A Highly Selective Turn-On Colorimetric, Red Fluorescent Sensor for Detecting Mobile Zinc in Living Cells

We describe ZRL1, a turn-on colorimetric and red fluorescent zinc ion sensor. The Zn2+-promoted ring opening of the rhodamine spirolactam ring in ZRL1 evokes a 220-fold fluorescence turn-on response. In aqueous media, ZRL1 turn-on luminescence is highly selective for Zn2+ ions, with no significant response to other competitive cations, including Na+, K+, Ca2+, Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Cd2+, or Hg2+. In addition to these characteristics, preliminary results indicate that ZRL1 can be delivered to living cells and can be used to monitor changes in intracellular Zn2+ levels

A Highly Selective Turn-On Colorimetric, Red Fluorescent Sensor for Detecting Mobile Zinc in Living Cells

We describe ZRL1, a turn-on colorimetric and red fluorescent zinc ion sensor. The Zn2+-promoted ring opening of the rhodamine spirolactam ring in ZRL1 evokes a 220-fold fluorescence turn-on response. In aqueous media, ZRL1 turn-on luminescence is highly selective for Zn2+ ions, with no significant response to other competitive cations, including Na+, K+, Ca2+, Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Cd2+, or Hg2+. In addition to these characteristics, preliminary results indicate that ZRL1 can be delivered to living cells and can be used to monitor changes in intracellular Zn2+ levels

A Homogeneous System for the Photogeneration of Hydrogen from Water Based on a Platinum(II) Terpyridyl Acetylide Chromophore and a Molecular Cobalt Catalyst

A Homogeneous System for the Photogeneration of Hydrogen from Water Based on a Platinum(II) Terpyridyl Acetylide Chromophore and a Molecular Cobalt Catalys

Covalent Cobalt Porphyrin Framework on Multiwalled Carbon Nanotubes for Efficient Water Oxidation at Low Overpotential

A noble-metal-free, efficient, and robust catalyst made of Earth-abundant elements for water oxidation is vital to achieve practical water splitting for future clean energy production. Herein, we report the synthesis of multilayer covalent cobalt porphyrin framework on multiwalled carbon nanotubes ((CoP)_<i>n</i>-MWCNTs) to produce a highly active electrocatalyst for water oxidation. A linear sweep voltammetry curve showed that a catalytic current density of 1.0 mA/cm² can be achieved under a potential of only 1.52 V (vs RHE, corresponding to an overpotential of only 0.29 V) in alkaline solution at pH 13.6. Such an onset potential is much lower than that of cobalt porphyrin monomer (CoP-TIPS) and pure MWCNTs. In addition, the chronopotentiometry data confirmed its excellent catalytic activity and suggested that the (CoP)<i>_n</i>-MWCNTs catalyst has good durability for water oxidation catalysis. A Tafel slope of 60.8 mV per decade was obtained by bulk electrolysis measurement, and the Faradaic efficiency of oxygen production was >86%

Photocatalytic Generation of Hydrogen from Water Using a Platinum(II) Terpyridyl Acetylide Chromophore

The cationic complex [Pt(tolylterpyridine)(phenylacetylide)]+ has been used as a photosensitizer for the reduction of aqueous protons in the presence of a sacrificial electron donor to make H2. In this system, triethanolamine (TEOA) acts as the sacrificial reducing agent, methyl viologen (MV2+) serves as an electron transfer agent, and colloidal Pt stabilized by polyacrylate functions as the catalyst for H2 generation. The Pt(II) chromophore undergoes both oxidative and reductive quenching, but H2 is only seen when both TEOA and MV2+ are present. Irradiation of the reaction solution for 10 h with λ > 410 nm leads to 85 turnovers and an overall yield of 34% based on TEOA. While H2 evolution is maximized for the system at pH 7, it is also seen at pH 5 and 9, in contrast with earlier reports using Ru(bpy)32+ as the photosensitizer. This is the first time that a Pt diimine or terpyridyl complex has been used as the photosensitizer for H2 generation from aqueous protons

In₂S₃/Cd_0.9Zn_0.1S Heterojunction for Efficient Photocatalytic Formic Acid Decomposition to Syngas (H₂ + CO) under Visible Light

