potent antitumor activities, among which compounds $5a_2$ and $5b_2$ were more effective than 5-FU.

A cholesterol-bridge-naphthopyran dyad (NP-MCB) was designed and synthesized. NP-MCB can readily self-assemble into gels under ultrasound-radiation in several organic solvents and the formed gels easily transfer to solution by heat. This reversible process can be repeated many times. Scanning Electron Microscopy results showed that the morphologies of all formed xerogels in different solvents have fibrillar microstructure. The gels formation was due to energy and pressure afforded by the ultrasonic process, resulting in formation of molecular hydrogen bonding and molecular aggregation. NP-MCB displayed the normal photochromism both in solution and gel states. The kinetic results confirm that the colored merocyanine in gels show a slower fading speed than that in solution due to the compact aggregation of NP-MCB molecules in gels. The xerogel film formed in polar gelling solvent had large surface wettability than that in nonpolar gelling solvent.

A three-dimensional (3D) $Co_3O_4$/mildly oxidized multiwalled carbon nanotubes (moCNTs)/reduced mildly oxidized graphene oxide (rmGO) ternary composite was prepared via a simple and green hydrolysishydrothermal approach by mixing $Co(Ac)_2{\cdot}4H_2O$ with moCNTs and mGO suspension in mixed ethanol/$H_2O$. As characterized by scanning electron microscopy and transmission electron microscopy, $Co_3O_4$ nanoparticles with size of 20-100 nm and moCNTs are effectively anchored in mGO. Cyclic voltammetry and galvanostatic charge-discharge measurements were adopted to investigate the electrochemical properties of $Co_3O_4$/moCNTs/rmGO ternary composite in 6 M KOH solution. In a potential window of 0-0.6 V vs. Hg/HgO, the composite delivers an initial specific capacitance of 492 $Fg^{-1}$ at 0.5 $Ag^{-1}$ and the capacitance remains 592 $Fg^{-1}$ after 2000 cycles, while the pure $Co_3O_4$ shows obviously capacitance fading, indicating that rmGO and moCNTs greatly enhance the electrochemical performance of $Co_3O_4$.

A new conjugated copolymer, poly{4,8-bis(triisopropylsilylethynyl)benzo[1,2-b:4,5-b']dithiophene-alt-4,7- bis(5-thiophen-2-yl)-5,6-difluoro-2-(heptadecan-9-yl)-2H-benzo[d][1,2,3]triazole} (PTIPSBDT-DFDTBTz), is synthesized by Stille coupling polycondensation. The synthesized polymer has a band gap energy of 1.9 eV, and it absorbs light in the range 300-610 nm. The hole mobility of a solution-processed organic thin-film transistor fabricated using PTIPSBDT-DFDTBTz is $3.8{\times}10^{-3}cm^2V^{-1}s^{-1}$. Bulk heterojunction photovoltaic cells are fabricated, with a conventional device structure of ITO/PEDOT:PSS/polymer:$PC_{71}BM$/Ca/Al ($PC_{71}BM$ = [6,6]-phenyl-$C_{71}$-butyric acid methyl ester); the device shows a power conversion efficiency (PCE) of 2.86% with an open-circuit voltage ($V_{oc}$) of 0.85 V, a short-circuit current density ($J_{sc}$) of 7.60 mA $cm^{-2}$, and a fill factor (FF) of 0.44. Inverted photovoltaic cells with the structure ITO/ethoxylated polyethlyenimine/ polymer:$PC_{71}BM/MoO_3$/Ag are also fabricated; the device exhibits a maximum PCE of 2.92%, with a $V_{oc}$ of 0.89 V, a $J_{sc}$ of 6.81 mA $cm^{-2}$, and an FF of 0.48.

