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A seriesof D−π–A organic dyes, X72–75,containing novel triarylamine electron donors have been synthesizedfor dye-sensitized solar cells (DSCs). The superiority of the asymmetricdesign of the triphenylamine electron donor over the symmetrical triphenylaminewhen applied in organic dyes for cobalt cells has been observed. UsingX72 with the cobalt(II/III) redox shuttle resulted in an overall powerconversion efficiency (PCE) of 9.18%, outperforming the state-of-the-artdye C218 under the same conditions. [ABSTRACT FROM AUTHOR]

Indolinedyes exhibit impressive short-circuit photocurrent (JSC) but show generally low open-circuit voltage (VOC) in dye-sensitized solar cells (DSCs). Toretard chargerecombination in DSCs, four indoline dyes (XS41, XS42, XS43, and XS44)featuring, respectively, dipropylfluorene, hexyloxybenzene, tert-butylbenzene, and hexapropyltruxene electron donors,have been engineered. The incorporation of bulky rigid groups (i.e.,dipropylfluorene and hexapropyltruxene unit) can notably retardthe charge recombination at the titania/electrolyte interface. Moreover,we have developed two organic dyes (TC1 and TC2) as alternative coadsorbentsto chenodeoxycholic acid (CDCA). Interestingly, it is found that regardlessof the dye selection coadsorption with TC2 shows an improved VOCas well as JSCin comparison with its TC1 analogues. Dependence of photovoltageon the structure of TC1/TC2 was also investigated. The results suggestthat the change in VOCis likely correlatedwith the molecular matching between the dyes and the coadsorbents.Combining the two contributions, high VOCin indoline-based DSCs can be realized. The results of XS41, uponcoadsorption with TC2, produce a JSCof16.1 mA cm–2, a VOCof770 mV, and a fill factorof 0.66, corresponding to a power conversion efficiency of 8.18% undersimulated AM1.5G solar light (100 mW cm–2). Thesefindings pave a new way to achieve further efficiencyenhancement of indoline dyes. [ABSTRACT FROM AUTHOR]

We have verified in our previous work that lignin peroxidase (LiP) mediates effective removal of selected natural and synthetic estrogens. The efficiency of these reactions was greatly enhanced in the presence of veratryl alcohol (VA), a chemical that is produced along with LiP by certain white rot fungi, for example, Phanerochaete chrysosporium. In this study, we systematically evaluated the kinetic behaviors of LiP-mediated reactions for six endocrine disrupting compounds (EDCs), that is, steroid estrogens and their structural analogs, in both the presence and absence of VA. Resulting kinetic parameters were then correlated with structural features of LiP/substrate binding complexes, as quantified using molecular simulation, to create quantitative structure-activity relationship (QSAR) equations. These equations suggest that binding distance between a substrate's phenolic proton and δN of HIS47's imidazole ring plays an important role in modulating substrate reactivity toward LiP in both the presence and absence of VA. This information provides insight into an important enzymatic reaction process that occurs in the natural environment affecting EDC transformation, a process that may be used in engineered systems to achieve EDC removal from water. [ABSTRACT FROM AUTHOR]

We have demonstrated in our earlier work that a few natural and synthetic estrogens can be effectively transformed through reactions mediated by lignin peroxidase (LiP). The behaviors of such reactions are variously influenced by the presence of natural organic matter (NOM) and/or veratryl alcohol (VA). Certain white rot fungi, e.g. Phanerochaete chrysosporium, produce VA as a secondary metabolite along with LiP in nature where NOM is ubiquitously present. Herein, we report a study on the products resulting from LiP-mediated oxidative coupling reactions of a representative estrogen, 17β-estradiol (E2), and how the presence of NOM and/or VA impacts the formation and distribution of the products. A total of six products were found, and the major products appeared to be oligomers resulting from E2 coupling. Our experiments revealed that these products likely formed colloidal solids in water that can be removed via ultrafiltration or settled during ultracentrifugation. Such a colloidal nature of the products could have important implications in their treatability and environmental transport. In the presence of VA, the products tended to shift toward higher-degree of oligomers. When NOM was included in the reaction system, cross-coupling between E2 and NOM appeared to occur. Data obtained from E-SCREEN test confirmed that the estrogenicity of E2 can be effectively eliminated following sequential reactions mediated by LiP. [ABSTRACT FROM AUTHOR]

