WorldWideScience

Sample records for 1,2-ethanedithiol

  1. Organic-Inorganic Hybrid Solution-Processed H-2-Evolving Photocathodes

    Lai, Lai-Hung; Gomulya, Widianta; Berghuis, Matthijs; Protesescu, Loredana; Detz, Remko J.; Reek, Joost N. H.; Kovalenko, Maksym V.; Loi, Maria A.

    2015-01-01

    Here we report for the first time an H-2-evolving photocathode fabricated by a solution-processed organic inorganic hybrid composed of CdSe and P3HT. The CdSe:P3HT (10:1 (w/w)) hybrid bulk heterojunction treated with 1,2-ethanedithiol (EDT) showed efficient water reduction and hydrogen generation. A

  2. Impact of Different Surface Ligands on the Optical Properties of PbS Quantum Dot Solids

    Fan Xu; Luis Felipe Gerlein; Xin Ma; Chelsea R. Haughn; Doty, Matthew F.; Cloutier, Sylvain G.

    2015-01-01

    The engineering of quantum dot solids with low defect concentrations and efficient carrier transport through a ligand strategy is crucial to achieve efficient quantum dot (QD) optoelectronic devices. Here, we study the consequences of various surface ligand treatments on the light emission properties of PbS quantum dot films using 1,3-benzenedithiol (1,3-BDT), 1,2-ethanedithiol (EDT), mercaptocarboxylic acids (MPA) and ammonium sulfide ((NH4)2S). We first investigate the influence of differen...

  3. Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

    Takanabe, Kazuhiro

    2015-03-05

    The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

  4. Narrow Band Gap Lead Sulfide Hole Transport Layers for Quantum Dot Photovoltaics.

    Zhang, Nanlin; Neo, Darren C J; Tazawa, Yujiro; Li, Xiuting; Assender, Hazel E; Compton, Richard G; Watt, Andrew A R

    2016-08-24

    The band structure of colloidal quantum dot (CQD) bilayer heterojunction solar cells is optimized using a combination of ligand modification and QD band gap control. Solar cells with power conversion efficiencies of up to 9.33 ± 0.50% are demonstrated by aligning the absorber and hole transport layers (HTL). Key to achieving high efficiencies is optimizing the relative position of both the valence band and Fermi energy at the CQD bilayer interface. By comparing different band gap CQDs with different ligands, we find that a smaller band gap CQD HTL in combination with a more p-type-inducing CQD ligand is found to enhance hole extraction and hence device performance. We postulate that the efficiency improvements observed are largely due to the synergistic effects of narrower band gap QDs, causing an upshift of valence band position due to 1,2-ethanedithiol (EDT) ligands and a lowering of the Fermi level due to oxidation.

  5. Au-nanoparticles grafted on plasma treated PE

    Svorcik, V., E-mail: vaclav.svorcik@vscht.c [Department of Solid State Engineering, Institute of Chemical Technology, 166 28 Prague (Czech Republic); Chaloupka, A. [Department of Solid State Engineering, Institute of Chemical Technology, 166 28 Prague (Czech Republic); Rezanka, P. [Department of Analytical Chemistry, Institute of Chemical Technology, Prague (Czech Republic); Slepicka, P. [Department of Solid State Engineering, Institute of Chemical Technology, 166 28 Prague (Czech Republic); Kolska, Z. [Department of Chemistry, J.E. Purkyne University, 400 96 Usti nad Labem (Czech Republic); Kasalkova, N.; Hubacek, T.; Siegel, J. [Department of Solid State Engineering, Institute of Chemical Technology, 166 28 Prague (Czech Republic)

    2010-03-15

    Polyethylene (PE) surface was treated with Ar plasma. Activated surface was grafted from methanol solution of 1,2-ethanedithiol. Then the sample was immersed into freshly prepared colloid solution of Au-nanoparticles. Finally Au layer was sputtered on the samples. Properties of the modified PE were studied using various methods: AFM, EPR, RBS and nanoindentation. It was shown that the plasma treatment results in degradation of polymer chain (AFM) and creation of free radicals by EPR. After grafting with dithiol, the concentration of free radicals declines. The presence of Au and S in the surface layer after the coating with Au-nanoparticles was proved by RBS. Plasma treatment changes PE surface morphology and increases surface roughness, too. Another significant change in surface morphology and roughness was observed after deposition of Au-nanoparticles. Nanoindentation measurements show that the grafting with Au-nanoparticles increases adhesion of subsequently sputtered Au layer.

  6. Au-nanoparticles grafted on plasma treated PE

    Švorčík, V.; Chaloupka, A.; Řezanka, P.; Slepička, P.; Kolská, Z.; Kasálková, N.; Hubáček, T.; Siegel, J.