Thirteen analogs of tridecapeptide ${\alpha}$-factor (WHWLQLKPGQPMY) of Saccharomyces cerevisiae with C- or N-terminal Trp extension and isosteric replacement by Aib at position 8 and 11, Trp at position 13, D-Ala at position 9, and Orn and Glu at position 6 were synthesized and assayed for their biological activity. Receptor binding assay was carried out using our newly developed spectrophotometric method with detector peptide 14. C- or N-terminal extended analogs, ${\alpha}$-factor-$[Trp]_n$ (n =1-5) 1-5 and $[N-Trp]_1$-${\alpha}$-factor 6, were all less active than native ${\alpha}$-factor and gradual decreases in both activity and receptor affinity were observed with greater Trp extension. Trp-substituted analog at position 13, $[Trp^{13}]{\alpha}$-factor 7, exhibited about 2-fold reductions in both activity and receptor affinity. Aib-substituted analogs, $[Aib^8]{\alpha}$-factor 8 and $[Aib^{11}]{\alpha}$-factor 9, showed 5- to 10-fold reduction in activity as well as 3-fold reduction in receptor affinity compared to native ${\alpha}$-factor. $[Orn^6]{\alpha}$-factor 10 demonstrated strong potency with a 7.0-fold increase in halo activity as well as 1.8-fold increase in receptor affinity compared to native ${\alpha}$-factor. For two double substituted analogs, [$Glu^6,{\small{D}}-Ala^9$]${\alpha}$-factor 12 showed the slightly decreased potency in halo activity compared to analog 10, whereas [$Orn^6,{\small{D}}-Ala^9$]${\alpha}$-factor 11 exhibited 15-fold higher halo activity as well as nearly 3-fold higher receptor affinity compared to native ${\alpha}$-factor.

In this study, maghemite (${\gamma}-Fe_2O_3$) nanoparticles were produced using gelatin protein as an effective mediator. Size, shape, surface morphology and magnetic properties of the prepared ${\gamma}-Fe_2O_3$ nanoparticles were characterized using XRD, FT-IR, TEM, SEM and VSM data. The effects of furnace temperature and time of heating together with the amount of gelatin on the produced gelatin-$Fe_3O_4$ nanocomposite were examined to prove the fundamental effect of gelatin; both as a capping agent in the nanoscale synthesis and as the director of the spinel ${\gamma}-Fe_2O_3$ synthesis among possible $Fe_2O_3$ crystalline structures.

${\alpha}-Fe_2O_3$ spherical particles having an average diameter of ca. 420 nm and ${\alpha}-Fe_2O_3$ fine particles (< 10 ${\mu}m$ particle size) were prepared to examine as catalysts for CO oxidation. Kinetic studies on the catalytic reactions were performed in a flow reactor using an on-line gas chromatography system operated at 1 atm. The apparent activation energies and the partial orders with respect to CO and $O_2$ were determined from the rates of CO disappearance in the reaction stage showing a constant catalytic activity. In the temperature range of $150-275^{\circ}C$, the apparent activation energies were calculated to be 13.7 kcal/mol on the ${\alpha}-Fe_2O_3$ spherical submicron clusters and 15.0 kcal/mol on the ${\alpha}-Fe_2O_3$ fine powder. The Pco and $Po_2$ dependencies of rate were investigated at various partial pressures of CO and $O_2$ at $250^{\circ}C$. Zero-order kinetics were observed for $O_2$ on both the catalysts, but the reaction order for CO was observed as first-order on the ${\alpha}-Fe_2O_3$ fine powder and 0.75-order on the ${\alpha}-Fe_2O_3$ spherical submicron clusters. The catalytic processes including the inhibition process by $CO_2$ on the ${\alpha}-Fe_2O_3$ spherical submicron powder are discussed according to the kinetic results. The catalysts were characterized using XRD (X-ray powder diffraction), FE-SEM (field emission-scanning electron microscopy), HR-TEM (high resolution-transmission electron microscopy), and $N_2$ sorption measurements.

Hydrofluoroethers (HFEs) are developed as a suitable for the replacement of environmentally hazardous CFCs and are termed as third generation refrigerants. One of the major products of decomposition of HFEs in the atmosphere is a fluoroester. The present study relates to the OH and Cl initiated oxidation of $CF_3C(O)OCH_2CF_3$ formed from the oxidation of HFE-356mff. The latter is used as a solvent in the industry and reaches the atmosphere without any degradation. Kinetics of the titled molecule has been studied at MPWB1K/6-31+G(d,p) level of theory. Single point energy calculations have been made at G2(MP2) level of theory and barrier heights are determined. The rate constants are calculated using canonical transition state theory. Tunnelling correction are made using one-dimensional Eckart potential barrier. The rate constant calculated during the present study are compared with the experimental values determined using relative rate method and FTIR detection technique.