Our experiments revealed that a few natural and synthetic estrogens can be effectively transformed through reactions that are mediated by lignin peroxidase (LiP), an extracellular enzyme that is produced by a white rot fungus Phanerochaete chrysosporium and is widely present in the natural environment We systematically assessed the reaction efficiencies at varying important conditions and identified the reaction products using mass spectrometry. In particular, we compared the reaction behaviors for systems variously containing natural organic matter and/or veratryl alcohol, a secondary metabolite that P. chrysosporium produces along with LiP in nature to play a role in mediating LiP activity. On the basis of the observed reaction behaviors and the molecular characteristics of the substrates and the enzyme, we postulate that the active binding site for estrogens is located within the LiP heme cavity, whereas that for veratryl alcohol is on the enzyme surface. Our study suggests that the processes mediated by LiP and other naturally occurring enzymes of similar nature may influence the environmental transformation and fate of estrogen contaminants. The findings in this study provide useful information for understanding LiP-mediated estrogen reactions and for potential development of novel enzymatic method to control estrogen contamination. [ABSTRACT FROM AUTHOR]

The reactions of the unsymmetrical ligand N-phenyl- N′-cyano-formamidine ( L) with AgX (X = NO 3−, SO 3CF 3−, and BF 4−) afforded the complexes [Ag L3NO 3] ( 1), [Ag LSO 3CF 3] ∞( 2) and [Ag LBF 4] ∞( 3), whereas the reactions of Lwith AgClO 4in tetrahydrofuran at room temperature and at refluxing temperature afforded two supramolecular isomers of [Ag LClO 4] ∞, ( 4) and ( 5), respectively. These complexes were characterized by X-ray crystallography, which confirmed that complexes 2− 5are coordination polymers. Complex 1is a triangular planar molecule with three L’s coordinating to the Ag(I) metal center through the cyano nitrogen atoms. While the cations of complexes 2− 4form one-dimensional zigzag chains, those of 5show helical chains that are interlinked through η 3π-donor behavior of the unsymmetrical ligand Lto form two-dimensional polymeric sheets. The Lligands in complex 1adopt the syn conformation, and those in 2– 5adopt the anti conformation. [ABSTRACT FROM AUTHOR]

We investigate an interlayer of 6,6'-bis(4-(bis(4-methoxyphenyl)amino)phenyl)-[1,1'-binaphthalene]-(2,2'-diyl)bis(oxy)bis(propane-3,1-diyl)bis(phosphonic acid) (BINOL-PA) with undoped poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) coverage. The incorporation of the 1,10-bi-2-naphthol central core enhances π-π stacking and reduces charge recombination at the interface. Compared to PTAA alone (0.95 eV), BINOL-PA/PTAA exhibits a shorter distance from the Fermi energy ( E F ) to the valence-band maximum (VBM) (0.36 eV). Two phosphoric acid units in BINOL-PA fine-tune the molecular dipoles. Theoretical calculations reveal electrostatic surface potential differences between BINOL-PA and PTAA in their backbone structure. Open-circuit voltage decay (OCVD) and electrochemical impedance spectroscopy (EIS) results suggest suppressed interface recombination. The photovoltaic conversion efficiency (PCE), short-circuit current density ( J SC ), open-circuit voltage ( V OC ), and fill factor (FF) for the BINOL-PA/PTAA device are measured as 21.02%, 22.67 mA cm -2 , 1.12 V, and 82.8%, respectively, all higher than those achieved by the PTAA device with a PCE of 18%. BINOL-PA/PTAA significantly elevates V OC and FF values compared with dopant-free PTAA alone. The champion device retains over 89% of its initial PCE after being exposed to an ambient environment without encapsulation for more than 30 days. The thermal aging test conducted under a nitrogen atmosphere demonstrates that the efficiency retention rate for BINOL-PA/PTAA displays 60% of its initial efficiency after 1500 h.

The selective oxidation of amines to imines under mild conditions has attracted much attention. Our study reveals that copper phenylacetylide (PhC 2 Cu) could serve as an efficient photocatalyst for imine synthesis under visible-light irradiation (>400 nm). Utilizing benzylamine as a model reactant, PhC 2 Cu achieves an imine yield of 50.4%, which is 5 times higher than that of P25 under the same conditions and comparable to the yield obtained by the 3 wt % Au/P25 photocatalyst (55.4%). Further loading 3.9 nm TiO 2 onto PhC 2 Cu through tetrabutyl titanate hydrolysis increases the imine yield to 84.7%, with a Ti:Cu atomic ratio of 3.65%. Control experiments, photoluminescence (PL) spectra, optical pump terahertz probe (OPTP) spectra, and electron spin resonance (ESR) tests confirm that the optimized TiO 2 modification promotes the separation of excited carriers and electron transfer in PhC 2 Cu and facilitates the activation of surface oxygen, thereby enhancing the formation of superoxide radicals, a key active oxygen species in the reaction system. This work presents a promising strategy for efficient imine synthesis via amine coupling and expands the application field of PhC 2 Cu-based photocatalysts.

