Radical Anions and Dianions of Naphthalenediimides Generated within Layer-by-Layer Zirconium Phosphonate Thin Films.

Chemical reduction of N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (PNDI) with the reducing agent sodium dithionite gave stable colored reduced species, both in homogeneous solutions and in self-assembled thin films. When colorless PNDI aqueous solutions were titrated with the reducing agent, stepwise reduction was observed, giving first the radical anion (PNDI-•) and then the dianion (PNDI2-) species, which were detected by UV-visible-NIR spectroscopy, allowing the unambiguous determination of absorption maxima and molar absorptivities for each species. The radical anion PNDI-• was found to form π-dimers in water, but monomeric PNDI-• was formed in the presence of the cationic surfactant cetyltrimethylammonium bromide, indicating association with the micelles. Thin films of PNDI with 25 layers were grown by the zirconium phosphonate method on quartz substrates. Reduction of the films with sodium dithionite also produced radical anions and dianions of PNDI. However, reduction in the films was much slower than in solution, evidencing the compactness of the films. Moreover, reduction in the films did not proceed to completion, even with excess of the reducing agent, which can be attributed to the repulsion of negative charges within the film.

Layer-by-Layer Naphthalenediimide/Zn Phosphonate Hybrid Films Grown from Aqueous Solutions by a Simple Deposition Technique.

Hybrid thin films containing N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (PNDI) and zinc cations (PNDI/Zn films) were built on silicon and indium tin oxide (ITO) substrates by a simple layer-by-layer deposition process. Silicon substrates primed with a layer of phosphonate groups were immersed alternately into zinc nitrate and PNDI aqueous solutions, yielding PNDI/Zn films containing up to 40 layers. ITO substrates, on the other hand, were used without priming, and the deposition sequence began with a PNDI layer. All film growth steps were conducted at room temperature, using aqueous solutions, thus assuring an environmentally clean process. The PNDI/Zn films were studied by X-ray reflectivity and grazing angle X-ray diffraction, using synchrotron radiation source. The films were constituted by crystallites, containing zinc phosphonate layers oriented nearly parallel to the substrate. PNDI/Zn films on ITO were reduced to stable free radicals, which were observed by UV-visible spectroscopy. Moreover, PNDI/Zn bulk materials with structural analogy with the films were produced.

Synthesis of Novel Periodic Mesoporous Organosilicas Containing 1,4,5,8-Naphthalenediimides within the Pore Walls and Their Reduction To Generate Wall-Embedded Free Radicals.

Novel periodic mesoporous organosilicas (PMOs) containing 1,4,5,8-Naphthalenediimide (NDI) chromophores as an integral part of the pore walls were synthesized in acidic conditions, in the presence of inorganic tetraethyl orthosilicate, using triblock copolymer surfactant Pluronic P-123 as a template. The NDI precursor, the bridged silsesquioxane N, N'-bis(3-triethoxysilylpropyl)-1,4,5,8-naphthalenediimide, was synthesized by reaction of 1,4,5,8-naphthalenetetracarboxylic dianhydride with excess 3-aminopropyltriethoxysilane. A series of samples containing up to 19% (weight %) of NDI were prepared (the materials were labeled PMONDIs). 13C and 29Si solid-state nuclear magnetic resonance revealed that the NDI moiety was intact in the PMONDIs and efficiently grafted to the silica network. Samples with up to 16% NDI load presented an ordered two-dimensional-hexagonal mesoscopic structure, according to small-angle X-ray scattering, transmission electron microscopy, and nitrogen adsorption isotherms. Fluorescence spectra of the PMONDIs showed excimer formation upon excitation, suggesting high flexibility of the organic moieties. Reduction of PMONDIs with aqueous sodium dithionite led to the formation of wall-embedded NDI anion radicals, as observed by the appearance of new visible/near-infrared absorption bands. The PMONDIs were also shown to be efficient photocatalysts in the degradation of sulfadiazine, an antibiotic selected here as a model pollutant, which is usually present in water bodies and wastewater.

Unraveling Interfacial Photoinduced Charge Transfer and Localization in CsPbBr3 Nanocrystals/Naphthalenediimide.