In the present study, ten metal free non-linear optical (NLO) compounds have been designed. These compounds have designed by structural modification of (2-cyano-5-(4-(phenyl(4-vinylphenyl)amino)phenyl) penta-2,4-dienoic acid (TC4). Density functional theory was used for structure optimization and determination of photo-physical properties. These compounds contain triphenylamine as electron-donor and cyanoacrylic acid as acceptor. Five ${\pi}$-spacers are used to connect the donor and acceptor. Two auxiliary donors are also used to assist the donor. Results of this study indicate that stronger electron-donating auxiliary groups and longer ${\pi}$-conjugation enhance NLO response. Major absorption peaks of all systems were in the visible region. These absorption peaks are associated with the ${\pi}-{\pi}^*$ transitions of the entire molecule. From calculations it is clear that all system will be good NLO material. The present calculations will provide new ways for experimentalists to synthesize high-performance NLO material.

The complete active space self-consist field method followed by the internally contracted multireference configuration interaction method has been used to compute the potential energy curves of $X^2\prod_g$, $a^4\prod_u$, $A^2\prod_u$, $b^4\sum_{g}^{-}$, and $B^2\sum_{g}^{-}$ states of $S{_2}^+$ cation with large correlation-consistent basis sets. Utilizing the potential energy curves computed with different basis sets, the spectroscopic parameters of these states were evaluated. Finally, the transition dipole moment and the Franck-Condon factors of the transition from $A^2\prod_u$ to $X^2\prod_g$ were evaluated. The radiative lifetime of $A^2\prod_u$ is calculated to be 887 ns, which is in good agreement with experimental value of $805{\pm}10$ ns.

The cycloaddition reactions of the N-heterocyclic carbene boryl azide with methyl acrylate, butenone, and hexafluoropropene have been investigated theoretically. Solvent effects on these reactions have been explored by calculation that included a polarizable continuum model (PCM) for the solvent (C6H6). The title reaction could produce 4- and 5-substituted 1,2,3-triazolines, respectively. The reaction systems have the higher chemical reactivity with the low barriers and could be favored. Yet the smaller differences have been found to occur in energetics, and the cycloaddition reactions occur for s-trans conformations over s-cis conformations. The calculations indicated that the cycloaddition reaction of the alkenes have certain regioselectivity.

Sex hormones are important metabolites in vertebrates' development and reproduction. For rapid screening sex hormones, matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is one of the promising analytical platforms, but MALDI MS faces many challenges in detecting steroids such as low ionization efficiency and matrix background interference. One potential strategy to overcome matrix interference in the low m/z region is using a cyclodextrin (CD)-supported matrix for steroid analysis since CD-supported matrixes are known to effectively suppress matrix-related ion signals. In this study, we aimed to find the optimal CD-supported matrix for the analysis of the nonderivatized sex steroids. Our results showed that the ${\alpha}CD$-supported 2,5-dihydroxybenzoic acid (DHB) matrix efficiently ionized all three major classes of sex hormones, estrogens, androgens, and progestagens, with low or no matrix background and also with high sensitivity. In addition, the ${\alpha}CD$-supported DHB matrix mainly generated molecular ions or protonated ions of sex hormones, and this enabled us to obtain information-rich tandem mass spectra which potentially lead to unambiguous identification of steroid species from complex metabolite mixtures.

A novel topological index (TG Index) has been introduced. The graphical matrix representation of the TG index includes the use of directed subgraphs for the first time in graph theory literature. The application of the TG index on certain properties of polyenes yielded very well correlation data.

Five new lanthanide coordination polymers, $[Ln_2(1,4-NDC)_2(1,4-HNDC)_2(phen)_2]_n$ (Ln = Er (1), Yb (2)), and $[Ln_2(1,4-NDC)_3(phen)_2(H_2O)_2]_n$ (Ln = Nd (3), Gd (4), Er (5)) ($1,4-H_2NDC$ = 1,4-naphthalenedicarboxylic acid, phen = 1,10-phenanthroline), have been successfully prepared via the reaction of corresponding trivalent lanthanide salt, $1,4-H_2NDC$ and phen in the presence of NaOH and pyridine under hydrothermal condition. Pyridine plays a key role in the synthesis of these lanthanide coordination polymers. Single-crystal X-ray diffraction analyses indicate that compounds 1-5 all form a 2-D network while different salt anions result in the diversity of crystal structures. These lanthanide coordination polymers showed a considerable thermal stability in TGA analyses.

