Ahmed El-Shafei

A novel carbazole-based dye outperformed the benchmark dye N719 for high efficiency dye-sensitized solar cells (DSSCs)

Two novel high molar extinction coefficient heteroleptic Ru(II) isomers, NCSU-10 and NCSU-10′, based on carbazole antenna were synthesized with the aid of Knoevenagel reaction, to study the influence of the carbazole antenna and anchoring group (COOH) isomerization on the light harvesting efficiency (LHE), ground and excited state oxidation potentials, incident-photon-to-current conversion efficiency (IPCE), short-circuit photocurrent density (JSC), and total solar-to-electric conversion efficiency (η) for DSSCs, and their device performances were compared to the benchmark dye N719. The photophysical and photoelectrochemical properties discussed herein addressed the significant impact of the carbazole antenna and the position of the anchoring group on JSC and η in DSSCs. Tetrabutylammonium (TBA) substituted NCSU-10 achieved efficient sensitization of nanocrystalline TiO2 over the whole visible range, extending into the near IR region (ca. 870 nm) with an excellent power conversion efficiency (η) of 9.37% under an irradiation of full sunlight (100 mW cm−2) with mask compared to 8.17% of N719 under optimized conditions. NCSU-10 outperformed N719 by 45% in molar absorptivity, 18.8% in JSC, and 14.6% in the total conversion efficiency. Molecular modeling studies (DFT/TD-DFT) of NCSU-10 and NCSU-10′ showed that the HOMO is delocalized not only on Ru and NCS but also on the carbazole with a large coefficient, indicating that the second charge generation transfer in the visible region at ∼400 nm is a mixture of metal-to-ligand charge transfer (MLCT) and strong ligand–ligand charge transfer (LLCT) with a significant HOMO coefficient originating from the carbazole antenna (π) to the bipyridyl electron acceptor (π*). Moreover, DFT calculations showed that the 4,4′-isomer (NCSU-10) is a significantly stronger electron acceptor than the 5,5′-isomer (NCSU-10′), which explained the inferior electron injection and significantly lower JSC of the 5,5′-isomer.

Synthesis, antitumor evaluation, molecular modeling and quantitative structure-activity relationship (QSAR) of some novel arylazopyrazolodiazine and triazine analogs.

The synthesis, in vivo and in vitro antitumor evaluation, and QSAR studies of some novel pyrazole analogs against Ehrlich Ascites Carcinoma (EAC) cells were described. In vitro results revealed that compounds 10, 6 and 4 were the most potent analogs against EAC, respectively. Moreover, in vivo evaluation of compounds 6 and 10 proved their capability to normalize the blood picture in comparison to 5-FU, a well known anticancer drug. These novel pyrazole analogs were molecularly designed with the goal of having significant potent cytotoxic effect against EAC cells. To develop a QSAR model capable of identifying the key molecular descriptors associated with the biological activity of the novel pyrazole analogs and predicting the cytotoxic effect for other novel pyrazole analogs against EAC cells, different QSAR models, using different physicochemical and topological molecular descriptors, were developed. Different molecular descriptors were predicted solely from the chemical structures of 16 pyrazolo-diazine and triazine analogs following the prediction of the equilibrium molecular geometry of each analog at the DFT level using B88-LYP functional energy and double zeta valence polarized (DZVP) basis set. It was found that dipole moment, excitation energy, the energy value of LUMO, solvent accessible surface area, and heat of formation were the key molecular descriptors in descriping the cytotoxic effect of those compounds against EAC.

Conferring flame retardancy on cotton using novel halogen-free flame retardant bifunctional monomers: synthesis, characterizations and applications

Two novel halogen-free phosphorous-nitrogen flame retardant bifunctional monomers were synthesized and characterized using attenuated total reflectance/Fourier transform-infrared (ATR/FT-IR) and electrospray ionization mass spectrometry ((+)ESI-MS). The monomers were applied separately and graft polymerized on cotton in the presence of the thermal initiator K(2)S(2)O(8). The performance of each monomer was evaluated using thermal gravimetric analysis (TGA), grafting efficiency, and vertical flame test. It was shown that the performance of N,N-dimethyl di(acryloyloxyethyl)phosphoramide (DMDAEP) (monomer 2) as flame retardant outperformed that of ethyl di(acryloyloxyethyl)phosphorodiamidate (EDAEP) (monomer 1). The superior performance of DMDAEP was attributed to the presence of more nitrogen atoms compared to EDAEP. The increased nitrogen content in DMDAEP increased the synergistic effect of the P-N system. Cotton treated using padding methods showed more promising results than cotton treated by exhaust methods.