The two-step sequential deposition strategy has garnered widespread usage in the fabrication of high-performance perovskite solar cells based on FAPbI 3 . However, the rapid reaction between FAI and PbI 2 during preparation often leads to incomplete reactions, reducing the device efficiency and stability. Herein, we introduced a multifunctional additive, 2-thiophenyl trifluoroacetone (TTA), into the FAI precursor. The incorporation of TTA has proven to be highly effective in slowing the reaction rate between FAI and PbI 2 , resulting in increased perovskite formation and improved efficiency and stability of the devices. TTA's CF 3 groups interact with FAI via hydrogen bonding, effectively suppressing FA + defects. The S and C═O groups share lone pair electrons with uncoordinated Pb 2+ , leading to a reduction in perovskite film defects and suppressing nonradiative recombination. Additionally, the CF 3 groups impart hydrophobicity, protecting the perovskite film from moisture-induced erosion. As a result, the TTA-modified perovskite film achieves a Champion efficiency of 23.42% compared to the control's 21.52, with 20.58% efficiency for a 25 cm 2 solar module. Remarkably, the unencapsulated Champion device retains 86% of its initial PCE after 1080 h under dark conditions (60 ± 5 °C, 35 ± 5% RH), indicating enhanced long-term stability. These findings offer a promising and cost-effective tactic for high-quality perovskite film fabrication.

Exploring polymeric hole-transporting materials (HTMs) with passivation functions represents a simplified and effective approach to minimize the perovskite defect density. To date, most of reported polymeric HTMs were applied to fabricate n-i-p regular perovskite solar cells (PSCs). The polymers compatible for p-i-n inverted PSCs were very limited. Moreover, the passivation polymers were devoted to passivate the uncoordinated Pb 2+ . However, the MA + cation defect has profound unwanted effect on device efficiency and long-term stability. In order to synchronously passivate the Pb 2+ and MA + defects in p-i-n inverted PSCs, a new nonfused polymer was intentionally explored via mild polymerization. The aromatic bridge instead of long alkyl chains enabled polymer BN-12 to achieve excellent thermal stability and good wettability of perovskite precursor. Furthermore, the incorporation of chemical anchor sites ("C═O" and "F") strongly controlled the crystallization of perovskite and restrained the MA + ion migration. As a result, a significant fill factor (FF) of 82.9% and an enhanced power conversion efficiency (PCE) of 20.28% were achieved for MAPbI 3 -based devices with the dopant-free BN-12, exceeding those with the commercial HTM PTAA (FF = 81.7%, PCE = 19.51%). More importantly, the unencapsulated devices based on BN-12 realized outstanding long-term stability, maintaining approximately 95% of its initial efficiency after stored for 85 days. By contrast, the PTAA-based device showed rapid decrease which retained only 50% of its initial value after 45 days.

Vehicular catalytic converters are used to regulate, reduce, and convert toxic and environmentally unfriendly compounds in exhaust gases into relatively inert and less harmful chemical species. The efficiency, however, is largely affected by the operating temperature of the converter which is set by the hot exhaust gas released from the combustion chamber. A major gas released during combustion is CO 2 , and its multiply substituted isotopocule, namely, 13 C 16 O 18 O, provides a window of opportunity to probe directly the effective temperature of the converter in operation. Here, we report multiple isotopic measurements in exhaust CO 2 (δ 13 C, δ 17 O, δ 18 O, and Δ 47 ) of diesel (trucks and buses) and gasoline (sedans, trucks, and two-wheel motorcycles)-powered vehicles. For investigating the efficiency of a converter in reducing toxic compounds, we studied NO x processes through isotopic analysis of the exhaust N 2 O. We found that the degree of N 2 O reduction to N 2 in gasoline-powered vehicles is high when the temperature is above 200 °C (inferred by Δ 47 ). In contrast, diesel-powered vehicles produce N 2 O in abundance, probably a consequence of selective catalytic reduction of NO x , and the reduction efficiency depends on the converter temperature. In other words, the catalytic converters act as sinks and sources of N 2 O to the atmosphere in gasoline- and diesel-operated vehicles, respectively. We also report a new set of field data by measuring the isotopic compositions of CO 2 and N 2 O in the Hsuehshan tunnel, a ∼13 km long highway tunnel in Taiwan. Elevated N 2 O concentrations inside the tunnel indicate that the emission of N 2 O by heavy-duty diesel vehicles is much higher compared to the reduction by gasoline-operated passenger cars, making the vehicular exhausts a net source of N 2 O to the atmosphere. The combined study of clumped isotopes and N 2 O concentration in exhaust gases suggests that it is useful to probe the operational temperature of catalytic converters and monitor the pollution level in operation, thus providing an opportunity for manufacturers to optimize the catalytic efficiency to reduce the level of toxic pollutants to the environment.

