High energy-efficiency decomplexation of metal-complexes by H*-mediated electro-reduction on hydroxyphenyl Co-porphyrin catalysts.

Electrochemical reduction of metal-organic complex pollutants has been recognized as an environmental benign method that operates at mild condition. However, the selective reduction of metal complexes and energy consumption in cathodic process are still a big challenge. Herein, we found that hydroxyphenyl Co-porphyrin catalyst (CoTH@NG) realizes the highly selective decomplexation of metal-organic complexes by H* -mediated reduction, and simultaneously the impressive recovery efficiency of metal ions.

Porphyrin-based covalent organic frameworks from design, synthesis to biological applications.

Covalent organic frameworks (COFs) constitute a class of highly functional porous materials composed of lightweight elements interconnected by covalent bonds, characterized by structural order, high crystallinity, and large specific surface area. The integration of naturally occurring porphyrin molecules, renowned for their inherent rigidity and conjugate planarity, as building blocks in COFs has garnered significant attention. This strategic incorporation addresses the limitations associated with free-standing porphyrins, resulting in the creation of well-organized porous crystal structures with molecular-level directional arrangements.

Perspective into ion storage of pristine metal-organic frameworks in capacitive deionization.

Metal-organic frameworks (MOFs), featuring tunable conductivity, tailored pore/structure and high surface area, have emerged as promising electrode nanomaterials for ion storage in capacitive deionization (CDI) and garnered tremendous attention in recent years. Despite the many advantages, the perspective from which MOFs should be designed and prepared for use as CDI electrode materials still faces various challenges that hinder their practical application. This summary proposes design principles for the pore size, pore environment, structure and dimensions of MOFs to precisely tailor the surface area, selectivity, conductivity, and Faradaic activity of electrode materials based on the ion storage mechanism in the CDI process.

Soft-hard interface design in super-elastic conductive polymer hydrogel containing Prussian blue analogues to enable highly efficient electrochemical deionization.

The poor cycling stability of faradaic materials owing to volume expansion and stress concentration during faradaic processes limits their use in large-scale electrochemical deionization (ECDI) applications. Herein, we developed a "soft-hard" interface by introducing conducting polymer hydrogels (CPHs), that is, polyvinyl alcohol/polypyrrole (PVA/PPy), to support the uniform distribution of Prussian blue analogues (, copper hexacyanoferrate (CuHCF)). In this design, the soft buffer layer of the hydrogel effectively alleviates the stress concentration of CuHCF during the ion-intercalation process, and the conductive skeleton of the hydrogel provides charge-transfer pathways for the electrochemical process.

Hormetic dose-response of halogenated organic pollutants on Microcystis aeruginosa: Joint toxic action and mechanism.

Quinolones (QNs), dechloranes (DECs), and chlorinated paraffins (CPs) are three kinds of new halogenated organic pollutants (HOPs), which originate from the use of flame retardants, lubricants and pesticides. Since QNs, DECs, and CPs are frequently detected in waters and sediments, it is necessary to investigate the toxic effects of these HOPs with dwelling phytoplankton, especially for cyanobacteria, to explore their potential hormetic effects and contributions to algal blooms. In the present study, we investigate single and joint toxicity of QNs, DECs and CPs on Microcystis aeruginosa (M.

Purely Organic Room-Temperature Phosphorescence Endowing Fast Intersystem Crossing from Through-Space Spin-Orbit Coupling.

Purely organic room-temperature phosphorescence endowing very fast intersystem crossing from through-space systems has not been well investigated. Here we report three space-confined bridged phosphors, where phenothiazine is linked with dibenzothiophene, dibenzofuran, and carbazole by a 9,9-dimethylxanthene bridge. Nearly pure phosphorescence is observed in the crystals at room temperature.

Investigations on the influence of energy source on time-dependent hormesis: A case study of sulfadoxine to Aliivibrio fischeri in different cultivation systems.

Hormesis is a biphasic dose-response relationship featured by low-dose stimulation and high-dose inhibition. Although the hormetic phenomenon has been extensively studied over the past decades, there is little information regarding the influence of energy source on the occurrence of hormesis, especially the time-dependent one. In this study, to explore the role of cultivation system's energy source in time-dependent hormesis, the toxic dose-responses of Aliivibrio fischeri (A.

Highly emissive phenylene-expanded [5]radialene.

