Electron-Affinity-Triggered Variations on the Optical and Electrical Properties of Dye Molecules Enabling Highly Efficient Dye-Sensitized Solar Cells.

The synthesis, characterization, and photovoltaic performance of a series of indacenodithiophene (IDT)-based D-π-A organic dyes with varying electron-accepting units is presented. By control of the electron affinity, perfectly matching energy levels were achieved with a copper(I/II)-based redox electrolyte, reaching a high open-circuit voltage (>1.1 V) while harvesting a large fraction of solar photons at the same time. Besides achieving high power conversion efficiencies (PCEs) for dye-sensitized solar cells (DSCs), that is, 11.2 % under standard AM 1.5 G sunlight, and 28.4 % under a 1000 lux fluorescent light tube, this work provides a possible method for the design and fabrication of low-cost highly efficient DSCs.

Cation Dynamics in Mixed-Cation (MA)x(FA)1-xPbI3 Hybrid Perovskites from Solid-State NMR.

Mixed-cation organic lead halide perovskites attract unfaltering attention owing to their excellent photovoltaic properties. Currently, the best performing perovskite materials contain multiple cations and provide power conversion efficiencies up to around 22%. Here, we report the first quantitative, cation-specific data on cation reorientation dynamics in hybrid mixed-cation formamidinium (FA)/methylammonium (MA) lead halide perovskites. We use 14N, 2H, 13C, and 1H solid-state MAS NMR to elucidate cation reorientation dynamics, microscopic phase composition, and the MA/FA ratio, in (MA)x(FA)1-xPbI3 between 100 and 330 K. The reorientation rates correlate in a striking manner with the carrier lifetimes previously reported for these materials and provide evidence of the polaronic nature of charge carriers in PV perovskites.

Four-electron oxygen reduction by tetrathiafulvalene.

The four-electron reduction of oxygen by tetrathiafulvalene (TTF) in acidified 1,2-dichloroethane and at the acidified water/1,2-dichloroethane interface has been observed. Spectroscopy and ion transfer voltammetry results suggest that the reaction proceeds by the fast protonation of TTF followed by the 4-electron reduction of oxygen to form water. Electronic structure computations give evidence of the formation of a helical tetramer assembly ([TTF(4)H(2)](2+)) of two protonated TTF and two neutral TTF molecules. The protonated tetramer is potentially able to deliver the four electrons needed for the oxygen reduction. The production of water was corroborated by (1)H NMR analysis.

High excitation transfer efficiency from energy relay dyes in dye-sensitized solar cells.

The energy relay dye, 4-(Dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), was used with a near-infrared sensitizing dye, TT1, to increase the overall power conversion efficiency of a dye-sensitized solar cell (DSC) from 3.5% to 4.5%. The unattached DCM dyes exhibit an average excitation transfer efficiency (ETE) of 96% inside TT1-covered, mesostructured TiO(2) films. Further performance increases were limited by the solubility of DCM in an acetonitrile based electrolyte. This demonstration shows that energy relay dyes can be efficiently implemented in optimized dye-sensitized solar cells, but also highlights the need to design highly soluble energy relay dyes with high molar extinction coefficients.

High-conversion-efficiency organic dye-sensitized solar cells with a novel indoline dye.

An indoline dye (D205), the synthesis method of which is disclosed in this report, gave high-efficiency organic dye-sensitized solar cells (9.52%) using an anti-aggregation reagent (chenodeoxycholic acid).

Safety and efficacy of a biomimetic monolayer of permanently bound multiphosphonic acid molecules on dental implants: 3 years post-loading results from a pilot quadruple-blinded randomised controlled trial.