    2010-03-01

    Polyethylene (PE) surface was treated with Ar plasma. Activated surface was grafted from methanol solution of 1,2-ethanedithiol. Then the sample was immersed into freshly prepared colloid solution of Au-nanoparticles. Finally Au layer was sputtered on the samples. Properties of the modified PE were studied using various methods: AFM, EPR, RBS and nanoindentation. It was shown that the plasma treatment results in degradation of polymer chain (AFM) and creation of free radicals by EPR. After grafting with dithiol, the concentration of free radicals declines. The presence of Au and S in the surface layer after the coating with Au-nanoparticles was proved by RBS. Plasma treatment changes PE surface morphology and increases surface roughness, too. Another significant change in surface morphology and roughness was observed after deposition of Au-nanoparticles. Nanoindentation measurements show that the grafting with Au-nanoparticles increases adhesion of subsequently sputtered Au layer.

  7. Impact of Different Surface Ligands on the Optical Properties of PbS Quantum Dot Solids

    Fan Xu

    2015-04-01

    Full Text Available The engineering of quantum dot solids with low defect concentrations and efficient carrier transport through a ligand strategy is crucial to achieve efficient quantum dot (QD optoelectronic devices. Here, we study the consequences of various surface ligand treatments on the light emission properties of PbS quantum dot films using 1,3-benzenedithiol (1,3-BDT, 1,2-ethanedithiol (EDT, mercaptocarboxylic acids (MPA and ammonium sulfide ((NH42S. We first investigate the influence of different ligand treatments on the inter-dot separation, which mainly determines the conductivity of the QD films. Then, through a combination of photoluminescence and transient photoluminescence characterization, we demonstrate that the radiative and non-radiative recombination mechanisms in the quantum dot films depend critically on the length and chemical structure of the surface ligands.

  8. Synthesis of nanoparticle/ligand composite thin films by sequential ligand self assembly and surface complex reduction.

    Muench, Falk; Fuchs, Anne; Mankel, Eric; Rauber, Markus; Lauterbach, Stefan; Kleebe, Hans-Joachim; Ensinger, Wolfgang

    2013-01-01

    Nanocomposite thin films consisting of ligand-connected metal nanoparticles were deposited by iteration of ligand assembly, surface complex formation and reduction. This novel and convenient approach combines characteristics of the layer-by-layer (LbL) and the successive ion layer adsorption and reaction (SILAR) techniques. In contrast to classical LbL assembly, the nanoparticle formation is performed in situ, avoiding separate reduction, protection and attachment steps. To demonstrate the versatility of the approach, different metal precursors (Pd, Ag and Au salts) and linkers (1,2-ethanedithiol, 1,4-benzenedithiol and polythiol) were applied. The formation of dithiol-linked nanoparticle films was confirmed by TEM and XPS. By combining the deposition protocol with ion track etched polycarbonate templates, nanotubes and nanowires with high aspect ratios of up to 300 could be fabricated.

  9. Dithiolate complexes of manganese and rhenium: X-ray structure and properties of an unusual mixed valence cluster Mn3(CO)6(mu-eta2-SCH2CH2CH2S)3.

    Begum, Noorjahan; Hyder, Md Iqbal; Kabir, Shariff E; Hossain, G M Golzar; Nordlander, Ebbe; Rokhsana, Dalia; Rosenberg, Edward

    2005-12-26

    Treatment of Mn(2)(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO.2H(2)O in CH(2)Cl(2) at room temperature afforded the dinuclear complexes Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (1), and Mn(2)(CO)(6)(mu-eta(4)-SCH(2)CH(2)S-SCH(2)CH(2)S) (2), respectively. Similar reactions of Re(2)(CO)(10) with 3,4-toluenedithiol, 1,2-benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (3), Re(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S) (4), and Re(2)(CO)(6)(SCH(2)CH(2)S-SCH(2)CH(2)S) (5), respectively. In contrast, treatment of Mn(2)(CO)(10) with 1,3-propanedithiol afforded the trimanganese compound Mn(3)(CO)(6)(mu-eta(2)-SCH(2)CH(2)CH(2)S)(3) (6), whereas Re(2)(CO)(10) gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques.

  10. Improved performance of nanowire-quantum-dot-polymer solar cells by chemical treatment of the quantum dot with ligand and solvent materials.