A pentagonal macrocycle (MC5-PER) with radialene topology was facilely synthesized through a selective one-pot Suzuki-Miyaura cross-coupling reaction. The resulting product is endowed with a pentagonal architecture as revealed by its single crystal structure, which affords the smallest ring strain and the best conjugation. As tetraphenylethene subunits are embedded, MC5-PER is highly emissive in the solid state due to the aggregation-induced emission effect.

Synthesis of poly(1,5-diaminonaphthalene) microparticles with abundant amino and imino groups as strong adsorbers for heavy metal ions.

Poly(1,5-diaminonaphthalene) microparticles with abundant reactive amino and imino groups on their surface were synthesized by one-step oxidative polymerization of 1,5-diaminonaphthalene using ammonium persulfate as the oxidant. The molecular, supramolecular, and morphological structures of the microparticles were systematically characterized by IR and UV-vis spectroscopies, elementary analysis, wide-angle X-ray diffractometry, and transmission electron microscopy. The microparticles demonstrate electrical semiconductivity and high resistance to strong acid and alkali, and strong adsorption capability for lead(II), mercury(II), and silver(I) ions.

Efficient synthesis of oligofluoranthene nanorods with tunable functionalities.

Strongly fluorescence-emitting oligofluoranthene (OFA) nanorods are readily synthesized by a direct template-free chemical oxidative oligomerization of fluoranthene in nitromethane containing ferric chloride as an oxidant. The OFAs likely consist of five fluoranthene units containing cyclic pentamers with crystalline order and tunable electrical conductivity across 12 orders of magnitude. The OFA nanorods are heat-resistant materials and efficient precursors for macroporous carbon materials with high carbon yield in argon at 1100 °C.

Interfacial chemical oxidative synthesis of multifunctional polyfluoranthene.

A novel polyfluoranthene (PFA) exhibiting strong visual fluorescence emission, a highly amplified quenching effect, and widely controllable electrical conductivity is synthesized by the direct cationic oxidative polymerization of fluoranthene in a dynamic interface between -hexane and nitromethane containing fluoranthene and FeCl, respectively. A full characterization of the molecular structure signifies that the PFAs have a degree of polymerization from 22-50 depending on the polymerization conditions. A polymerization mechanism at the interface of the hexane/nitromethane biphasic system is proposed.

Synthesis of semiconducting polymer microparticles as solid ionophore with abundant complexing sites for long-life Pb(II) sensors.

Intrinsically electrically semiconducting microparticles of semiladder poly(m-phenylenediamine-co-2-hydroxy-5-sulfonic aniline) structures containing abundant functional groups, like -NH-, -N=, -NH2, -OH, -SO3H as complexation sites, were efficiently synthesized by chemical oxidative copolymerization of m-phenylenediamine and 2-hydroxy-5-sulfonic aniline. The obtained copolymers were found to be nonporous spherical microparticles that were able to achieve greater π-conjugated structure, smaller particle aggregate size, and stronger interaction with Pb(II) ions than poly(m-phenylenediamine) containing only -NH-, -N=, and -NH2. A potentiometric Pb(II) sensor was fabricated on the basis of the copolymer microparticles as a crucial solid ionophore component within plasticized PVC.

Combinatorial screening of potentiometric Pb(II) sensors from polysulfoaminoanthraquinone solid ionophore.

A potentiometric Pb(II)-selective sensor was fabricated by a combinatorial screening of electrically conducting polysulfoaminoanthraquinone (PSA) nanoparticles as a solid ionophore, ion exchangers (oleic acid (OA) and NaTPB), plasticizers in a polyvinyl chloride (PVC) matrix, membrane thickness, inner filling ion species, and concentration. The membrane sensor with the composition of PSA/PVC/DOP (dioctyl phthalate)/OA (1.0:33:61:5.

Lead-ion potentiometric sensor based on electrically conducting microparticles of sulfonic phenylenediamine copolymer.

A potentiometric sensor to detect lead ions using newly synthesized conducting copolymer microparticles as an ionophore in self-supporting poly(vinyl chloride) membrane matrix plasticized with dioctyl phthalate was developed. The copolymer microparticles containing many ligating functional groups including amino, imino and sulfonic groups were synthesized by a chemical oxidative copolymerization of m-phenylenediamine (mPD) and p-sulfonic-m-phenylenediamine (SPD) in pure water. Due to the presence of -NH-, -N=, -NH2, and -SO3H ligating groups on the microparticles, a linear Nernstian response is obtained within a Pb(II) activity range from 1.

