Supramolecular Self-Assembled Nanostructures Derived from Amplified Structural Isomerism of Zn(II)−Sn(IV)−Zn(II) Porphyrin Triads and Their Visible Light Photocatalytic Degradation of Pollutants †
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PROVIDER: S-EPMC11243107 | biostudies-literature | 2024 Jun
REPOSITORIES: biostudies-literature
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Project description:Three isomeric Zn(II)-Sn(IV)-Zn(II) porphyrin-based triads (T2, T3, and T4) were synthesized by the reaction of common Zn(II) porphyrins (ZnL) with different Sn(IV) porphyrins (SnP n ). The Sn(IV) porphyrin precursors differ with respect to the position of the pyridyl-N atoms. All compounds were characterized by 1H NMR, UV-vis, fluorescence spectroscopy, electrospray ionization-mass spectrometry, and field-emission scanning electron microscopy measurements. In these structures, the intramolecular cooperative metal-ligand coordination of the 3-pyridyl nitrogen in SnP 3 with axial ZnL and the π-π interactions between the adjacent porphyrin triad are the determining factors affecting the nanostructures of T3. Owing to the geometrical constraints of the SnP 2 center, this type of interaction is not possible for T2. Therefore, only the π-π interactions affect the self-assembly process. In the case of SnP 4 , intermolecular coordinative interactions and then π-π interactions are responsible for the nanostructure of T4. The morphology-dependent photocatalytic degradation of methyl orange (MO) dye in aqueous solution under visible light irradiation was observed for these photocatalysts, and the degradation ratio of MO varied from 76 to 94% within 100 min. Nanorod-shaped T3 exhibited higher performance compared to nanosphere T2 and nanoflake T4.
| S-EPMC8945165 | biostudies-literature
Project description:Two robust Sn(IV)-porphyrin-based supramolecular arrays (1 and 2) were synthesized via the reaction of trans-Pd(PhCN)2Cl2 with two precursor building blocks (SnP1 and SnP2). The structural patterns in these architectures vary from 2D to 3D depending on the axial ligation of Sn(IV)-porphyrin units. A discrete 2D tetrameric supramolecule (1) was constructed by coordination of {(trans-dihydroxo)[5,10-bis(4-pyridyl)-15,20-bis(phenyl) porphyrinato]}tin(IV) (SnP1) with trans-PdCl2 units. In contrast, the coordination between the {(trans-diisonicotinato)[5,10-bis(4-pyridyl)-15,20-bis(phenyl)porphyrinato]}tin(IV) (SnP2) and trans-PdCl2 units formed a divergent 3D array (2). Axial ligation of the Sn(IV)-porphyrin building blocks not only alters the supramolecular arrays but also significantly modifies the nanostructures, including porosity, surface area, stability, and morphology. These structural changes consequently affected the photocatalytic degradation efficiency under visible-light irradiation towards acid orange 7 (AO) dye in an aqueous solution. The degradation efficiency of the AO dye in the aqueous solution was observed to be between 86% to 91% within 90 min by these photocatalysts.
| S-EPMC9696627 | biostudies-literature
Project description:In this study, two distinct photocatalysts, namely tin(IV)porphyrin-sensitized titanium dioxide nanotubes (SnP-TNTs) and titanium dioxide nanofibers (TNFs), were synthesized and characterized using various spectroscopic techniques. SnP-TNTs were formed through the hydrothermal reaction of NaOH with TiO2 (P-25) nanospheres in the presence of Sn(IV)porphyrin (SnP), resulting in a transformation into Sn(IV)porphyrin-imbedded nanotubes. In contrast, under similar reaction conditions but in the absence of SnP, TiO2 (P-25) nanospheres evolved into nanofibers (TNFs). Comparative analysis revealed that SnP-TNTs exhibited a remarkable enhancement in the visible light photodegradation of model pollutants compared to SnP, TiO2 (P-25), or TNFs. The superior photodegradation activity of SnP-TNTs was primarily attributed to synergistic effects between TiO2 (P-25) and SnP, leading to altered conformational frameworks, increased surface area, enhanced thermo-chemical stability, unique morphology, and outstanding visible light photodegradation of cationic methylene blue dye (MB dye). With a rapid removal rate of 95% within 100 min (rate constant = 0.0277 min-1), SnP-TNTs demonstrated excellent dye degradation capacity, high reusability, and low catalyst loading, positioning them as more efficient than conventional catalysts. This report introduces a novel direction for porphyrin-incorporated catalytic systems, holding significance for future applications in environmental remediation.