    Nadarajah, A; Smith, T; Könenkamp, R

    2012-12-07

    We report a nanowire-quantum-dot-polymer solar cell consisting of a chemically treated CdSe quantum dot film deposited on n-type ZnO nanowires. The electron and hole collecting contacts are a fluorine-doped tin-oxide/zinc oxide layer and a P3HT/Au layer. This device architecture allows for enhanced light absorption and an efficient collection of photogenerated carriers. A detailed analysis of the chemical treatment of the quantum dots, their deposition, and the necessary annealing processes are discussed. We find that the surface treatment of CdSe quantum dots with pyridine, and the use of 1,2-ethanedithiol (EDT) ligands, critically improves the device performance. Annealing at 380 °C for 2 h is found to cause a structural conversion of the CdSe from its initial isolated quantum dot arrangement into a polycrystalline film with excellent surface conformality, thereby resulting in a further enhancement of device performance. Moreover, long-term annealing of 24 h leads to additional increases in device efficiency. Our best conversion efficiency reached for this type of cell is 3.4% under 85 mW cm(-2) illumination.

  11. Gallium sulfide and indium sulfide nanoparticles from complex precursors: Synthesis and characterization

    Dutta, D.P. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)]. E-mail: duttadimple@yahoo.co.in; Sharma, G. [Materials Science Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Tyagi, A.K. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Kulshreshtha, S.K. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

    2007-03-15

    Nanocrystalline gallium sulfide (Ga{sub 2}S{sub 3}) and indium sulfide (In{sub 2}S{sub 3}) have been prepared by a two-step process. The first step involves metathesis reaction of trimethyl gallium/indium ether adduct (Me{sub 3}Ga/In.OEt{sub 2}) with 1,2-ethanedithiol (HSCH{sub 2}CH{sub 2}SH) resulting in the formation of a polymeric precursor. The precursor complex has been characterized using Ga/In analysis, IR, proton NMR and mass spectroscopy. The thermal behavior of both complexes has been studied using thermogravimetric (TG) analysis. In the second step, these precursor complexes have been pyrolysed in furnace under flowing nitrogen atmosphere whereupon they undergo thermodestruction to yield nanometer-sized particles of gallium/indium sulfide. The nanoparticles obtained were characterized using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDS). The average size of the nanoparticles ranged from 10 to 12 nm for Ga{sub 2}S{sub 3} and 20 to 22 nm for In{sub 2}S{sub 3}, respectively. This is the first report on use of a binary single source precursor to synthesize {beta}-Ga{sub 2}S{sub 3} nanoparticles.

  12. Surface Passivation of GaN Nanowires for Enhanced Photoelectrochemical Water-Splitting.

    Varadhan, Purushothaman; Fu, Hui-Chun; Priante, Davide; Retamal, Jose Ramon Duran; Zhao, Chao; Ebaid, Mohamed; Ng, Tien Khee; Ajia, Idirs; Mitra, Somak; Roqan, Iman S; Ooi, Boon S; He, Jr-Hau

    2017-03-08

    Hydrogen production via photoelectrochemical water-splitting is a key source of clean and sustainable energy. The use of one-dimensional nanostructures as photoelectrodes is desirable for photoelectrochemical water-splitting applications due to the ultralarge surface areas, lateral carrier extraction schemes, and superior light-harvesting capabilities. However, the unavoidable surface states of nanostructured materials create additional charge carrier trapping centers and energy barriers at the semiconductor-electrolyte interface, which severely reduce the solar-to-hydrogen conversion efficiency. In this work, we address the issue of surface states in GaN nanowire photoelectrodes by employing a simple and low-cost surface treatment method, which utilizes an organic thiol compound (i.e., 1,2-ethanedithiol). The surface-treated photocathode showed an enhanced photocurrent density of -31 mA/cm(2) at -0.2 V versus RHE with an incident photon-to-current conversion efficiency of 18.3%, whereas untreated nanowires yielded only 8.1% efficiency. Furthermore, the surface passivation provides enhanced photoelectrochemical stability as surface-treated nanowires retained ∼80% of their initial photocurrent value and produced 8000 μmol of gas molecules over 55 h at acidic conditions (pH ∼ 0), whereas the untreated nanowires demonstrated only surface passivation of nanostructured photoelectrodes for photoelectrochemical applications.

  13. Structure/Processing Relationships of Highly Ordered Lead Salt Nanocrystal Superlattices

    Hanrath, Tobias

    2009-10-27

    We investigated the influence of processing conditions, nanocrystal/substrate interactions and solvent evaporation rate on the ordering of strongly interacting nanocrystals by synergistically combining electron microscopy and synchrotron-based small-angle X-ray scattering analysis. Spin-cast PbSe nanocrystal films exhibited submicrometer-sized supracrystals with face-centered cubic symmetry and (001)s planes aligned parallel to the substrate. The ordering of drop-cast lead salt nanocrystal films was sensitive to the nature of the substrate and solvent evaporation dynamics. Nanocrystal films drop-cast on rough indium tin oxide substrates were polycrystalline with small grain size and low degree of orientation with respect to the substrate, whereas films drop-cast on flat Si substrates formed highly ordered face-centered cubic supracrystals with close-packed (111)s planes parallel to the substrate. The spatial coherence of nanocrystal films drop-cast in the presence of saturated solvent vapor was significantly improved compared to films drop-cast in a dry environment. Solvent vapor annealing was demonstrated as a postdeposition technique to modify the ordering of nanocrystals in the thin film. Octane vapor significantly improved the long-range order and degree of orientation of initially disordered or polycrystalline nanocrystal assemblies. Exposure to 1,2-ethanedithiol vapor caused partial displacement of surface bound oleic acid ligands and drastically degraded the degree of order in the nanocrystal assembly. © 2009 American Chemical Society.