Convergent all-electron multi-reference configuration-interaction (MRCI) calculations are performed for a lithium dimer with Kaufmann's Rydberg basis functions. A comparison of the results of these calculations with those of the effective core potential/core polarization potential (ECP/CPP) method and experimental data reveals the deficiency of the all-electron ab initio method. The deficiency is related to the mere 51.9% attainment of electron correlation for the ground state. The percent attainment of electron correlation for the first excited state is slightly better than that for the ground state, preventing us from obtaining better agreements with experimental data by means of increasing the size of basis sets. The Kaufmann basis functions are then used with the ECP/CPP method to obtain the accurate convergent potential energy curves for the $^1\prod_u$ states correlated to Li(2p) + Li(2p) and Li(2s) + Li(n = 2, 3, 4). Quantum defect curves (QDCs) calculated for both the $X^2\sum_g$ and 1 $^2\prod_u$ states of the $Li{_2}^+$ ion and the Lu-Fano plot reveal a strong series-series interaction between the two $2snp{\pi}$ and $2pnp{\pi}$ Rydberg series. The QDCs are then used to resolve assignment problems in the literature. The reassignments, performed by Jedrzejewski-Szemek et al., of the dissociation product of the D $^1\prod$ state from (2s+3d) to (2s+3p) and that of the 6 $^1\prod_u$ from (2s+4d) to (2s+4p) are found to be incorrect. It may be more natural to assign their $2snp{\pi}$ Rydberg series as a $2snd{\pi}$ series. The state, assigned as 5p $^1\prod_u$ by Ross et al. and 4d $^1\prod$ by Jedrzejewski-Szemek et al., is assigned as the 7 $^1\prod_u$ state, correlated to the Li(2s) + Li(4f) limit.

We report on the influence of water as an electrolyte on the photovoltaic performances. The photovoltaic performance was shown to be quite sensitive to the substituent on the donor group. An optimized efficiency of 4.41% in the presence of 100% water content using $I^-/I{_3}^-$ redox couple was obtained using the D21L6 organic dye.

Co(II)-tetrasulfonated phthalocyanine (CoTSP) is known to be aggregated to dimer at high concentration levels in water. A study on the aggregation of CoTSP using multivariate curve resolution analysis of the visible absorbance spectra over a concentration range of 30, 40 and 50 ${\mu}M$ in the presence of dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), acetonitrile (AN) and ethanol (EtOH) in the concentration range of 0 to 3.57 M is conducted. A hard modeling-based multivariate curve resolution method was applied to determine the dissociation constants of the CoTSP aggregates at various temperatures ranging from 25, 45 and $65^{\circ}C$ and in the presence of various co-solvents. Dissociation constant for aggregation was increased and then decrease by temperature and concentration of phthalocyanine, respectively. Utilizing the vant Hoff relation, the enthalpy and entropy of the dissociation equilibriums were calculated. For the dissociation of both aggregates, the enthalpy and entropy changes were positive and negative, respectively. Molecular dynamics simulation of cosolvent effect on CoTSP aggregation was done to confirm spectroscopy results. Results of radial distribution function (RDF), root mean square deviation (RMSD) and distance curves confirmed more effect of polar solvent to decrease monomer formation.

The co-sensitization of N719 with a cyclic thiourea functionalized organic dye, coded AZ5, for dye-sensitized solar cells (DSSCs) was demonstrated. Due to its intensive absorption in ultraviolet region, AZ5 could compensate the loss of light harvest induced by triiodide, thereby the short-circuit photocurrent density ($J_{sc}$) was increased for co-sensitized (N719+AZ5) DSSC. Moreover, the electron recombination and dye aggregation were retarded upon N719 cocktail co-sensitized with AZ5, thus the open-circuit voltage ($V_{oc}$) of co-sensitized device was enhanced as well. The increased $J_{sc}$ (17.9 $mA{\cdot}cm^{-2}$) combined with the enhanced $V_{oc}$ (698 mV) ultimately resulted in an improved power conversion efficiency (PCE) of 7.91% for co-sensitized DSSC, which was raised by 8.6% in comparison with that of N719 (PCE = 7.28%) sensitized alone. In addition, co-sensitized DSSC exhibited a better stability than that of N719 sensitized device probably due to the depression of dye desorption.