Structure–property relationship of extended π-conjugation of ancillary ligands with and without an electron donor of heteroleptic Ru(II) bipyridyl complexes for high efficiency dye-sensitized solar cells

Two new heteroleptic Ru(II) bipyridyl complexes MH06 and MH11 were designed, synthesized and characterized for DSSCs. While the ancillary ligand of MH06 was molecularly engineered with a strong electron donating group coupled with an extended π-conjugated system, the ancillary ligand of MH11 contained a longer π-conjugated system only. Molecular modeling, photophysical, and photovoltaic properties were compared under the same experimental conditions against the benchmark N719. In an effort to understand the structure-property relationship, their photovoltaic and photoelectrochemical properties including Jsc, Voc, ground and excited state oxidation potentials, UV-Vis absorption, and molar extinction coefficients were studied. The UV-Vis results showed intense MLCT absorption peaks of MH06 and MH11 in the visible region with a red shift of 12 and 18 nm, respectively, with significantly higher molar extinction coefficients compared to N719. Tetrabutylammonium (TBA) substituted MH11-TBA demonstrated the most efficient IPCE of over 90% in the plateau region covering the entire visible spectrum and extending into the near IR region (ca. 890 nm), which showed a solar-to-power conversion efficiency (η) of 10.06%, significantly higher than that of the benchmark N719 dye (9.32%). The superior performance in terms of the IPCE and Jsc of MH11 can be attributed to the bulky and highly hydrophobic nature of the pyrene-based ancillary ligand, which behaves as a shielding barrier for hole-transport recombination between TiO2 and the electrolyte. In addition, the IMPS results showed that the contribution of dyes to the conduction band shift of the TiO2 level is almost similar, regardless of different substitutions on the bipy-moiety. This implies that the open-circuit photovoltage (Voc) increases with reduced charge recombination in the presence of a thick layer of tetrabutyl ammonium ions (TBA) of the dye anchored on the surface of TiO2.

Ag-encapsulated Au plasmonic nanorods for enhanced dye-sensitized solar cell performance

In this article, Ag-encapsulated Au nanorods (Au@Ag NRs) are prepared and introduced into dye-sensitized solar cells (DSSCs). As a unique plasmonic nanostructure, this composite exhibits the superiorities of enhanced light-harvesting as well as restrained charge recombination of DSSCs. Remarkably, the enhanced light absorption of the photoanode can be obtained via the surface plasmon resonance (SPR) effect of the Au@Ag NRs, whereas a broadened absorption in the red and near-infrared (NIR) region ensures the full utilization of the solar energy. Beyond the dominated optical utility, the presence of the Au@Ag NRs promotes the suppression of the charge recombination, further enhancing the photochemical catalysis of DSSCs. An optimized Au@Ag NR modified DSSC is achieved with a power conversion efficiency of 8.43%, which is significantly superior to that of the pure TiO2 DSSC with a PCE of 5.91%.

Donor–acceptor dyes incorporating a stable dibenzosilole π-conjugated spacer for dye-sensitized solar cells

Four novel organic dyes including three based on dibenzosilole (YS01–03) and one based on fluorene (YS04) were synthesized, and their photophysical properties and dye-sensitized solar cell (DSC) performances were characterized. The silicon-containing dibenzosilole-based dyes (YS01–03) were superior to the carbon analogue fluorene-based dye YS04 in incident-photon-to-current conversion efficiency (IPCE), and total solar-to-electric conversion efficiency (η), with YS03, which has the bulkiest and most branched electron donor group, achieving the highest η of 5.07% compared to 2.88% of YS04. To better understand how silicon influences the excited state oxidation potentials (S+/*) and absorption maxima (λmax), the equilibrium molecular geometries of dyes YS01–04 were calculated using density functional theory (DFT) utilizing B3LYP energy functional and DGDZVP basis set. It was shown that the torsion angles (θ1 and θ2) across the biphenyl linkages of dyes containing silicon (YS01–03) were less twisted than that of the silicon-free dye (YS04), which enhanced the π–π* overlap, and that translated into photocurrent enhancements in the silicon-containing dyes YS01–03. Moreover, the vertical electronic excitations and S+/* of dyes YS01–04 were studied using different long-range corrected time-dependent DFT methods, including CAM-B3LYP, LC-BLYP, WB97XD, and LC-wPBE at the basis set level DGDZVP. Excellent agreement between the calculated, using CAM-B3LYP/DGDZVP, and experimental results was found.

Structure-property relationship of naphthalene based donor-π-acceptor organic dyes for dye-sensitized solar cells: Remarkable improvement of open-circuit photovoltage

Four new donor–π–acceptor organic dyes (YF01–04), containing naphthalene-substituted amines as an electron donor and cyanoacrylic acid as an electron acceptor, were designed and synthesized, and their photophysical properties and dye-sensitized solar cells (DSCs) performances were characterized. Dyes YF02 and YF04, with 2,6-disubstituted naphthalene frameworks, were superior than their analog dyes YF03 and YF01, having 1,2-disubstituted naphthalene moiety, in incident-photo-to-current conversion efficiency (IPCE) and total solar-to-electric conversion efficiency (η). The DSCs based on YF02, comprised of diphenylamine moiety as the donor, produced the highest η of 5.29% compared to 4.03% of the analog dye YF04, which has pyrrolidine as the donor. Remarkably, a high open-circuit photovoltage (Voc) of 0.799–0.807 V was achieved in the cases of YF02–03, which have diphenylamine-donors. To better understand the structure–property relationship for DSCs application, molecular modelling was performed on YF01–04 and vertical electronic excitations were calculated using long-range corrected energy functional WB97XD and CAM-B3LYP at the basis set level DGDZVP, which were in excellent agreement with the experimental results. Moreover, the equilibrium molecular geometries of dyes YF01–04 were calculated at the density function theory (DFT) level using the hybrid energy functional B3LYP and basis set DGDZVP. The torsion angles (θ) between the naphthalene moiety and diphenylamine donor in YF02 and YF03 were more twisted than that of the pyrrolidine-donor dyes YF01 and YF04, precluding efficient intermolecular π–π charge transfer, which translated into high Voc. Compared to the reference dye TA-St-CA, which is based on diphenylamine as an electron donor linked to a phenyl ring, YF02 achieved higher Voc, which indicated that naphthalene substituted with diphenylamine is more efficient in retarding charge recombinations.