  14. Sulfonated Magnetic Nanocomposite Based on Reactive PGMA-MAn Copolymer@Fe3O4 Nanoparticles: Effective Removal of Cu(II Ions from Aqueous Solutions

    Reza Hasanzadeh

    2016-01-01

    Full Text Available Chelating magnetic nanocomposites have been considered as suitable materials for removal of heavy metal ions for water treatment. In this work poly(glycidyl methacrylate-maleic anhydride copolymer (PGMA-MAn is modified with 4-aminobenzenesulfonic acid (ABSAc and subsequently the product reacted with modified Fe3O4 nanoparticles and 1,2-ethanedithiol (EDT in the presence of ultrasonic irradiation for preparation of tridimensional chelating magnetic nanocomposite. Synthesized magnetic nanocomposite was characterized by Fourier transform infrared spectroscopy (FT-IR, scanning electron microscopy (SEM, X-ray diffraction analysis (XRD, vibrating sample magnetometer (VSM, energy dispersive X-ray analysis (EDX, elemental mapping analysis (EMA, Brunauer-Emmett-Teller (BET, and thermal gravimetric analysis (TGA. The adsorption behavior of Cu(II ions was investigated by synthesized nanocomposite in various parameters such as pH, contact time, metal ion concentration, and adsorbent dosage. The equilibrium distribution coefficient (kd was determined and the findings prove that the kd value is approximately high in the case of all selected metal ions. The synthesized nanocomposite exhibited good tendency for removing Cu(II ions from aqueous solutions even at an acidic pH.

  15. Dithiol-mediated incorporation of CdS nanoparticles from reverse micellar system into Zn-doped SBA-15 mesoporous silica and their photocatalytic properties.

    Hirai, Takayuki; Nanba, Masanori; Komasawa, Isao

    2003-12-15

    CdS nanoparticles, as prepared in reverse micellar systems, were incorporated into alkanedithiol-modified Zn-doped SBA-15 mesoporous silica (dtz.sbnd;ZnSBA-15; pore diameter, ca. 4 nm), which were themselves prepared via hydrolysis of tetraethylorthosilicate (TEOS) in the presence of Zn(NO(3))(2) and triblock copolymer, as a nonsurfactant template and pore-forming agent, followed by contact with dithiol molecules. A particle-sieving effect for the dtz.sbnd;ZnSBA-15 was observed, in that the incorporation of the nanoparticles was remarkably decreased with increasing the nanoparticle size. The resulting CdSz.sbnd;ZnSBA-15 composite was then used as photocatalysts for the generation of H(2) from 2-propanol aqueous solution. Under UV irradiation (lambda>300 nm), a high photocatalytic activity was observed for this composite material. This is effected by electron transfer from the photoexcited ZnS (dithiol-bonded Zn on SBA-15) to CdS nanoparticles. The photocatalytic activity is increased with a decrease in the number of methylene groups in the dithiol molecules, according to the rank order 1,10-decanedithiol < 1,6-hexanedithiol < 1,2-ethanedithiol.

  16. Oligomerization of Indole Derivatives with Incorporation of Thiols

    Jarl E.S. Wikberg

    2008-08-01

    Full Text Available Abstract: Two molecules of indole derivative, e.g. indole-5-carboxylic acid, reacted with one molecule of thiol, e.g. 1,2-ethanedithiol, in the presence of trifluoroacetic acid to yield adducts such as 3-[2-(2-amino-5-carboxyphenyl-1-(2-mercaptoethylthioethyl]-1Hindole-5-carboxylic acid. Parallel formation of dimers, such as 2,3-dihydro-1H,1'H-2,3'-biindole-5,5'-dicarboxylic acid and trimers, such as 3,3'-[2-(2-amino-5-carboxyphenyl ethane-1,1-diyl]bis(1H-indole-5-carboxylic acid of the indole derivatives was also observed. Reaction of a mixture of indole and indole-5-carboxylic acid with 2-phenylethanethiol proceeded in a regioselective way, affording 3-[2-(2-aminophenyl-1-(phenethylthioethyl]-1H-indole-5-carboxylic acid. An additional product of this reaction was 3-[2-(2-aminophenyl-1-(phenethylthioethyl]-2,3-dihydro-1H,1'H-2,3'-biindole-5'-carboxylic acid, which upon standing in DMSO-d6 solution gave 3-[2-(2-aminophenyl-1-(phenethylthioethyl]-1H,1'H-2,3'-biindole-5'-carboxylic acid. Structures of all compounds were elucidated by NMR, and a mechanism for their formation was suggested.