Halide perovskites have attracted much attention for energy conversion. However, efficient charge carrier generation, separation, and mobility remain the most important issues limiting the higher efficiency of solar cells. An efficient interfacial charge transfer process associated with exciton dynamics between all-inorganic CsPbBr3 nanocrystals and organic electron acceptors has been suggested. We observed a strong PL quenching of 78% in thin films when silane-functionalized naphthalenediimides (SNDI), used as electron-acceptors, are anchored on CsPbBr3 nanocrystals. Optical and structural characterizations confirm the charge transfer process without QDs degradation. The issue of whether these transferred charges are indeed available for utilization in solar cells remains uncertain. Our results reveal that the CsPbBr3 nanocrystals capped with these electron-acceptor SNDI molecules show a drastic increase in the electrical resistance and the absence of a photoconductivity effect. The results suggest charge transfer followed by strong localization of the charge carriers, preventing their extraction toward the electrodes of solar cell devices. We hope that this crucial aspect to attract attention and unveil a potential mechanism for charge delocalization, which could, in turn, lead to a groundbreaking enhancement in solar cell efficiency.

Rashba Spin Splitting Limiting the Application of 2D Halide Perovskites for UV-Emitting Devices.

Layered lead halide perovskites have attracted much attention as promising materials for a new generation of optoelectronic devices. To make progress in applications, a full understanding of the basic properties is essential. Here, we study 2D-layered (BA)2PbX4 by using different halide anions (X = I, Br, and Cl) along with quantum confinement. The obtained cell parameter evolution, supported by experimental measurements and theoretical calculations, indicates strong lattice distortions of the metal halide octahedra, breaking the local inversion symmetry in (BA)2PbCl4, which strongly correlates with a pronounced Rashba spin-splitting effect. Optical measurements reveal strong photoluminescence quenching and a drastic reduction in the PL quantum yield in this larger band gap compound. We suggest that these optical results are closely related to the appearance of the Rashba effect due to the existence of a local electric dipole. The results obtained in ab initio calculations showed that the (BA)2PbCl4 possesses electrical polarization of 0.13 µC/cm2 and spin-splitting energy of about 40 meV. Our work establishes that local octahedra distortions induce Rashba spin splitting, which explains why obtaining UV-emitting materials with high PLQY is a big challenge.

Synthesis and Characterization of Two Novel Naphthalenediimide/Zinc Phosphonate Crystalline Materials Precipitated from Different Solvents.

Hybrid naphthalenediimide/zinc phosphonate materials (NDI/Zn) were prepared by mixing solutions of N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (PNDI) and zinc nitrate, resulting in the precipitation of the desired compounds. Samples precipitated from water and N,N-dimethylformamide (DMF) were produced. The obtained samples had the expected elemental composition, and the presence of naphthalenediimides (NDI) was ascertained by infrared and UV-visible spectroscopy. All the samples were crystalline, according to powder X-ray diffraction. Nitrogen adsorption isotherms showed the presence of porosity in the NDI/Zn samples. Mesopores with a diameter = 4.1 nm were present in the sample from DMF, with total pore volume reaching 0.13 cm3/g.

Periodic mesoporous organosilicas containing naphthalenediimides as organic sensitizers for sulfadiazine photodegradation.

In this work, periodic mesoporous organosilicas (PMO) functionalized with the organic sentisizer naphthalenediimide (NDI) were employed as heterogeneous catalysts for the photodegradation of the antibiotic sulfadiazine (SDZ), taken as a model for contaminants of emerging concern (CECs). The catalysts, designated as PMONDI, were prepared by surfactant-directed co-condensation of the precursor N,N'-bis(3-triethoxysilylpropyl)- 1,4,5,8-naphthalenediimide with tetraethoxysilane. The synthesized PMONDI were characterized using transmission electron microscopy, nitrogen adsorption isotherms and small and large angle x-ray scattering. The performance of PMONDI catalysts in the photodegradation of SDZ was compared to that of TiO2 nanoparticles impregnated into SBA-15 mesoporous silica (TiO2/SBA-15), under irradiation with a Hg lamp with a bandpass filter of 320-500 nm. Under optimal conditions, PMONDI degraded 100% of the SDZ in 45 min, while the total degradation of SDZ was achieved only after 150 min with TiO2/SBA-15. PMONDI also performed better than TiO2/SBA-15 in reuse tests. The mechanism of photodegradation with PMONDI involves the formation of excited triplet states of NDI (3NDI*) upon irradiation, which can then react with molecular oxygen to form reactive oxygen species, which degrade SDZ. Analysis of the SDZ degradation products indicated two main pathways: (1) hydroxylation of the aniline ring and (2) SO2 extrusion and rearrangement, followed by oxidation of the aniline ring to nitrobenzene. In conclusion, the great potential of the PMONDI materials as photocatalysts for CECs degradation was demonstrated in this work, encouraging further research on these materials for the degradation of pollutants.