Influence of Number of Benzodioxan-Stilbazole-based Ancillary Ligands on Dye Packing, Photovoltage and Photocurrent in Dye-Sensitized Solar Cells

Two novel heteroleptic Ru(II) bipyridyl complexes, HD-2 and HD-2-mono, were molecularly engineered, synthesized and characterized for dye-sensitized solar cells (DSCs). The influences of mono versus bis electron-donor benzodioxan ancillary ligands on optical, dye packing, electrochemical and photovoltaic properties were examined and compared to the benchmark N719. HD-2 and HD-2-mono achieved solar-to-power conversion efficiencies (%η) of 9.64 and 9.50, respectively, compared to 9.32 for N719 under the same experimental device conditions. Optical results showed that HD-2 and HD-2-mono have much higher molar extinction coefficients, longer excited state lifetimes and narrower HOMO-LUMO gaps compared to N719. Although the molar extinction coefficient of HD-2-mono was 27% less than that of HD-2, it outperformed HD-2 in photovoltaic performance when anchored on TiO2, owing to better dye packing and loading of the former. Charge recombination at the dye/TiO2 interface by impedance spectroscopy analysis showed that the recombination resistance and the lifetime of injected electron in TiO2 conduction band is directly proportional to the open-circuit voltage (Voc) observed. Furthermore, compared to HD-2 and HD-2-mono, the greater Voc of N719 can be attributed to the greater negative free energy for dye regeneration. Both HD-2 and HD-mono have almost the same negative free energy, which explains why they achieved almost the same Voc. Decay dynamic analysis for solar devices fabricated from the named dyes, by time correlated single photon counting (TCSPC), elucidated that the lowest excited state decay lifetime for HD-2-mono, HD-2 and N719 are 3, 10 and 20 ps, respectively. The shorter the decay lifetime, the less kinetic redundancy, which leads to better photocurrent, and that explanation is consistent with the measured photocurrent and total solar-to-power conversion efficiency of the named dyes in the order of HD-2-mono > HD-2 > N719.

Influence of cyclic versus acyclic oxygen-containing electron donor ancillary ligands on the photocurrent, photovoltage and photostability for high efficiency dye-sensitized solar cells

Three novel heteroleptic amphiphilic polypyridyl Ru-complexes, MH01, MH03, and MH05, with oxygen-containing-electron-donor stilbazole-based ancillary ligands were synthesized to study the influence of the cyclic-electron-donor (MH01), the presence of the cyclic electron donor coupled to acyclic electron-donor auxochromes (MH03) ortho to the CHCH bridge of stilbazole, and the presence of only acyclic electron-donor methoxy group (MH05) on molar extinction coefficient, light harvesting efficiency (LHE), ground and excited state oxidation potentials, and photovoltaic performance for DSSCs. Although MH05 has three electron donor methoxy groups, it achieved the lowest molar extinction coefficient of 18 250 M−1 cm−1 and exhibited the lowest photocurrent. The highest photocurrent density (JSC) was observed for the longest interatomic distance between the CHCH bridge of the stilbazole moiety and cyclic-electron-donor auxochromes (MH01). It was also shown that while incorporation of acyclic electron-donor auxochromes ortho to the CHCH bridge (MH03) has little effect on the ground and excited state oxidation potentials, λmax of the low energy MLCT, and molar absorptivity, the lowest photovoltage and %η were observed. When compared under the same experimental device conditions using 0.3 M tert-butylpyridine (TBP), only MH01-TBA achieved 18% more in JSC and 8.6% greater in η than the benchmark dye N719. To probe the interrelationship among the cyclic-vs.-acyclic oxygen-containing electron donors of the ancillary ligands, photocurrent and photovoltage of these dyes, the equilibrium molecular geometries of the ancillary ligands were calculated using DFT. The HOMO distribution on cyclic-vs.-acyclic electron donors and the position of OMe in the ancillary ligands rationalized the fundamental science behind the photovoltaic performance and photostability of these dyes.

Metallization of non-genotoxic direct dyes

Abstract Copper (II) salts were used as metallizing agents in the synthesis of new direct dyes for cotton. In this regard, direct dyes possessing ortho -propoxy, ortho′ -hydroxy-substituted systems formed the corresponding dye–metal complexes. The complexes were characterized by neutron activation and spectrometric analyses and evaluated on cotton for color fastness.