  17. Atomic layer deposition effect on the electrical properties of Al{sub 2}O{sub 3}-passivated PbS quantum dot field-effect transistors

    So, Hye-Mi; Shim, Hyung Cheoul [Department of Nano Mechanics, Nanomechanical Systems Research Division, Korea Institute of Machinery and Materials (KIMM), 156 Gajeongbuk-Ro, Yuseong-Gu, Daejeon 305-343 (Korea, Republic of); Choi, Hyekyoung; Lee, Seung-Mo; Jeong, Sohee; Chang, Won Seok, E-mail: paul@kimm.re.kr [Department of Nano Mechanics, Nanomechanical Systems Research Division, Korea Institute of Machinery and Materials (KIMM), 156 Gajeongbuk-Ro, Yuseong-Gu, Daejeon 305-343 (Korea, Republic of); Department of Nano-Mechatronics, Korea University of Science and Technology (UST), 217 Gajeong-Ro, Yuseong-Gu, Daejeon 305-333 (Korea, Republic of)

    2015-03-02

    We have investigated the effect of atomic layer deposition (ALD) on the electrical properties of colloidal PbS quantum dot field-effect transistors (PbS QD-FETs). Low-temperature Al{sub 2}O{sub 3} ALD process was used to fill up the pore spaces of PbS QD films containing 1, 2-ethanedithiol ligands. Upon deposition of Al{sub 2}O{sub 3} on PbS film, the PbS QD-FETs showed ambipolar behavior. The treated film retained this property for over 2 months, despite of exposure to air. This change in the electrical properties of the PbS QD-FETs is attributed to the formation of electron channels in the Al{sub 2}O{sub 3}-passivated PbS film. We conclude that these electron transport channels in the Al{sub x}O{sub y}-PbS film are formed due to substitution of the Pb sites by Al metal and chemical reduction of Pb{sup 2+} ions, as determined by an analysis of the depth profile of the film using secondary ion mass spectrometry and X-ray photoelectron spectroscopy.

  18. An anti-fouling nanoplasmonic SERS substrate for trapping and releasing a cationic fluorescent tag from human blood solution.

    Sivashanmugan, Kundan; Liu, Po-Chun; Tsai, Kai-Wei; Chou, Ying-Nien; Lin, Chen-Hsueh; Chang, Yung; Wen, Ten-Chin

    2017-02-23

    In bioenvironmental detection, surface-enhanced Raman scattering (SERS) signals are greatly affected by anti-specific biomolecule adsorption, which generates strong background noise, reducing detection sensitivity and selectivity. It is thus necessary to modify the SERS substrate surface to make it anti-fouling to maintain excellent SERS signals. Herein, we propose a zwitterionic copolymer, namely poly(glycidyl methacrylate-co-sulfobetaine methacrylate) (poly(GMA-co-SBMA)), for the surface modification of SERS substrates, which were fabricated and characterized spectroscopically. The copolymer was grafted onto Ag nanocubes (NCs) on an Ag surface with massive nanogaps via 1,2-ethanedithiol, which acted as a metal-insulator-metal (MIM) substrate. The high density of poly(GMA-co-SBMA) grafted near NCs favored the formation of connections between adjacent NCs, causing strong surface plasmon resonance at these junctions. With the zwitterionic-copolymer-modified surface, the adhesion of large biomolecules in platelet-rich plasma (PRP) solution can be effectively resisted, as determined from immunoassay and fibrinogen adsorption results. The SERS signals for malachite green (MG) in PRP solution (10(-6) M) were effectively distinguished using the copolymer-grafted MIM substrate. MG was deposited on adjacent copolymer-grafted NCs, which amplified the SERS signals. Moreover, the copolymer connected adjacent NCs, inducing the electromagnetic effect at copolymer-grafted surfaces, which improved the SERS mechanism. The hydration process restructured the MG-trapped copolymer-grafted surface, decreasing the number of MG characteristic peak regions and increasing that of the copolymer regions. These results reveal that grafting a copolymer onto an MIM substrate allows MG to be easily trapped and released in complex biomatrices and increases surface reproducibility due to anti-fouling, leading to high SERS enhancement.

  19. Study of Exciton Hopping Transport in PbS Colloidal Quantum Dot Thin Films Using Frequency- and Temperature-Scanned Photocarrier Radiometry

    Hu, Lilei; Mandelis, Andreas; Melnikov, Alexander; Lan, Xinzheng; Hoogland, Sjoerd; Sargent, Edward H.