| S-EPMC11013583 | biostudies-literature
Project description:Two hybrid composite photocatalysts, denoted as SnP/AA@ZnO and SnP@ZnO, were fabricated by a reaction of trans-dihydroxo[5,10,15,20-tetrakis(4-pyridyl)porphyrinato]tin(IV) (SnP) and ZnO with and without pretreatment of adipic acid (AA), respectively. In SnP@ZnO, SnP and ZnO are likely held together by a coordinative interaction between the pyridyl N atoms of SnP and the Zn atoms on the surface of ZnO. In the case of SnP/AA@ZnO, the SnP centers were robustly coupled with ZnO nanoparticles through the AA anchors. SnP/AA@ZnO exhibited largely enhanced photocatalytic activities for the degradation of anionic amaranth (AM) dye under a visible light irradiation, compared to SnP, ZnO, and SnP@ZnO. The degradation efficiency of AM by SnP/AA@ZnO was 95% within 60 min at a rate constant of 0.048 min-1. The remarkable photocatalytic oxidation performance of SnP/AA@ZnO was mainly attributed to the synergistic effect between SnP and ZnO. This study is valuable for the development of highly effective composite photocatalytic systems in advanced oxidation processes and is of importance for the treatment of wastewater containing dyes.
| S-EPMC10536602 | biostudies-literature
Project description:Two hybrid composites (SnP@MCM-41 and SnP@SiO2) were fabricated by chemical adsorption of (trans-dihydroxo)(5,10,15,20-tetraphenylporphyrinato)tin(IV) (SnP) on mesoporous structured Mobil Composition of Matter No. 41 (MCM-41) and SiO2 nanoparticles. These materials were characterized by Fourier-transform infrared spectroscopy, ultraviolet-visible spectroscopy, fluorescence spectroscopy, transmission electron microscopy, and field-emission scanning electron microscopy techniques. The incorporation of SnP into MCM-41 and SiO2 supports efficient photocatalytic degradation of the anionic erioglaucine, cationic rhodamine B, and neutral m-cresol purple dyes under visible light irradiation in an aqueous solution. The performances of degradation of these dyes by these photocatalysts under visible light irradiation varied from 87 to 95%. The pseudo-first-order degradation rate constant of organic dyes for SnP@MCM-41 was higher than those of SnP@SiO2 and SnP. These visible light photocatalysts showed remarkable stability and reliable reusability.
| S-EPMC9966349 | biostudies-literature
Project description:A single crystal of penta-lanthanum dizinc stannide, La(5)Zn(2)Sn, was obtained from the elements in a resistance furnace. It belongs to the Mo(5)SiB(2) structure type, which is a ternary ordered variant of the Cr(5)B(3) structure type. The space is filled by bicapped tetra-gonal anti-prisms from lanthanum atoms around tin atoms sharing their vertices. Zinc atoms fill voids between these bicapped tetra-gonal anti-prisms. All four atoms in the asymmetric unit reside on special positions with the following site symmetries: La1 (..m); La2 (4/m..); Zn (m.2m); Sn (422).