We report a sensitive and reliable FRET-based nanotechnology assay for efficient detection and quantification of bisulfite-unmodified or modified DNA. Bisulfite-untreated DNA or bisulfite-treated DNA is subjected to PCR amplification with biotin-conjugated primers so that the amounts of bisulfite-untreated and treated DNA can be differentiated. Streptavidin-coated quantum dots (QDs) are used to capture biotinylated PCR products intercalated with SYBR Green, enabling FRET measurement. Key features of our method include its low intrinsic background noise, high resolution, and high sensitivity, enabling detection of as little as 1.75 ng of bisulfite-untreated DNA in the presence of an approximately 1,000-fold excess of bisulfite-untreated DNA compared to bisulfate-treated DNA, with the use of PCR reduced (as low as 15 cycles). SYBR Green as an intercalating dye as well as a FRET acceptor allows for a single-step preparation without the need for primers or probes to be chemically conjugated to an organic fluorophore. Multiple acceptors per FRET donor significantly enhance the signal-to-noise ratio as well. In consideration of the high relevance of bisulfite treatment to DNA methylation quantitation, our system for FRET measurement between QDs and intercalating dyes can be generally utilized to analyze DNA methylation and to potentially benefit the scientific and clinical community.

The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at $35.0^{\circ}C$. The two strong ${\pi}$-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Br$\ddot{o}$nsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (${\rho}_{XY}$ = -6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (${\rho}_{XY}$ = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ${\rho}_{XY}$ values imply frontside nucleophilic attack transition state.

In this study, an intermediate temperature ionic conductor, $Ce_{0.95}Eu_{0.05}P_2O_7$, was prepared by solid state reaction. The variation of conductivities with the pressure $pH_2O$ or time were studied. The highest conductivity of $Ce_{0.95}Eu_{0.05}P_2O_7$ sample was observed in dry air atmosphere at $300^{\circ}C$ to be $1.1{\times}10^{-4}S{\cdot}cm^{-1}$ and in wet air atmosphere ($pH_2O=7.4{\times}10^3Pa$) at $100^{\circ}C$ to be $1.4{\times}10^{-3}S{\cdot}cm^{-1}$, respectively. The log ${\sigma}$ ~ log ($pO_2$) plot result indicated that $Ce_{0.95}Eu_{0.05}P_2O_7$ was almost a pure ionic conductor under high oxygen partial pressure and a mixed conductor of ion and electron under low oxygen partial pressure.

Use of acetonitrile in electrolytes promotes better operation of supercapacitors. Recent efforts show that electrolytes containing acetonitrile can also function in a wide range of operating temperatures. Therefore, this paper addresses the dielectric relaxation processes, structure and dynamic properties of the bulk acetonitrile at various temperatures. Systems of acetonitrile were modeled using canonical ensemble and simulated by employing Molecular Dynamics method. Results show that interactions among the molecules were correlated within a cut-off radius while parallel and anti-parallel arrangements are observed beyond this radius at relatively high and low temperatures respectively. Furthermore, effects of C-C-N and C-H bending modes were greatly appreciated on the power spectral density of time rate change of dipole-dipole correlations whereas frequency shifts were observed on all modes at the lowest temperature under consideration. Linear variations with temperature were depicted for reorientation times and self-diffusion coefficients. Shear viscosity was also computed with a good accuracy within a certain range of the temperature as well.

Based on the full optimized molecular geometric structures at B3LYP/cc-pvtz method, a new designed compound, 4,6,8-trinitro-4,5,7,8-tetrahydro-6H-furazano[3,4-f ]-1,3,5-triazepine was investigated in order to look for high energy density compounds (HEDCs). The analysis of the molecular structure indicates that the seven-membered ring adopts chair conformation and there exist intramolecular hydrogen bond interactions. IR spectrum and heat of formation (HOF) were predicted. The detonation velocity and pressure were evaluated by using Kamlet-Jacobs equations based on the theoretical density and condensed HOF. The bond dissociation energies and bond orders for the weakest bonds were analyzed to investigate the thermal stability of the title compound. The results show that $N_1-N_6$ bond is the trigger bond. The crystal structure obtained by molecular mechanics belongs to $Pna2_1$ space group, with lattice parameters Z = 4, a = 15.3023 ${\AA}$, b = 5.7882 ${\AA}$, c = 11.0471 ${\AA}$, ${\rho}=2.06gcm^{-3}$. In addition, the analysis of frontier molecular orbital shows the title compound has good stability and high chemical hardness.