    2017-01-01

    Solution-processed colloidal quantum dots (CQDs) are promising materials for realizing low-cost, large-area, and flexible photovoltaic devices. The study of charge carrier transport in quantum dot solids is essential for understanding energy conversion mechanisms. Recently, solution-processed two-layer oleic-acid-capped PbS CQD solar cells with one layer treated with tetrabutylammonium iodide (TBAI) serving as the main light-absorbing layer and the other treated with 1,2-ethanedithiol (EDT) acting as an electron-blocking/hole-extraction layer were reported. These solar cells demonstrated a significant improvement in power conversion efficiency of 8.55% and long-term air stability. Coupled with photocarrier radiometry measurements, this work used a new trap-state mediated exciton hopping transport model, specifically for CQD thin films, to unveil and quantify exciton transport mechanisms through the extraction of hopping transport parameters including exciton lifetimes, hopping diffusivity, exciton detrapping time, and trap-state density. It is shown that PbS-TBAI has higher trap-state density than PbS-EDT that results in higher PbS-EDT exciton lifetimes. Hopping diffusivities of both CQD thin film types show similar temperature dependence, particularly higher temperatures yield higher hopping diffusivity. The higher diffusivity of PbS-TBAI compared with PbS-EDT indicates that PbS-TBAI is a much better photovoltaic material than PbS-EDT. Furthermore, PCR temperature spectra and deep-level photothermal spectroscopy provided additional insights to CQD surface trap states: PbS-TBAI thin films exhibit a single dominant trap level, while PbS-EDT films with lower trap-state densities show multiple trap levels.

  20. Synthesis, structure, properties and immobilization on a gold surface of the monoribbed-functionalized tris-dioximate cobalt(II) clathrochelates and an electrocatalytic hydrogen production from H+ ions.

    Voloshin, Y Z; Belov, A S; Vologzhanina, A V; Aleksandrov, G G; Dolganov, A V; Novikov, V V; Varzatskii, O A; Bubnov, Y N

    2012-05-28

    The cycloaddition of the mono- and dichloroglyoximes to the cobalt(II) bis-α-benzyldioximate afforded the cobalt(II) mono- and dichloroclathrochelates in moderate yields (40-60%). These complexes undergo nucleophilic substitution of their reactive chlorine atoms with aliphatic amines, alcohols and thiolate anions. In the case of ethylenediamine and 1,2-ethanedithiol, only the macrobicyclic products with α,α'-N(2)- and α,α'-S(2)-alicyclic six-numbered ribbed fragments were obtained. The cobalt(II) cage complexes with terminal mercapto groups were synthesized using aliphatic dithiols. The crystal and molecular structures of the six cobalt(II) clathrochelates were obtained by X-ray diffraction. Their CoN(6)-coordination polyhedra possess a geometry intermediate between a trigonal prism and a trigonal antiprism, and the encapsulated cobalt(II) ions are shifted from their centres due to the structural Jahn-Teller effect with the Co-N distances varying significantly (by 0.10-0.26 Å). The electrochemistry of the complexes obtained was studied by cyclic voltammetry (CV). The anodic waves correspond to the quasi-reversible Co(2+/3+) oxidations, whereas the cathodic ranges contain the quasi-reversibile waves assigned to the Co(2+/+) reductions; all the cobalt(i)-containing clathrochelate anions formed are stable in the CV time scale. The electrocatalytic properties of the cobalt complexes obtained were studied in the production of hydrogen from H(+) ions: the addition of HClO(4) resulted in the formation of the same catalytic cathodic reduction Co(2+/+) waves. The controlled-potential electrolysis with gas chromatography analysis confirmed the production of H(2) in high Faraday yields. The efficiency of this electrocatalytic process was enhanced by an immobilization of the complexes with terminal mercapto groups on a surface of the working gold electrode.

  1. Revisiting the Valence and Conduction Band Size Dependence of PbS Quantum Dot Thin Films

    Miller, Elisa M.; Kroupa, Daniel M.; Zhang, Jianbing; Schulz, Philip; Marshall, Ashley R.; Kahn, Antoine; Lany, Stephan; Luther, Joseph M.; Beard, Matthew C.; Perkins, Craig L.; van de Lagemaat, Jao