| S-EPMC3246910 | biostudies-literature
Project description:Gold nanoparticles show important electronic and optical properties, owing to their size, shape, and electronic structures. Indeed, gold nanoparticles containing no more than 30-40 atoms are only luminescent, while nanometer-sized gold nanoparticles only show surface plasmon resonance. Therefore, it appears that gold nanoparticles can alternatively be luminescent or plasmonic and this represents a severe restriction for their use as optical material. The aim of our study was the fabrication of nanoscale assembly of Au nanoparticles with bi-functional porphyrin molecules that work as bridges between different gold nanoparticles. This functional architecture not only exhibits a strong surface plasmon, due to the Au nanoparticles, but also a strong luminescence signal due to porphyrin molecules, thus, behaving as an artificial organized plasmonic and fluorescent network. Mutual Au nanoparticles-porphyrin interactions tune the Au network size whose dimension can easily be read out, being the position of the surface plasmon resonance strongly indicative of this size. The present system can be used for all the applications requiring plasmonic and luminescent emitters.
| S-EPMC7558707 | biostudies-literature
Project description:A series of porphyrin triads (1-4), in which each triad is composed of a Sn(IV) porphyrin and two free-base (or Zn(II)) porphyrins, was synthesized and their self-assembled nanostructures were studied. Depending on the substituent on porphyrin moieties, each triad was self-assembled into a different nanostructure. In particular, the cooperative coordination of 3-pyridyl groups in the Sn(IV) porphyrin with the axial Zn(II) porphyrins in triad 4 leads to forming uniform nanofibers with an average width of 10-22 nm. Other triads without the coordinating interaction between the central Sn(IV) porphyrin and the axial porphyrins formed irregularly shaped aggregates in contrast. The morphologies of nanofiber changed drastically upon the addition of pyrrolidine, in which pyrrolidine molecules break down the self-assembly process by coordinating with the axial Zn(II) porphyrins. All porphyrin aggregates exhibited efficient photocatalytic performances on the degradation of methylene blue dye under visible light irradiation. The degradation efficiencies after 2 h were observed to be between 70% and 95% for the aggregates derived from the four triads.
| S-EPMC7700138 | biostudies-literature
Project description:A simple strategy for synthesizing supramolecular hybrids was developed for the preparation of bioavailable nanohybrid photosensitizers by assembling visible-light-sensitive Pt(II) meso-tetrakis(4-carboxyphenyl)porphyrinporphyrin (PtTCPP)/tomatine analogues. The hybrids were self-assembled into nanofibrous or nanosheet structures approximately 3-5 nm thick and several micrometers wide. α-Tomatine generated a unique fibrous vesicle nanostructure based on intermolecular interactions, while dehydrotomatine generated nanosheet structures. Nanoassembly of these fibrous vesicles and sheets directly affected the properties of the light-responsive photosensitizer for tumor photodynamic therapy (PDT), depending on the nanostructure of the hybrid PtTCPP/tomatine analogues. The cytotoxicity of PtTCPP to cancer cells under photoirradiation was significantly enhanced by a tomatine assembly with a fibrous vesicle nanostructure, attributable to increased incorporation of the drug into cells.
| S-EPMC8158828 | biostudies-literature
Project description:Structure-specific ligands are convenient tools for the recognition, targeting or probing of non-canonical DNA structures. Porphyrin derivatives exhibit a preference for interaction with G-quadruplex (G4) structures over canonical duplex DNA and are able to cause photoinducible damage to nucleic acids. Here, we show that Zn(II) 5,10,15,20-tetrakis(N-carboxymethyl-4-pyridinium)porphyrin ( ZNP1: ) interacts with different conformations of the telomeric sequence d(TAGGG(TTAGGG)3) at submicromolar concentrations without any detectible disturbance of the particular fold. Among different folds, potassium (3+1) hybrid G4-structure. reveal the highest affinity to ZNP1: The pattern of guanine oxidation is specific for each telomeric DNA conformation and may serve as an additional tool for probing the G4 topology. The potassium (3+1) and parallel G4 conformations are more susceptible to light-induced oxidation than the sodium G4 conformation or double helix of the telomeric DNA. The major products of the guanine modifications are spiroiminodihydantoin (Sp) and 8-oxoguanine (8-oxoG). ZNP1: -induced oxidation of guanines results in the structural rearrangement of parallel and (3+1) G4 conformations yielding an antiparallel-like G4 conformation. The mechanism of the observed light-induced conformational changes is discussed.
| S-EPMC5137456 | biostudies-literature