Functionalized mesoporous silicas SBA-15 for heterogeneous photocatalysis towards CECs removal from secondary urban wastewater.

The photocatalytic activity of TiO2 nanoparticles (NPs) supported on mesoporous silica SBA-15 (TiO2/SBA-15) was evaluated for the photodegradation of sulfadiazine (SDZ), as target contaminant of emerging concern (CEC), using either pure water solutions (PW) or a real secondary urban wastewater (UWW) spiked with SDZ. For this purpose, TiO2/SBA-15 samples with 10, 20 and 30% TiO2 (w/w) were prepared by the sol-gel post synthetic method on pre-formed SBA-15, using titanium (IV) isopropoxide as a precursor. The TiO2/SBA-15 materials were characterized by HRTEM, SAXS and XRD, nitrogen adsorption isotherms and UV-vis diffuse reflectance spectroscopy. TiO2 NPs were shown to be attached onto the external surface, decorating the SBA-15 particles. The TiO2/SBA-15 catalysts were active in SDZ photodegradation using the annular FluHelik photoreactor, when irradiated with UVA light. The 30% TiO2/SBA-15 sample presented the best performance in optimization tests performed using PW, and it was further used for the tests with UWW. The photocatalytic activity of 30% TiO2/SBA-15 was higher (56% SDZ degradation) than that of standard TiO2-P25 (32% SDZ degradation) in the removal of SDZ spiked in the UWW ([SDZ] = 2 mg L-1). The photodegradation of SDZ with 30% TiO2/SBA-15 eached 90% for UWW spiked with a lower SDZ concentration ([SDZ] = 40 µg L-1). Aside of SDZ, a suit of 65 other CECs were also identified in the UWW sample using LC-MS spectrometry. A fast-screening test showed the heterogeneous photocatalytic system was able to remove most of the detected CECs from UWW, by either adsorption and/or photocatalysis.

Aggregation of 3,4,9,10-perylenediimide radical anions and dianions generated by reduction with dithionite in aqueous solutions.

Aqueous solutions of N,N'-bis(2-phosphonoethyl)-3,4,9,10-perylenediimide (PPDI) were titrated with sodium dithionite, generating radical anions (PPDI(-*)) and dianions (PPDI(2-)). In aqueous ethanol (1:1 v/v), PPDI existed as monomers and remained in the monomeric form in all reduced states. In water, on the other hand, PPDI formed dimers, which were transformed into a pi-stacked aggregated form upon one-electron reduction to PPDI(-*). Addition of a second electron, however, resulted in dissociation of the aggregates, giving the dianion PPDI(2-) in the monomeric form. The presence of CTAB micelles prevented the aggregation of PPDI(-*) in water, indicating that the radical anions were incorporated into the micellar phase. Reduction of PPDI in ethanol solution, where the dye was aggregated, resulted in the formation of soluble mixed stacks containing both PPDI(-*) and PPDI(2-). These mixed stacks stabilized the radical anion form, preventing further reduction to the dianion.

Spectroscopic, structural, and functional characterization of the alternative low-spin state of horse heart cytochrome C.