    2016-03-22

    We use a high signal-to-noise X-ray photoelectron spectrum of bulk PbS, GW calculations, and a model assuming parabolic bands to unravel the various X-ray and ultraviolet photoelectron spectral features of bulk PbS as well as determine how to best analyze the valence band region of PbS quantum dot (QD) films. X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) are commonly used to probe the difference between the Fermi level and valence band maximum (VBM) for crystalline and thin-film semiconductors. However, we find that when the standard XPS/UPS analysis is used for PbS, the results are often unrealistic due to the low density of states at the VBM. Instead, a parabolic band model is used to determine the VBM for the PbS QD films, which is based on the bulk PbS experimental spectrum and bulk GW calculations. Our analysis highlights the breakdown of the Brillioun zone representation of the band diagram for large band gap, highly quantum confined PbS QDs. We have also determined that in 1,2-ethanedithiol-treated PbS QD films the Fermi level position is dependent on the QD size; specifically, the smallest band gap QD films have the Fermi level near the conduction band minimum and the Fermi level moves away from the conduction band for larger band gap PbS QD films. This change in the Fermi level within the QD band gap could be due to changes in the Pb:S ratio. In addition, we use inverse photoelectron spectroscopy to measure the conduction band region, which has similar challenges in the analysis of PbS QD films due to a low density of states near the conduction band minimum.

  2. Postsynthetically Modified Covalent Organic Frameworks for Efficient and Effective Mercury Removal.

    Sun, Qi; Aguila, Briana; Perman, Jason; Earl, Lyndsey D; Abney, Carter W; Cheng, Yuchuan; Wei, Hao; Nguyen, Nicholas; Wojtas, Lukasz; Ma, Shengqian

    2017-02-22

    A key challenge in environmental remediation is the design of adsorbents bearing an abundance of accessible chelating sites with high affinity, to achieve both rapid uptake and high capacity for the contaminants. Herein, we demonstrate how two-dimensional covalent organic frameworks (COFs) with well-defined mesopore structures display the right combination of properties to serve as a scaffold for decorating coordination sites to create ideal adsorbents. The proof-of-concept design is illustrated by modifying sulfur derivatives on a newly designed vinyl-functionalized mesoporous COF (COF-V) via thiol-ene "click" reaction. Representatively, the material (COF-S-SH) synthesized by treating COF-V with 1,2-ethanedithiol exhibits high efficiency in removing mercury from aqueous solutions and the air, affording Hg(2+) and Hg(0) capacities of 1350 and 863 mg g(-1), respectively, surpassing all those of thiol and thioether functionalized materials reported thus far. More significantly, COF-S-SH demonstrates an ultrahigh distribution coefficient value (Kd) of 2.3 × 10(9) mL g(-1), which allows it to rapidly reduce the Hg(2+) concentration from 5 ppm to less than 0.1 ppb, well below the acceptable limit in drinking water (2 ppb). We attribute the impressive performance to the synergistic effects arising from densely populated chelating groups with a strong binding ability within ordered mesopores that allow rapid diffusion of mercury species throughout the material. X-ray absorption fine structure (XAFS) spectroscopic studies revealed that each Hg is bound exclusively by two S via intramolecular cooperativity in COF-S-SH, further interpreting its excellent affinity. The results presented here thus reveal the exceptional potential of COFs for high-performance environmental remediation.

  3. Synthesis, characterisation, and evaluation of a cross-linked disulphide amide-anhydride-containing polymer based on cysteine for colonic drug delivery.

    Lim, Vuanghao; Peh, Kok Khiang; Sahudin, Shariza

    2013-12-18

    The use of disulphide polymers, a low redox potential responsive delivery, is one strategy for targeting drugs to the colon so that they are specifically released there. The objective of this study was to synthesise a new cross-linked disulphide-containing polymer based on the amino acid cysteine as a colon drug delivery system and to evaluate the efficiency of the polymers for colon targeted drug delivery under the condition of a low redox potential. The disulphide cross-linked polymers were synthesised via air oxidation of 1,2-ethanedithiol and 3-mercapto-N-2-(3-mercaptopropionamide)-3-mercapto propionic anhydride (trithiol monomers) using different ratio combinations. Four types of polymers were synthesised: P10, P11, P151, and P15. All compounds synthesised were characterised by NMR, IR, LC-MS, CHNS analysis, Raman spectrometry, SEM-EDX, and elemental mapping. The synthesised polymers were evaluated in chemical reduction studies that were performed in zinc/acetic acid solution. The suitability of each polymer for use in colon-targeted drug delivery was investigated in vitro using simulated conditions. Chemical reduction studies showed that all polymers were reduced after 0.5-1.0 h, but different polymers had different thiol concentrations. The bacterial degradation studies showed that the polymers were biodegraded in the anaerobic colonic bacterial medium. Degradation was most pronounced for polymer P15. This result complements the general consensus that biodegradability depends on the swellability of polymers in an aqueous environment. Overall, these results suggest that the cross-linked disulphide-containing polymers described herein could be used as coatings for drugs delivered to the colon.

