Structural, Optical and Electrochromic Properties of Nanocrystalline TiO

Nanocrystalline TiO2 thin filmswere prepared by spin coating on covered glass substrates with an indium tin oxide (ITO) layer. The structural, electrochromic and optical properties of the films were investigated. The films are crystallized predominantly in the anatase phase with lattice parameters a = b = 0.378 nm and c = 0.958 nm . The crystallite size was found to be of the order of 14 nm. The films showed reversible coloration/bleaching cycles as demonstrated by cyclic voltametry and current–time transients. The transmission of the blue colored films decreased and their absorption edge was less sharp and shifted to higher wavelengths as a result of the intercalation of Li+ ions

Locating the Binding Sites of Pb(II) Ion with Human and Bovine Serum Albumins

Lead is a potent environmental toxin that has accumulated above its natural level as a result of human activity. Pb cation shows major affinity towards protein complexation and it has been used as modulator of protein-membrane interactions. We located the binding sites of Pb(II) with human serum (HSA) and bovine serum albumins (BSA) at physiological conditions, using constant protein concentration and various Pb contents. FTIR, UV-visible, CD, fluorescence and X-ray photoelectron spectroscopic (XPS) methods were used to analyse Pb binding sites, the binding constant and the effect of metal ion complexation on HSA and BSA stability and conformations. Structural analysis showed that Pb binds strongly to HSA and BSA via hydrophilic contacts with overall binding constants of KPb-HSA = 8.2 (±0.8)×104 M−1 and KPb-BSA = 7.5 (±0.7)×104 M−1. The number of bound Pb cation per protein is 0.7 per HSA and BSA complexes. XPS located the binding sites of Pb cation with protein N and O atoms. Pb complexation alters protein conformation by a major reduction of α-helix from 57% (free HSA) to 48% (metal-complex) and 63% (free BSA) to 52% (metal-complex) inducing a partial protein destabilization

Competing charge transfer pathways at the photosystem II-electrode interface.

The integration of the water-oxidation enzyme photosystem II (PSII) into electrodes allows the electrons extracted from water oxidation to be harnessed for enzyme characterization and to drive novel endergonic reactions. However, PSII continues to underperform in integrated photoelectrochemical systems despite extensive optimization efforts. Here we carried out protein-film photoelectrochemistry using spinach and Thermosynechococcus elongatus PSII, and we identified a competing charge transfer pathway at the enzyme-electrode interface that short-circuits the known water-oxidation pathway. This undesirable pathway occurs as a result of photo-induced O2 reduction occurring at the chlorophyll pigments and is promoted by the embedment of PSII in an electron-conducting fullerene matrix, a common strategy for enzyme immobilization. Anaerobicity helps to recover the PSII photoresponse and unmasks the onset potentials relating to the QA/QB charge transfer process. These findings impart a fuller understanding of the charge transfer pathways within PSII and at photosystem-electrode interfaces, which will lead to more rational design of pigment-containing photoelectrodes in general.This work was supported by the U.K. Engineering and Physical Sciences Research Council (EP/H00338X/2 to E. Reisner), the U.K. Biology and Biotechnological Sciences Research Council (BB/K010220/1 to E. Reisner), a Marie Curie International Incoming Fellowship (PIIF-GA-2012-328085 RPSII to J.J.Z.). N.P. was supported by the Winton Fund for the Physics of Sustainability. E. Romero. and R.v.G. were supported by the VU University Amsterdam, the Laserlab-Europe Consortium, the TOP grant (700.58.305) from the Foundation of Chemical Sciences part of NWO, the Advanced Investigator grant (267333, PHOTPROT) from the European Research Council, and the EU FP7 project PAPETS (GA 323901). R.v.G. gratefully acknowledges his `Academy Professor' grant from the Royal Netherlands Academy of Arts and Sciences (KNAW). We would also like to thank Miss Katharina Brinkert and Prof A. William Rutherford for a sample of T. elongatus PSII, and H. v. Roon for preparation of the spinach PSII samples

Cellulose nanofiber backboned Prussian blue nanoparticles as powerful adsorbents for the selective elimination of radioactive cesium

On 11 March 2011, the day of the unforgettable disaster of the 9 magnitude Tohoku earthquake and quickly followed by the devastating Tsunami, a damageable amount of radionuclides had dispersed from the Fukushima Daiichi’s damaged nuclear reactors. Decontamination of the dispersed radionuclides from seawater and soil, due to the huge amounts of coexisting ions with competitive functionalities, has been the topmost difficulty. Ferric hexacyanoferrate, also known as Prussian blue (PB), has been the most powerful material for selectively trapping the radioactive cesium ions; its high tendency to form stable colloids in water, however, has made PB to be impossible for the open-field radioactive cesium decontamination applications. A nano/nano combinatorial approach, as is described in this study, has provided an ultimate solution to this intrinsic colloid formation difficulty of PB. Cellulose nanofibers (CNF) were used to immobilize PB via the creation of CNF-backboned PB. The CNF-backboned PB (CNF/PB) was found to be highly tolerant to water and moreover, it gave a 139 mg/g capability and a million (106) order of magnitude distribution coefficient (Kd) for absorbing of the radioactive cesium ion. Field studies on soil and seawater decontaminations in Fukushima gave satisfactory results, demonstrating high capabilities of CNF/PB for practical applications.National Science Foundation (U.S.) (DMR-1507806

Photoinduced electron transfer between 1,2,5-triphenylpyrrolidinofullerene cluster aggregates and electron donors

Fullerene derivative 1,2,5-triphenylpyrrolidinofullerene (TPPF) forms optically transparent clusters (mean diameter of ~180 nm) in toluene/acetonitrile mixtures. The bimolecular rate constants for the quenching of a singlet excited state of TPPF clusters by various electron donors (substituted anilines and heteroaromatics) were found to be significantly higher than that of the corresponding monomeric analogue. The local concentration of the fullerene molecules is much higher in these clusters because the microheterogeneous environment facilitates trapping of donor molecules. Formation of long-lived electron-transfer products, following the photoexcitation of the TPPF cluster and various electron donors, was confirmed through flash photolysis studies. The TPPF cluster-donor assemblies when deposited as a thin film on a nanostructured SnO2 semiconductor film, act as a photosensitive electrode material. Light energy can be harvested using an intermolecular electron transfer between the TPPF cluster film and the corresponding electron donor in a photoelectrochemical cell. Photocurrents of up to 0.4 μA/cm2 have been achieved in the TPPF-N-methylphenothiazine cluster system under visible light irradiation

Clusters of bis- and tris-fullerenes

Bis- and tris-fullerene derivatives [bis-(C60) and tris-(C60)] form suspendable clusters in mixed solvents (80% acetonitrile and 20% toluene). These clusters are optically transparent and exhibit interesting nanostructures with sizes ranging from 100 nm to 1 µm and shapes varying from elongated wires to entangled spheres. Ground- and excited-state properties of the clusters of the mono-, bis-, and tris-fullerene derivatives are compared with the corresponding properties of their monomeric forms through steady-state and time-resolved transient absorption spectroscopy. The singlet excited-state quenching of bis- and tris-fullerene derivatives by N-methylphenothiazine (NMP) occurs with rate constants of 5.5 × 109 and 5.3 × 109 M-1 s-1, respectively. The charge separation in these clustered fullerene derivatives is probed by monitoring the formation and decay of the C60 radical anion and the radical cation of NMP. An increase in the number of fullerene moieties in the molecule helps in the formation of ordered cluster aggregates and this has a beneficial effect in stabilizing the electron-transfer products