We have designed and developed a new ladder type tetrafused ${\pi}$-conjugated building block such as dihydroindolo[3,2-b]indole (DINI) and investigated its role as an electron rich unit. The photovoltaic properties of a new semiconducting ${\pi}$-conjugated polymer, poly[[5,10-bisoctyl-5,10-dihydroindolo[3,2-b]indole-[5,6- bis(octyloxy)-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole]], represented by PDINI-OBTC8 are described. The new polymer PDINI-OBTC8 was synthesized in donor-acceptor (D-A) fashion, where fused ${\pi}$-conjugated tetracyclic DINI, and 5,6-bis(octyloxy)-4,7-di(thiophen-2-yl) benzo[c][1,2,5]thiadiazole (OBTC8) were employed as electron rich (donor) and electron deficient (acceptor) moieties, respectively. The conventional bulk heterojunction (BHJ) device structure ITO/PEDOT:PSS/PDINI-OBTC8:PCB71M/LiF/Al was utilized to fabricate polymer solar cells (PSCs), which comprises the blend of PDINI-OBTC8 and [6,6]-phenyl-$C_{71}$-butyric acid methyl ester ($PC_{71}BM$) in BHJ network. A BHJ PSC that contain PDINI-OBTC8 delivered power conversion efficiency (PCE) value of 1.68% with 1 vol% of 1,8-diidooctane (DIO) under the illumination of A.M 1.5G 100 $mW/cm^2$.

High-crystallinity poly(3-hexylthiophene) (P3HT) thin films were prepared by aging the precursor solutions, prepared using a good solvent, chloroform, at low temperatures prior to spin-casting. Lower solution temperatures significantly improved the molecular ordering in the spin-cast P3HT films and, therefore, the electrical properties of field-effect transistors prepared using these films. Solution cooling enhanced the electrical properties by shifting the P3HT configuration equilibrium away from random coils and toward more ordered aggregates. At room temperature, the P3HT molecules were completely solvated in chloroform and adopted a random coil conformation. Upon cooling, however, the chloroform poorly solvated the P3HT molecules, favoring the formation of ordered P3HT aggregates, which then yielded more highly crystalline molecular ordering in the P3HT thin films produced from the solution.

Two new complexes with 5-methyl-1-(pyridine-3-yl)-1H-1,2,3-triazole-4-carboxylic acid (Hmptc) ligand: [$Cd(mptc)_2(H_2O)_4$] (1) and $[Cu(mptc)_4{\cdot}2H_2O]_n$ (2) were prepared and their crystal structures were determined by single crystal X-ray diffraction analyses. In complex 1, the Cd(II) ions coordinates with the pyridyl nitogen atom from the Hmptc ligand, forming a mononuclear Cd(II) compound. Complex 2 exhibits a novel two-dimensional (2D) polymer in which four Hmptc ligands stabilize the Cu(II) atom. And the coordination involves one nitrogen atom of the triazole, one oxygen atom of the carboxylic acid and the pyridyl nitrogen atom. In addition, FT-IR and solid-state fluorescent emission spectroscopy of two compounds have been determined.

Molecular dynamics simulations were performed to understand the structural arrangement of water molecules around highly charged nanoparticles under aqueous conditions. The effect of two highly charged nanoparticles on the solvation charge asymmetry has been examined. We calculated the radial distribution functions of the components of water molecules around nanoparticles which have four charge types at two different salt concentrations. Even though the distributions of water molecules surrounding a sodium ion and a chloride ion are hardly affected by the charges of nanoparticles and the salt concentrations, those around highly charged nanoparticles are strongly influenced by the charges of nanoparticles, but hardly by the charges of nanoparticles and salt concentrations. We find that the distributions of hydrogen atoms in water molecules around one highly charged nanoparticle are dependent on the magnitude of the nanoparticle charge.