The core plays a crucial role in achieving high performance of linear hole transport materials (HTMs) toward the perovskite solar cells (PSCs). Most studies focused on the development of fused heterocycles as cores for HTMs. Nevertheless, nonfused heterocycles deserve to be studied since they can be easily synthesized. In this work, we reported a series of low-cost triphenylamine HTMs (M101-M106) with different nonfused cores. Results concluded that the introduced core has a significant influence on conductivity, hole mobility, energy level, and solubility of linear HTMs. M103 and M104 with nonfused oligothiophene cores are superior to other HTMs in terms of conductivity, hole mobility, and surface morphology. PSCs based on M104 exhibited the highest power conversion efficiency of 16.50% under AM 1.5 sun, which is comparable to that of spiro-OMeTAD (16.67%) under the same conditions. Importantly, the employment of M104 is highly economical in terms of the cost of synthesis as compared to that of spiro-OMeTAD. This work demonstrated that nonfused heterocycles, such as oligothiophene, are promising cores for high performance of linear HTMs toward PSCs.

Asymmetric 8H-thieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]pyrrole (TTP) unit has been synthesized and used as a rigid and coplanar π-bridge to construct four new metal-free sensitizers W05-08. These dyes sensitized solar cells exhibit high photocurrent due to strong light harvesting capability. Among these dyes, the W05-based cell in conjunction with cobalt(II/III) redox shuttle exhibits the best power conversion efficiency up to 9.22%.

Quantification of contributions from various sources of CO 2 is important for understanding the atmospheric CO 2 budget. Considering the number and diversity of sources and sinks, the widely used proxies such as concentration and conventional isotopic compositions (δ 13 C and δ 18 O) are not always sufficient to fully constrain the CO 2 budget. Additional constraints may help in understanding the mechanisms of CO 2 production and consumption. The anomaly in triple oxygen isotopes or 17 O excess (denoted by Δ 17 O) and molecules containing two rare isotopes, called clumped isotopes, are two recently developed tracers with potentials to independently constrain some important processes that regulate CO 2 in the atmosphere. The clumped isotope for CO 2 , denoted by Δ 47 , is the excess of 13 C 16 O 18 O over a random distribution of isotopes in a CO 2 molecule. We measured the concentrations of δ 13 C, δ 18 O, Δ 17 O, and Δ 47 in air CO 2 samples collected from the Hsuehshan tunnel (length: 12.9 km), and applied linear and polynomial regressions to obtain the fossil fuel end-members for all these isotope proxies. The other end-members, the values of all these proxies for background air CO 2 , are either assumed or taken as the values obtained over the tunnel and ocean. The fossil fuel (anthropogenic) CO 2 end-member values for δ 13 C, δ 18 O, Δ 17 O, and Δ 47 are estimated using the two component mixing approach: the derived values are -26.76 ± 0.25‰, 24.57 ± 0.33‰, -0.219 ± 0.021‰, and 0.267 ± 0.036‰, respectively. These four major CO 2 isotope tracers along with the concentration were used to estimate the anthropogenic contribution in the atmospheric CO 2 in urban and suburban locations. We demonstrate that Δ 17 O and Δ 47 have the potential to independently estimate anthropogenic contribution, and the advantages of these two over the conventional isotope proxies are discussed.