PURPOSE: To evaluate the safety and clinical efficacy of a novel surface treatment (SurfLink, Nano Bridging Molecules, Gland, Switzerland) on titanium dental implants. SurfLink consists of a monolayer of permanently bound multiphosphonic acid molecules, which mimics the surface of naturally occurring hydroxyapatite. MATERIALS AND METHODS: Twenty-three patients requiring at least two single dental implants had their sites randomised according to a split-mouth design to receive one titanium grade 4 implant treated with SurfLink and one untreated control implant. Additional SurfLink-treated implants were placed if needed. Implants were submerged for 3 months in mandibles and 6 months in maxillae, then loaded with definitive metal-ceramic crowns and followed for 3 years after loading. Outcome measures were crown/implant failures, any complication, radiographic peri-implant marginal bone level changes and marginal bleeding. RESULTS: Three patients dropped out but all remaining patients were followed up to 3-years post-loading. No implant failed. Complications were reported for three patients, affecting both types of implant in two patients and only SurfLink implant in one patient. No differences for complications between the two implant types was observed (McNemar test, P = 1, difference in proportions = -0.04, 95% CI: -0.22 to 0.14). No bleeding was observed when a periodontal probe was run in the peri-implant soft tissues around any of the implants, with the exception of three implants affected by peri-implantitis. There were no statistically significant differences in marginal bone level changes between the two groups (at 3 years post-loading P = 0.86, mean difference = -0.05; SD = 1.15; 95% CI: -0.56 to 0.47). CONCLUSIONS: Medium-term data (3-years post-loading) of implants with a biomimetic monolayer of permanently bound multiphosphonic acid molecules (SurfLink surface treatment) presented no safety issues. Clinical healing in both control and SurfLink-treated implant groups was uneventful and did not differ significantly. More challenging clinical situations need to be investigated to evaluate the real effectiveness of this surface treatment. Conflict-of-interest statement: Marco Esposito and Ivan Dojcinovic declare that they have no conflict of interest, and they acted as consultants for Nano Bridging Molecules (NBM). Sabrina Buchini, Péter Péchy and Björn-Owe Aronsson are employed at NBM. NBM, the manufacturer of the SurfLink surface treatment, supported and carefully monitored this trial without interfering with the presentation of its results.

High-efficiency (7.2%) flexible dye-sensitized solar cells with Ti-metal substrate for nanocrystalline-TiO2 photoanode.

High-efficiency flexible dye-sensitized solar cells were fabricated with a Ti-metal foil substrate for photo anode and using a Pt-electrodeposited counter electrode on ITO/polyethylene naphthalate (ITO/PEN); these devices were characterized by incident photon-to-current efficiency (IPCE), optical transmittance and electrical impedance spectroscopy.

Control of dark current in photoelectrochemical (TiO2/I--I3-)) and dye-sensitized solar cells.

The ruthenium complex bis-tetrabutylammonium cis-dithiocyanato-N,N'-bis-2,2'-bipyridine-4-carboxylic acid, 4'-carboxylate ruthenium(II), N-719, was found to block the dark current of dye sensitized solar cells (DSC), based on mesoporous TiO2 films deposited on a F-doped tin oxide electrode and the effect was compared to surface treatment by TiCl4 and the introduction of a compact TiO2 blocking layer.

A novel multi-phosphonate surface treatment of titanium dental implants: a study in sheep.

The aim of the present study was to evaluate a new multi-phosphonate surface treatment (SurfLink®) in an unloaded sheep model. Treated implants were compared to control implants in terms of bone to implant contact (BIC), bone formation, and biomechanical stability. The study used two types of implants (rough or machined surface finish) each with either the multi-phosphonate Wet or Dry treatment or no treatment (control) for a total of six groups. Animals were sacrificed after 2, 8, and 52 weeks. No adverse events were observed at any time point. At two weeks, removal torque showed significantly higher values for the multi-phosphonate treated rough surface (+32% and +29%, Dry and Wet, respectively) compared to rough control. At 52 weeks, a significantly higher removal torque was observed for the multi-phosphonate treated machined surfaces (+37% and 23%, Dry and Wet, respectively). The multi-phosphonate treated groups showed a positive tendency for higher BIC with time and increased new-old bone ratio at eight weeks. SEM images revealed greater amounts of organic materials on the multi-phosphonate treated compared to control implants, with the bone fracture (from the torque test) appearing within the bone rather than at the bone to implant interface as it occurred for control implants.

Safety and efficacy of a biomimetic monolayer of permanently bound multi-phosphonic acid molecules on dental implants: 1 year post-loading results from a pilot quadruple-blinded randomised controlled trial.