A kinetic study on nucleophilic substitution reaction of 5-nitro-8-quinolyl picolinate (6) with alkali-metal ethoxides (EtOM; M = K, Na, and Li) in anhydrous ethanol is reported. The plot of $k_{obsd}$ vs. [EtOM] curves upward in the absence of crown ethers but is linear with significantly decreased reactivity in the presence of crown ethers. Dissection of $k_{obsd}$ into $k_{EtO}$- and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is significantly more reactive than the dissociated $EtO^-$ (e.g., $k_{EtOM}/k_{EtO^-}$ = 33.4-141). This indicates that the reaction of 6 is catalyzed by $M^+$ ions in the order $Na^+$ > $Li^+$ > $K^+$ and the catalytic effect disappears in the presence of a proper crown ether. Picolinate ester 6 is much more reactive and is more strongly catalyzed by $M^+$ ions than 5-nitro-8-quinolyl benzoate (5). It has been concluded that $M^+$ ions catalyze the reaction of 6 by increasing electrophilicity of the reaction center through a cyclic transition state, which is structurally not possible for the reaction of 5.

The multiconfiguration second-order perturbation theory (CASPT2) and complete active space self-consistent field (CASSCF) methods were employed to calculate the geometries and energy levels for the low-lying electronic states of 1,3,5-$C_6H_3Cl{_3}^+$ ion. The CASPT2 values for the 1,3,5-$C_6H_3Cl{_3}^+$ ion were in reasonable agreement with the available experimental values. The current calculations augmented previous theoretical investigations on the ground state and assigned the low-lying excited electronic states of the 1,3,5-$C_6H_3Cl{_3}^+$ ion. The Jahn-Teller distortion in the excited electronic state for the 1,3,5-$C_6H_3Cl{_3}^+$ ion were reported for the first time.

A series of 20 wt % $(NH_4)_2SO_4$ and 3 wt % $Al_2O_3$ surface treatments were applied to $Li[Li_{0.2}Mn_{0.54}Co_{0.13}Ni_{0.13}]O_2$ substrates. The $Li[Li_{0.2}Mn_{0.54}Co_{0.13}Ni_{0.13}]O_2$ substrates were synthesized using a co-precipitation method. Sample (a) was left pristine and variations of the 20 wt % $(NH_4)_2SO_4$ and 3 wt % $Al_2O_3$ were applied to samples (b), (c) and (d). XRD was used to verify the space group of the samples as R$\bar{3}$m. Additional morphology and particle size data were obtained using SEM imagery. The $Al_2O_3$ coating layers of sample (b) and (d) were confirmed by TEM images and EDS mapping of the SEM images. 2032-type coin cells were fabricated in a glove box in order to investigate their electrochemical properties. The cells were charged and discharged at room temperature ($25^{\circ}C$) between 2.0V and 4.8V during the first cycle. The cells were then charged and discharged between 2.0V and 4.6V in subsequent cycles. Sample (d) exhibited lower irreversible capacity loss (ICL) in the first charge-discharge cycle as compared to sample (c). Sample (d) also had a higher discharge capacity of ~250 mAh/g during the first and second charge-discharge cycles when compared with sample (c). The rate capability of the $Al_2O_3$-coated sample (b) and (d) was lower when compared with sample (a) and (c). Sample (d), coated with $Al_2O_3$ after the surface treatment with $(NH_4)_2SO_4$, showed an improvement in cycle performance as well as an enhancement of discharge capacity. The thermal stability of sample (d) was higher than that of the sample (c) as the result of DSC.

Silicon quantum dots (Si QDs) were synthesized by etching silicon nanopowder with aqueous hydrofluoric acid (HF) and nitric acid ($HNO_3$). Then, the hydride-terminated Si QDs (H-Si QDs) were functionalized by 1- octadecene (ODE). By only controlling the etching time, the maximum luminescence peak of octadecylterminated Si QDs (ODE-Si QDs) was tuned from 404 nm to 507 nm. The average optical gap was increased from 2.60 eV (ODE-Si QDs-5 min) for 5 min of etching to 3.20 eV (ODE-Si QDs-15 min) for 15 min of etching, and to 3.40 eV (ODE-Si QDs-30 min) for 30 min of etching. The electron affinities (EA), ionization potentials (IP), and quasi-particle gap (${\varepsilon}^{qp}_{gap}$) of the Si QDs were determined by cyclic voltammetry (CV). The quasi-particle gaps obtained from the CV were in good agreement with the average optical gap values from UV-vis absorption. In the case of the ODE-Si QDs-30 min sample, the difference between the quasi-particle gap and the average optical gap gives the electron-hole Coulombic interaction energy. The additional electronic levels of the ODE-Si QDs-30 min and ODE-Si QDs-15 min samples determined by the CV results are interpreted to have originated from the Si=O bond terminating Si QD.