With respect to the electron-withdrawing acceptors of D-A-π-A organic dyes, reports on the second electron-donating donors for D-D-π-A organic dyes are very limited. Both of the dyes have attracted significant attention in the field of dye-sensitized solar cells (DSCs). In this work, four new D-D-π-A organic dyes with dithieno[3,2-b:2',3'-d]pyrrole (DTP) or bis(amine) donor have been designed and synthesized for a investigation of the influence of the terminal electron donor in D-D-π-A organic dye-sensitized solar cells. It is found that DTP is a promising building block as the terminal electron donor when introduced in the dithiophenepyrrole direction, but not just a good bridge, which exhibits several characteristics: (i) efficiently increasing the maximum molar absorption coefficient and extending the absorption bands; (ii) showing stronger charge transfer interaction as compared with the pyrrole direction; (iii) beneficial to photocurrent generation of DSCs employing cobalt electrolytes. DSCs based on M45 with the Co-phen electrolyte exhibit good light-to-electric energy conversion efficiencies as high as 9.02%, with a short circuit current density (JSC) of 15.3 mA cm(-2), open circuit voltage (VOC) of 867 mV and fill factor (FF) of 0.68 under AM 1.5 illumination (100 mW cm(-2)). The results demonstrate that N,S-heterocycles such as DTP unit could be promising candidates for application in highly efficient DSCs employing cobalt electrolyte.

We used magnetofection (MF) to achieve high transfection efficiency into human mesenchymal stem cells (MSCs). A custom-made magnet array, matching well-to-well to a 24-well plate, was generated and characterized. Theoretical predictions of magnetic force distribution within each well demonstrated that there was no magnetic field interference among magnets in adjacent wells. An optimized protocol for efficient gene delivery to human hair follicle derived MSCs (hHF-MSCs) was established using an egfp-encoding plasmid, reaching approximately ∼50% transfection efficiency without significant cytotoxicity. Then we applied the optimized MF protocol to express the pluripotency-associated transcription factor NANOG, which was previously shown to reverse the effects of organismal aging on MSC proliferation and myogenic differentiation capacity. Indeed, MF-mediated NANOG delivery increased proliferation and enhanced the differentiation of hHF-MSCs into smooth muscle cells (SMCs). Collectively, our results show that MF can achieve high levels of gene delivery to MSCs and, therefore, may be employed to moderate or reverse the effects of cellular senescence or reprogram cells to the pluripotent state without permanent genetic modification.

Dye-sensitized solar cells (DSCs) have gained widespread attentions owing to their low production cost, tunable optical response, and high light-to-electricity conversion. In DSCs, the performance of redox mediators with iodide/triiodide or iodine-free redox couples is vital to internal quantum efficiency. For a long time, iodide/triiodide based electrolytes are the most widely used mediators because of their desirable kinetics. Recently, exciting progress has been made with respect to iodine-free metallorganic and pure organic redox shuttles. Their tunable redox potential and diverse electron transfer behaviors enable the rational screening of electrolyte composition for enhancing the light-to-electricity conversion efficiency of DSCs toward the Shockley-Queisser limit. In this Account, we emphasize on current knowledge of two distinct but interrelated interfacial processes (electron recombination and dye regeneration), particularly for DSCs with iodine-free redox couples. We show that a deeper understanding of electron transfer kinetics of the alternative redox couples is fundamental to develop rational strategies for cell optimization. Compared with iodine electrolyte, iodine-free metallorganic redox couples such as iron, cobalt, and nickel complexes display much faster electron transfer kinetics in dye regeneration and interfacial recombination. Evidently, rapid regeneration enables the employment of more positive metal complex for attaining a higher photovoltage. However, severe recombination reactions have to be well controlled by using several effective surface treatments such as the addition of Brönsted bases and atomic layer deposition. Although these methods offer different pathways in surface passivation, a trade-off between charge injection efficiency and electron diffusion length is always observed. It follows that an appropriate LUMO level of sensitizer is essential to ensure efficient electron injection at the passivated TiO2 surface. Apart from fast recombination behavior, bulky metal complexes suffer from inefficient charge transport. Thus, the combination of thinner TiO2 film and sensitizers with high mole extinction coefficient has been employed for both enhancing diffusion-limited current and maintaining light-harvesting efficiency. Unlike metal complexes, most of organic sulfur redox couples in DSCs exhibit slow recombination kinetics. This allows the use of thicker TiO2 film to achieve an optimized light harvesting. However, the concomitant sluggish behavior of dye regeneration requires the use of sensitizers with more positive HOMO level, which is beneficial to efficient regeneration. Moreover, lower level of TiO2 band edge in DSCs based on organic sulfur mediators hinders the achievement of desirable photovoltage, spurring future explorations on this class of redox mediator. Based on the comparison of electron transfer behavior between iodine-free metallorganic complexes and pure organic redox couples, we aim to provide a comprehensive Account of the intriguing interfacial processes in iodine-free DSCs as the key scientific point is linked with the kinetics of interfacial reactions. This demonstrates the advantages as well as disadvantages of each class of iodine-free electrolyte and should shed light on to judicious selection of the energy levels for redox mediators, sensitizers, and the conduction band of TiO2 for DSCs. The knowledge of the reaction kinetics in DSCs should be also beneficial to the interface engineering on recent developed perovskite cells.