The alternative low-spin states of Fe(3+) and Fe(2+) cytochrome c induced by SDS or AOT/hexane reverse micelles exhibited the heme group in a less rhombic symmetry and were characterized by electron paramagnetic resonance, UV-visible, CD, magnetic CD, fluorescence, and Raman resonance. Consistent with the replacement of Met(80) by another strong field ligand at the sixth heme iron coordination position, Fe(3+) ALSScytc exhibited 1-nm Soret band blue shift and epsilon enhancement accompanied by disappearance of the 695-nm charge transfer band. The Raman resonance, CD, and magnetic CD spectra of Fe(3+) and Fe(2+) ALSScytc exhibited significant changes suggestive of alterations in the heme iron microenvironment and conformation and should not be assigned to unfold because the Trp(59) fluorescence remained quenched by the neighboring heme group. ALSScytc was obtained with His(33) and His(26) carboxyethoxylated horse cytochrome c and with tuna cytochrome c (His(33) replaced by Asn) pointing out Lys(79) as the probable heme iron ligand. Fe(3+) ALSScytc retained the capacity to cleave tert-butylhydroperoxide and to be reduced by dithiothreitol and diphenylacetaldehyde but not by ascorbate. Compatible with a more open heme crevice, ALSScytc exhibited a redox potential approximately 200 mV lower than the wild-type protein (+220 mV) and was more susceptible to the attack of free radicals.

Peroxidase catalytic cycle of MCM-41-entrapped microperoxidase-11 as a mechanism for phenol oxidation.

The encapsulation of microperoxidases (MPs) into molecular sieves with controlled pore size, such as the mesoporous silica MCM-41, represents a nanotechnology strategy to control the catalytic properties of MPs and mimic the enzymatic activity of hemoproteins. In this work, the ferric microperoxidase-11 (MP-11), obtained from trypsin-catalyzed hydrolysis of horse-heart cytochrome c, was entrapped in MCM-41, thus resulting in a catalyst (Fe(III)MP11MCM41) with catalase and monooxygenase properties. The entrapment of MP-11 inside MCM-41 was confirmed by elemental analysis and UV-visible spectrum, with a red shift in the Soret band indicating that the heme group was in a hydrophobic microenvironment. Similarly to catalase, the catalyst Fe(III)MP11MCM41 exhibited specificity for hydrogen peroxide to be converted to a high-valence oxidized intermediate, Compound II. Also mimicking catalase, the cleavage of hydrogen peroxide by MP11MCM41 resulted in O2 production detected by a Clark electrode. Phenol was able to act as reducing agent of MP11MCM41 Compound II leading to the completion of a peroxidase cycle, as confirmed by UV-visible spectrometry and EPR measurements. The analysis of the reaction products by high performance liquid chromatogram coupled to tandem mass spectrometry (HPLC/MS) revealed 2,4-dihydroxyphenol as the product of phenol oxidation by MP11MCM41. Therefore, in addition to catalase activity, the catalyst MP11MCM41 also displayed monooxygenase properties, which was possible because the MP-11 heme iron promotes homolytic cleavage of the hydrogen peroxide generating hydroxyl radicals. With such characteristics, MCM-41-entrapped MP-11 is a promising catalyst for nanobiotechnological devices.

Stable photoinduced charge separation in nanostructured films containing a 1,4,5,8-naphthalenetetracarboxylic diimide and cytochrome c.

Photoinduced electron transfer between 1,4,5,8-naphthalenetetracarboxylic diimides (NDI) and the redox protein cytochrome c (cyt c) was studied in solution and in spin-coated thin films. The NDI derivatives employed in this study were N,N'-bis(butyl)-1,4,5,8-naphthalenetetracarboxylic diimide (BNDI) and N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenetetracarboxylic diimide (PNDI). Irradiation of the NDI in solution with UV light (365 nm), in the presence of cyt c, resulted in the reduction of the heme iron from the Fe3+ to the Fe2+ state. When PNDI and cyt c were co-deposited by spin-coating on quartz, glass, and silicon substrates, photoactive films were obtained. Exposition of the films to a UV lamp or natural sun light resulted in photoreduction of the protein, generating a stable charge-separated state. Thin films containing segregated layers of BNDI and cyt c were also prepared. Irradiation of these films, however, resulted in protein degradation. The results can be explained through the formation of imide radicals, which transfer an electron to cyt c in the co-deposited films. In the case of segregated films, protein photodegradation suggests the formation of singlet oxygen within the films.