Photocatalytic decomposition of formic acid (FA) to syngas (H2 + CO) is a valuable sustainable energy conversion strategy. In this study, we combine In2S3 nanoparticles with Cd0.9Zn0.1S nanorods (In2S3/CZS) to construct heterojunctions for directly converting formic acid to syngas under visible light (λ > 420 nm) irradiation. The In2S3/CZS composite was facilely synthesized by a hydrothermal reaction. In2S3/CZS showed excellent photocatalytic activity for FA decomposition. The optimal generation rates of H2 and CO can reach 200 and 204 μmol·h–1, respectively, which is one of the best performances in the photocatalytic decomposition of formic acid for synthesizing syngas. Under irradiation with 420 nm monochromatic light, H2 and CO exhibit apparent quantum yields of 9.7% and 10.6%, respectively. The test date confirms the formation of a type II heterojunction between Cd0.9Zn0.1S nanorods and In2S3 nanoparticles. It can effectively promote the transport and separation of the interfacial charges. This work also provides insight into the development of an efficient photocatalytic system for syngas production

Synthesis and Structural Characterization of a New Vapochromic Pt(II) Complex Based on the 1-Terpyridyl-2,3,4,5,6-pentaphenylbenzene (TPPPB) Ligand

A novel terpyridine ligand containing a pentaphenylphenyl moiety linked to the terpyridyl core (1-terpyridyl-2,3,4,5,6-pentaphenyl-benzene (TPPPB)) has been synthesized in good yield and reacted with Pt(DMSO)2Cl2, to produce the cationic complex [Pt(TPPPB)Cl]Cl (5). 5 was studied structurally and spectroscopically. It is observed to be brightly luminescent in the solid state at room temperature and at 77 K, with no change in λemmax. The complex exhibits reversible vapochromic behavior upon exposure to methylene chloride vapors, changing color from red (5-R) to green (5-G). The shift to higher energy in the emission maximum from 654 to 514 nm is the largest vapochromic shift (140 nm) yet reported. The [Pt(TPPPB)Cl]Cl complex exhibits high selectivity for certain volatile organic compounds (VOCs) including methylene chloride, ethanol, ethyl acetate, and acetonitrile. The crystal structures of both the green and red forms have been determined by single-crystal X-ray diffraction. In both forms, the cationic Pt(II) complex possesses the anticipated square-planar coordination geometry that is distorted as a consequence of constraints from the terpyridyl binding. Analysis of the crystal packing of the green form (5-G) reveals the presence of non-interacting Pt···Pt separations with distances of 3.9092(9) and 4.5483(11) Å and a zigzag arrangement between neighboring Pt(II) ions. The red form (5-R) contains complexes that are stacked with Pt···Pt separations of 3.2981(14) and 3.3427(14) Å, indicative of metallophilic interaction. The change in the emitting state, as a consequence of the effect of the volatile organic compounds, results from a disruption of the d8−d8 metallophilic interactions in the red form and its metal−metal-to-ligand charge transfer (MMLCT) excited state to a more-localized Pt(dπ)-to-tpy(π*) metal-to-ligand charge transfer (MLCT) excited state in the green form

Ultrathin MOF Coupling with Molecular Cobaloxime to Construct an Efficient Hybrid Hematite Photoanode for Photocatalytic Water Splitting

It is a great challenge to develop efficient artificial photosynthesis systems by mimicking natural photosynthesis. In this present work, an organo-inorganic hybrid photoanode was fabricated by depositing ultrathin NiFe MOF nanolayers and molecular cobaloxime cocatalyst on the surface of Ti-doped porous hematite (Ti-PH). This hybrid photoanode exhibited a high photocurrent density of 2.45 mA/cm2 at 1.23 V vs the reversible hydrogen electrode (RHE) under AM 1.5 G illumination with excellent stability. Moreover, the optimal incident photon-to-current efficiency (IPCE) of the hybrid photoanode reached 83.0% at 365 nm and the surface charge injection efficiency (ηinj) was improved to 87.5% at 1.23 V vs RHE. Detailed investigations reveal that NiFe MOFs can effectively facilitate charge separation as a hole-transport layer and molecular cobaloxime cocatalyst can passivate surface trap states to increase water oxidation kinetics