PURPOSE: To evaluate the safety and clinical efficacy of a novel surface treatment (SurfLink®, Nano Bridging Molecules, Gland, Switzerland) on titanium dental implants. SurfLink consists of a monolayer of permanently bound multi-phosphonic acid molecules, which mimics the surface of naturally occurring hydroxyapatite. MATERIALS AND METHODS: Twenty-three patients requiring at least two single dental implants had their sites randomised according to a split-mouth design to receive one titanium grade 4 implant treated with SurfLink and one untreated control implant. Additional SurfLink-treated implants were placed if needed. Implants were submerged for 3 months in mandibles and 6 months in maxillae, were loaded with definitive metal-ceramic crowns, and followed up for 1 year after loading. Outcome measures were crown/implant failures, any complication, radiographic peri-implant marginal bone level changes and marginal bleeding. RESULTS: One patient dropped out after abutment connection. All remaining patients were followed up to 1 year post-loading. No implant failed and only 1 postoperative complication (pain) occurred, but it may not have been related to the implant treatment. No bleeding was observed when a periodontal probe was used to examine the peri-implant soft tissues around the implants. There were no statistically significant differences in marginal bone level changes between the two groups (P = 0.057, mean difference = -0.27, SE = 0.13; 95% CI -0.55 to 0.01). CONCLUSIONS: Preliminary short-term data (1 year post-loading) of implants with a biomimetic monolayer of permanently bound multi-phosphonic acid molecules (SurfLink surface treatment) presented no safety issues. Clinical healing in both the control and SurfLink-treated implant group was uneventful and did not differ significantly between groups. More challenging clinical situations need to be investigated to evaluate the real effectiveness of this surface treatment.

Molecular-scale interface engineering of nanocrystalline titania by co-adsorbents for solar energy conversion.

The use of mixed self-assembled monolayers, combining hydrophobic co-adsorbents with the sensitizer, has been demonstrated to enhance the efficiency of dye-sensitized solar cells (DSCs). Herein, the influence of the anchoring groups of the co-adsorbents on the performance of the DSCs is carefully examined by selecting two model molecules: neohexyl phosphonic acid (NHOOP) and bis-(3,3-dimethyl-butyl)-phosphinic acid (DINHOP). The effect of these co-adsorbents on the photovoltaic performance (J-V curves, incident photon-to-electron conversion efficiency) is investigated. Photoelectron spectroscopy and electrochemical impedance spectroscopy are performed to assess the spatial configuration of adsorbed dye and co-adsorbent molecules. The photoelectron spectroscopy studies indicate that the ligands of the ruthenium complex, containing thiophene groups, point out away from the surface of TiO(2) in comparison with the NCS group.

Passivation of nanocrystalline TiO2 junctions by surface adsorbed phosphinate amphiphiles enhances the photovoltaic performance of dye sensitized solar cells.

We report a new class of molecular insulators that electronically passivate the surface of nanocrystalline titania films for high performance dye sensitized solar cells (DSC). Using electrical impedance measurements we demonstrate that co-adsorption of dineohexyl bis-(3,3-dimethyl-butyl)-phosphinic acid (DINHOP), along with the amphiphilic ruthenium sensitizer Z907Na increased substantially the power output of the cells mainly due to a retardation of interfacial recombination of photo-generated charge carriers. The use of phosphinates as anchoring groups opens up new avenues for modification of the surface by molecular insulators, sensitizers and other electro-active molecules to realize the desired optoelectronic performance of devices based on oxide junctions.

Dye-sensitized solar cells incorporating a "liquid" hole-transporting material.

We present the first application of an amorphous "liquid" organic semiconductor in an optoelectronic device, demonstrating that it is highly suited for use as a hole-transporting material in nanostructured dye-sensitized solar cells. For such devices, we obtain power conversion efficiencies of up to 2.4% under simulated air mass 1.5 solar spectrum at 100 mWcm(-2), and incident photon-to-electron quantum efficiencies in excess of 50%.

Osteoblast culture on polished titanium disks modified with phosphonic acids.

Titanium is widely used in dental implants due to its suitable physical properties and its good biocompatibility. However, it is integrated into bone only passively, and the resulting fixation in the bone, which is necessary for the function, is mainly mechanical in nature. With the objective of increasing the chemical interaction between the implant and the bone tissue, several phosphonic acids were synthesized and grafted onto titanium disks. Here we report on the proliferation, differentiation, and protein production of rat osteoblastic cells (CRP10/30) on phosphonic-acid-modified titanium surfaces studied in vitro. No statistical differences were found in osteoblast proliferation among the phosphonic-acid-modified titanium, unmodified titanium, and tissue culture plastic (used as a positive control), indicating that the phosphonic acids used were not cytotoxic to the osteoblasts used. For all surfaces (modified or not), the alkaline phosphatase activity was at least as good as it was on tissue culture plastic. However, the total amount of protein, and especially the collagen type I synthesis, was sensitive to surface modification. On titanium modified with ethane-1,1,2-triphosphonic acid, the total amount of synthesized protein was significantly higher than it was on unmodified titanium surfaces. A significant increase (up to 16%) of collagen type I production was observed on titanium surfaces modified with this acid or with methylenediphosphonic acid compared to unmodified titanium surfaces.