Photoinduced electron transfer between cytochrome c and a novel 1,4,5,8-naphthalenetetracarboxylic diimide with amphiphilic character.

N-dodecyl-N'-(2-phosphonoethyl)-1,4,5,8-naphthalenetetracarboxylic diimide (DNDI) is a novel naphthalenic diimide with amphiphilic character. DNDI was synthesized through the sequential reaction of 1,4,5,8-naphthalenetetracarboxylic dianhydride, first with dodecylamine and then with 2-aminoethylphosphonic acid. Fluorescence measurements showed that DNDI forms excimers in water at sufficiently high concentrations. The fluorescence quantum yield of DNDI in diluted solutions is sensitive to the polarity of the microenvironment, decreasing as going from water to less polar solvents. This property allowed to monitor the incorporation of DNDI into cetyl trimethyl ammonium bromide (CTAB) micelles, with a binding constant of 1.2x10(4) M-1. UV irradiation (365 nm) of solutions containing DNDI and the redox protein cytochrome c (cyt c) resulted in the reduction of the heme iron from the Fe(III) to the Fe(II) state, a reaction that was inhibited by the incorporation of DNDI into CTAB micelles. DNDI formed host-guest complexes with alpha-cyclodextrin (alpha-CD) through the inclusion of the dodecyl group, resulting in an increased aqueous solubility of the compound.

Photochemical reduction of cytochrome c by a 1,4,5,8-naphthalenediimide radical anion.

Steady-state UV irradiation of aqueous solutions containing cytochrome c (cyt c) and N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (BPNDI), a water-soluble aromatic imide, resulted in the reduction of the heme iron from the Fe(III) to the Fe(II) oxidation state. The reaction kinetics were followed by the increase of the ferrocytochrome c absorbance band at 549 nm. The rate of the photochemical reaction was pH dependent, reaching its maximum values over the pH range 4-7. Addition of electrolyte (NaCl) at pH 5 resulted in a decrease in the reaction rate, as expected for reactions between oppositely charged species. Flash photolysis studies revealed that the actual reductant in the reaction was a photogenerated BPNDI radical anion, which transferred an electron to the cyt c heme iron. The participation of imide radicals in the process was confirmed by the ready reduction of cyt c by BPNDI radicals chemically generated with sodium dithionite.

Modification of molecular sieves MCM-41 and SBA-15 with covalently grafted pyromellitimide and 1,4,5,8-naphthalenediimide.

This article describes the covalent grafting of pyromellitimide and 1,4,5,8-naphthalenediimide, which are organic semiconductors with very interesting electro-optical properties, onto the walls of mesoporous molecular sieves. The mesoporous materials MCM-41 and SBA-15 were first treated with 3-aminopropyltriethoxysilane, generating materials with a surface coverage of primary amino groups. These materials were further reacted with either pyromellitic dianhydride or 1,4,5,8-naphthalenetetracarboxylic dianhydride, generating surface-bound pyromellitimide or 1,4,5,8-naphthalenediimide, respectively. The success of the modification reactions was confirmed by elemental and thermogravimetric analyses, X-ray diffraction patterns and infrared, reflectance and fluorescence spectroscopies. The results indicated that the mesoporous structure of the new materials was preserved after the modification reactions and that the chromophores were included inside the mesoporous channels with stacked aromatic rings.

Highly stable 3,4,9,10-perylenediimide radical anions immobilized in robust zirconium phosphonate self-assembled films.

Self-assembled thin films of 3,4,9,10-perylenediimides (PDIs) containing up to 50 PDI layers were grown on quartz slides using the zirconium phosphonate technique. When the films were immersed in aqueous solutions of the sodium dithionite reducing agent, in situ reduction of the dye was observed, generating a purple film containing PDI radical anions. The PDI radical anions formed within the films were rather stable, persisting for several minutes in the presence of atmospheric oxygen. Atomic force microscopy (AFM) images showed that the film surface was rather smooth and pinhole-free.