  4. Synthesis, Characterisation, and Evaluation of a Cross-Linked Disulphide Amide-Anhydride-Containing Polymer Based on Cysteine for Colonic Drug Delivery

    Vuanghao Lim

    2013-12-01

    Full Text Available The use of disulphide polymers, a low redox potential responsive delivery, is one strategy for targeting drugs to the colon so that they are specifically released there. The objective of this study was to synthesise a new cross-linked disulphide-containing polymer based on the amino acid cysteine as a colon drug delivery system and to evaluate the efficiency of the polymers for colon targeted drug delivery under the condition of a low redox potential. The disulphide cross-linked polymers were synthesised via air oxidation of 1,2-ethanedithiol and 3-mercapto-N-2-(3-mercaptopropionamide-3-mercapto propionic anhydride (trithiol monomers using different ratio combinations. Four types of polymers were synthesised: P10, P11, P151, and P15. All compounds synthesised were characterised by NMR, IR, LC-MS, CHNS analysis, Raman spectrometry, SEM-EDX, and elemental mapping. The synthesised polymers were evaluated in chemical reduction studies that were performed in zinc/acetic acid solution. The suitability of each polymer for use in colon-targeted drug delivery was investigated in vitro using simulated conditions. Chemical reduction studies showed that all polymers were reduced after 0.5–1.0 h, but different polymers had different thiol concentrations. The bacterial degradation studies showed that the polymers were biodegraded in the anaerobic colonic bacterial medium. Degradation was most pronounced for polymer P15. This result complements the general consensus that biodegradability depends on the swellability of polymers in an aqueous environment. Overall, these results suggest that the cross-linked disulphide-containing polymers described herein could be used as coatings for drugs delivered to the colon.

  5. Solid Phase Synthesis and Anti-microbial Activities of the Antibacterial Peptide IB-367%抗菌肽IB-367的固相合成与抑菌活性

    王小青; 高杨; 尹志峰; 宫闻婧; 赵红玲; 王良友

    2016-01-01

    采用固相合成方法,以Rink Amide树脂为载体,Fmoc保护氨基酸为原料,经苯并三唑-1-四甲基六氟磷酸酯( HBTU)/N,N-二异丙基乙胺( DIEA)缩合,三氟乙酸/苯甲硫醚/乙二硫醇/苯甲醚裂解体系脱除保护基制得IB-367线性肽(4);4经双氧水氧化制得IB-367一环肽(5);5经碘乙醇溶液氧化合成抗菌肽IB-367(6),收率34.1%,纯度>95.0%,其结构经MS(ESI)和氨基酸组成分析确证。抑菌活性研究结果表明:6对大肠杆菌和金黄色葡萄球菌的最小抑菌浓度为5.0μg· mL-1。%The linear peptides of IB-367(4) was synthesized according to its peptide sequence by con-densation with O-( benzotriazol-yl )-N, N, N′, N′-tetramethy-luronium ( HBTU )/N-Ethyldiisopropyl-amine( DIEA) and deprotection with trifluoroacetic acid/thioanisole/1,2-ethanedithiol/anisole, using rink amide resin as the solid supporter , and Fmoc-amino acids as raw materials .The cyclic peptide of IB-367(5) was formed by oxidation of 4 with H2O2.The antibacterial peptide IB-367(6) with yield of 34.1%and purity>95.0% was obtained by oxidation of 5 with I2 .The structure was confirmed by MS(ESI) and amino acid composition analysis .MIC of 6 on Escherichia coli and Staphylococcus aureus was 5.0 μg· mL-1 .

  6. A novel approach for the fabrication of all-inorganic nanocrystal solids: Semiconductor matrix encapsulated nanocrystal arrays

    Moroz, Pavel

    matrix-encapsulated PbS nanocrystal films containing a tunable fraction of insulating ZnS domains, we uniquely distinguish the dynamics of charge scattering on defects from other processes of exciton dissociation. The measured times are subsequently used to estimate the diffusion length and the carrier mobility for each film type within hopping transport regime. It is demonstrated that nanocrystal films encapsulated into semiconductor matrices exhibit a lower probability of charge scattering than nanocrystal solids cross-linked with either 3-mercaptopropionic acid or 1,2-ethanedithiol molecular linkers. The suppression of carrier scattering in matrix-encapsulated nanocrystal films is attributed to a relatively low density of surface defects at nanocrystal/matrix interfaces. High stability and low density of defects made it possible to fabricate infrared-emitting nanocrystal solids. Presently, an important challenge facing the development of nanocrystal infrared emitters concerns the fact that both the emission quantum yield and the stability of colloidal nanoparticles become compromised when nanoparticle solutions are processed into solids. Here, we address this issue by developing an assembly technique that encapsulates infrared-emitting PbS NCs into crystalline CdS matrices, designed to preserve NC emission characteristics upon film processing. Here, the morphology of these matrices was designed to suppress the nonradiative carrier decay, whereby increasing the exciton lifetime up to 1 mus, and boosting the emission quantum yield to an unprecedented 3.7% for inorganically encapsulated PbS NC solids.