Indoline photosensitizers exhibit impressive short-circuit photocurrent but generally low molar extinction coefficient and rapid charge recombination, which limits their application in thin-film dye-sensitizerd solar cells (DSCs). Here, we incorporate a new dithieno[3,2-b:2',3'-d]pyrrole (DTP) segment (i.e., dihexyloxy-triphenylamine (DHO-TPA) substituted DTP) as the conjugated π-linker to construct a series of high molar absorption coefficient indoline dyes (XW69, XW70, and XW71) for DSCs employing a cobalt(II/III) redox electrolyte. Interestingly, this DTP linker is demonstrated as an efficient building block, not only slowing down the kinetics of charge recombination of titania electrons with tris(1,10-phenanthroline)cobalt(III) ions but also making a great contribution to the light absorption properties in comparison with the dihexylaniline substituted DTP. With respect to the dihexyloxy-triphenylamine dye (XW68), these new indoline dyes exhibit stronger light-harvesting and thus better power conversion efficiency of DSCs made from thin titania films. Benefitting from the bulky rigidity of the donor and π-conjugation unit, the XW70 dye displays a promising conversion efficiency as high as 8.78%, with a short-circuit current density (J(SC)) of 13.3 mA cm(-2), open-circuit voltage (V(OC)) of 943 mV, and fill factor (FF) of 0.70 under AM 1.5 illumination (100 mW cm(-2)). Furthermore, the effect of light irradiation on these dyes adsorbed on nanocrystalline TiO2 films was investigated, proving the photostability of these indoline chromophores. Our work has valued the feasibility of judicious design of indoline chromophores to obtain organic photosensitizers for high-efficiency iodine-free DSCs made from thin titania films.

The isotopic composition of carbon dioxide provides a powerful tool and has been widely used for constraining the sources and sinks of atmospheric CO2. In this work, we demonstrate a simple, rapid, and clean way for measuring the triple oxygen isotope ratio of carbon dioxide with high precision. The method depends on isotope exchange between O2 and CO2 in the presence of platinum at high temperature and allows rapid measurement of Δ(17)O of CO2. The method has been established and confirmed through several tests by using artificially made CO2 with known Δ(17)O values. The analytical precision obtained for determining Δ(17)O in CO2 is 0.045‰ (1 - σ standard deviation).

Two ruthenium complexes featuring bulky ancillary ligands, XS48 and XS49, were synthesized and studied as dyes in dye-sensitized solar cells (DSCs). Both dyes exhibit higher solar-to-electrical energy conversion efficiency when compared to a commonly used N3 sensitizer under the same conditions. To examine the influence of the bulky ancillary ligands and alleviate the electron recombination in cells, we have developed a dual functioned truxene-based coadsorbent (MXD1) as an alternative candidate to chenodeoxycholic acid (CDCA). This coadsorbent not only effectively shields the back electron transfer from the TiO(2) to I(3)(-) ions but also enhances the light harvesting ability in the short wavelength regions. The photovoltaic performance of XS48-sensitized DSC was independent of the coadsorbents, while XS49 with large bulky ancillary ligand presented better performance when coadsorbent was employed. Interestingly, the simultaneous adsorption-to-sequential adsorption of XS48/49 and MXD1 has caused a notably improved photovoltage, which can be primarily ascribed to the enhanced dye adsorption and retardation of charge recombination. These results not only provide a new vision on how ancillary ligands affect the performance of ruthenium complexes but also open up a new way to achieve further efficiency enhancement of ruthenium complexes.

A new class of organic sensitizers incorporating a benzo[1,2-b:4,5-b']dithiophene (BDT) unit as conjugated spacer has been synthesized and successfully used for dye-sensitized solar cells (DSSCs). The length of the π-conjugated spacers has a strong impact on electro-optical properties of these dyes, leading to the conversion efficiencies ranging from 4.17 to 5.68% under AM 1.5 G irradiation. This result indicates that the BDT unit is a promising candidate in organic sensitizers., (© 2011 American Chemical Society)