Characterization of a novel water-soluble 3,4,9,10-perylenetetracarboxylic diimide in solution and in self-assembled zirconium phosphonate thin films.

The properties of N,N'-bis(2-phosphonoethyl)-3,4,9,10-perylenetetracarboxylic diimide (PPDI), a water-soluble perylene dye, have been studied in solution and in thin films. Absorption spectra showed that PPDI exists in the monomeric form in water/ethanol (1:1) and water/dimethyl sulfoxide (DMSO) (3:7) mixtures, but forms dimers in water and higher aggregates in ethanol. The PPDI monomer is highly fluorescent, in contrast to the dimers and aggregates, which are nonfluorescent. The monomer/dimer equilibrium was conveniently followed in a water/ethanol (7:3) mixture by varying the dye concentration. An equilibrium constant of K = 1.25 x 10(5) M(-1) was estimated for the dimerization process in this solvent mixture. The addition of cetyl trimethylammonium bromide (CTAB), a cationic surfactant, to aqueous solutions of PPDI resulted in the dissociation of the dimers, showing that the dye was incorporated into the micellar phase. Self-assembled thin films of PPDI were grown on both silica gel particles and flat surfaces, using zirconium phosphonate chemistry. The growth of multilayered films on flat surfaces was monitored by ellipsometry (silicon substrates) and UV/Vis spectroscopy (quartz slides), and was linear with the number of deposition cycles. No fluorescence was detected from the PPDI films, and the absorption spectra of the films were quite similar to the spectrum of the compound in ethanol, indicating that the dye molecules were stacked in the films. Mixed monolayers containing PPDI and N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (PNDI) on quartz were also prepared. Monolayers obtained by codeposition from solutions containing both PPDI and PNDI were richer in PPDI, even when the solution contained a large excess of the naphthalene derivative, showing that pi-stacking of PPDI is an important driving force in the formation of the films.

Reaction route control by microperoxidase-9/CTAB micelle ratios.

Microperoxidases (MP) as water-soluble models attract interest to studying the reaction mechanism of peroxidases because these heme peptides are able to form the same enzyme intermediates during the reaction with peroxides. In this work we have demonstrated that the association of Fe(III)MP-9 and Fe(III)MP-11 with CTAB micelles (MP-9/CTAB and MP11/CTAB) provides a microenvironment with an alkaline interface and a hydrophobic core that exhibits peroxidase behavior. This microenvironment shifts positively the redox potential of microperoxidases by approximately 100 mV. tert-Butylhydroperoxide (t-BuOOH) when added to the medium, converted Fe(III)MP-9/CTAB to MP-9/CTAB Compound II, a high valence oxidized intermediate of the heme peptide. Subsequent addition of diphenylacetaldehyde (DPAA) to MP-9/CTAB Compound II regenerated the native form of the enzyme, Fe(III)MP-9/CTAB, what characterizes the occurrence of a peroxidase cycle. Fe(III)MP-9/CTAB regenerated during the peroxidase cycle reacted with residual DPAA in the medium to form Fe(II)MP-9/CTAB, which indicates that both Fe(III)MP-9/CTAB and its oxyferryl form can use aldehydes as reducing agents. According to the determined reduction potential, Fe(III)MP-9 and Fe(III)MP-9/CTAB should be able to oxidize DPAA (reduction potential -630 mV). The reaction of MP-9/CTAB with DPAA produced benzophenone as final product, detected by infrared spectroscopy and mass spectrometry. Interestingly, a significant difference was observed in the benzophenone yield according to the micelle/MP-9 molar ratio.

Zirconium phosphonate/1, 4, 5, 8-naphthalenediimides self-assembled films

The formation and characterization of self-assembled films of zirconium phosphonate / N,N'-di(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (DPN) is presented. The films were produced on glass substrates by deposition of alternating layers of Zr+4 and DPN. Films containing up to 16 layers on each side of the substrate were obtained and monitored by absorption spectroscopy and ellipsometry. When irradiated, the initially colorless films turned to a persistent pinky color reminiscent of that of DPN anion radical. These films are a promising material to the development of photovoltaic devices.