Synthesis and Structural Characterization of a New Vapochromic Pt(II) Complex Based on the 1-Terpyridyl-2,3,4,5,6-pentaphenylbenzene (TPPPB) Ligand

A novel terpyridine ligand containing a pentaphenylphenyl moiety linked to the terpyridyl core (1-terpyridyl-2,3,4,5,6-pentaphenyl-benzene (TPPPB)) has been synthesized in good yield and reacted with Pt(DMSO)2Cl2, to produce the cationic complex [Pt(TPPPB)Cl]Cl (5). 5 was studied structurally and spectroscopically. It is observed to be brightly luminescent in the solid state at room temperature and at 77 K, with no change in λemmax. The complex exhibits reversible vapochromic behavior upon exposure to methylene chloride vapors, changing color from red (5-R) to green (5-G). The shift to higher energy in the emission maximum from 654 to 514 nm is the largest vapochromic shift (140 nm) yet reported. The [Pt(TPPPB)Cl]Cl complex exhibits high selectivity for certain volatile organic compounds (VOCs) including methylene chloride, ethanol, ethyl acetate, and acetonitrile. The crystal structures of both the green and red forms have been determined by single-crystal X-ray diffraction. In both forms, the cationic Pt(II) complex possesses the anticipated square-planar coordination geometry that is distorted as a consequence of constraints from the terpyridyl binding. Analysis of the crystal packing of the green form (5-G) reveals the presence of non-interacting Pt···Pt separations with distances of 3.9092(9) and 4.5483(11) Å and a zigzag arrangement between neighboring Pt(II) ions. The red form (5-R) contains complexes that are stacked with Pt···Pt separations of 3.2981(14) and 3.3427(14) Å, indicative of metallophilic interaction. The change in the emitting state, as a consequence of the effect of the volatile organic compounds, results from a disruption of the d8−d8 metallophilic interactions in the red form and its metal−metal-to-ligand charge transfer (MMLCT) excited state to a more-localized Pt(dπ)-to-tpy(π*) metal-to-ligand charge transfer (MLCT) excited state in the green form

Synthesis and Structural Characterization of a New Vapochromic Pt(II) Complex Based on the 1-Terpyridyl-2,3,4,5,6-pentaphenylbenzene (TPPPB) Ligand

A novel terpyridine ligand containing a pentaphenylphenyl moiety linked to the terpyridyl core (1-terpyridyl-2,3,4,5,6-pentaphenyl-benzene (TPPPB)) has been synthesized in good yield and reacted with Pt(DMSO)2Cl2, to produce the cationic complex [Pt(TPPPB)Cl]Cl (5). 5 was studied structurally and spectroscopically. It is observed to be brightly luminescent in the solid state at room temperature and at 77 K, with no change in λemmax. The complex exhibits reversible vapochromic behavior upon exposure to methylene chloride vapors, changing color from red (5-R) to green (5-G). The shift to higher energy in the emission maximum from 654 to 514 nm is the largest vapochromic shift (140 nm) yet reported. The [Pt(TPPPB)Cl]Cl complex exhibits high selectivity for certain volatile organic compounds (VOCs) including methylene chloride, ethanol, ethyl acetate, and acetonitrile. The crystal structures of both the green and red forms have been determined by single-crystal X-ray diffraction. In both forms, the cationic Pt(II) complex possesses the anticipated square-planar coordination geometry that is distorted as a consequence of constraints from the terpyridyl binding. Analysis of the crystal packing of the green form (5-G) reveals the presence of non-interacting Pt···Pt separations with distances of 3.9092(9) and 4.5483(11) Å and a zigzag arrangement between neighboring Pt(II) ions. The red form (5-R) contains complexes that are stacked with Pt···Pt separations of 3.2981(14) and 3.3427(14) Å, indicative of metallophilic interaction. The change in the emitting state, as a consequence of the effect of the volatile organic compounds, results from a disruption of the d8−d8 metallophilic interactions in the red form and its metal−metal-to-ligand charge transfer (MMLCT) excited state to a more-localized Pt(dπ)-to-tpy(π*) metal-to-ligand charge transfer (MLCT) excited state in the green form