Carbon nanotube-templated polyaniline nanofibers: synthesis, flash welding and ultrafiltration membranes.

Electro-active switchable ultrafiltration membranes are of great interest due to the possibility of external control over permeability, selectivity, anti-fouling and cleaning. Here, we report on hybrid single-walled carbon nanotube (SWCNT)-polyaniline (PANi) nanofibers synthesized by in situ polymerization of aniline in the presence of oxidized SWCNTs. The composite nanofibers exhibit unique morphology of core-shell (SWCNT-PANi) structures with average total diameters of 60 nm with 10 to 30 nm thick PANi coatings.

Interfacial synthesis and functionality of self-stabilized polydiaminonaphthalene nanoparticles.

A simple and effective template-free synthesis method for nanosized conducting polymers with self-stability and functionality is a main challenge. Herein, a strategy is reported for the facile synthesis of poly(1,5-diaminonaphthalene) nanospherical particles by an interfacial miniemulsion oxidative polymerization of 1,5-diaminonaphthalene at mobile microinterfaces between a stirred biphase without external emulsifiers. The size of the nanospheres was carefully optimized by controlling the polymerization conditions.

Ultrasensitive Pb(II) potentiometric sensor based on copolyaniline nanoparticles in a plasticizer-free membrane with a long lifetime.

A newly designed Pb(II) potentiometric sensor based on intrinsically conducting nanoparticles of solid poly(aniline-co-2-hydroxy-5-sulfonic aniline) possessing many ligating functional groups like -NH-, -N=, -OH, -SO(3)H, -NH(2) as ionophores in plasticizer-free vinyl resin solid membranes has been fabricated. A linear Nernstian response is obtained within a wide Pb(II) activity range from 1.0 × 10(-3) to 1.

Lead ion-selective electrodes based on polyphenylenediamine as unique solid ionophores.

A novel membrane electrode for Pb(II) ion detection based on semi-conducting poly(m-phenylenediamine) microparticles as a unique solid ionophore was fabricated. The electrode exhibited significantly enhanced response towards Pb(II) over the concentration range from 3.16×10(-6) to 0.

Carbon nanotube/polyaniline composite nanofibers: facile synthesis and chemosensors.

An initiator is applied to synthesize single-walled carbon nanotube/polyaniline composite nanofibers for use as high-performance chemosensors. The composite nanofibers possess widely tunable conductivities (10(-4) to 10(2) S/cm) with up to 5.0 wt % single-walled carbon nanotube (SWCNT) loadings.

Facile synthesis of water-dispersible conducting polymer nanospheres.

Water-dispersible polypyrrole nanospheres with diameters of less than 100 nm were synthesized in high yield without any templates, surfactants, or functional dopants by the introduction of 2,4-diaminodiphenylamine as an initiator into a reaction mixture of pyrrole monomer, oxidant, and acid. The initiator plays a critical role in tailoring the nanostructures of polypyrrole. 2,4-Diaminodiphenylamine interacts with acid to form cations, which combine with various anions to self-assemble resulting in different size nanomicelles.

Redox sorption and recovery of silver ions as silver nanocrystals on poly(aniline-co-5-sulfo-2-anisidine) nanosorbents.

Poly[aniline(AN)-co-5-sulfo-2-anisidine(SA)] nanograins with rough and porous structure demonstrate ultrastrong adsorption and highly efficient recovery of silver ions. The effects of five key factors-AN/SA ratio, Ag(I) concentration, sorption time, ultrasonic treatment, and coexisting ions-on Ag(I) adsorbability were optimized, and AN/SA (50/50) copolymer nanograins were found to exhibit much stronger Ag(I) adsorption than polyaniline and all other reported sorbents. The maximal Ag(I) sorption capacity of up to 2034 mg g(-1) (18.

Simple efficient synthesis of strongly luminescent polypyrene with intrinsic conductivity and high carbon yield by chemical oxidative polymerization of pyrene.

A wholly aromatic polypyrene was synthesized by direct chemical oxidative polymerization of pyrene with ferric chloride as oxidant in hexane/nitromethane. Successful synthesis of polypyrene was thoroughly confirmed by IR, UV/Vis, 1D (1)H NMR, 2D (1)H-(1)H COSY, 2D (1)H-(13)C HSQC, MALDI-TOF MS, elemental analysis, and X-ray diffraction methods. The results indicated that the polypyrene was formed mainly through dehydro coupling between 2- or 1- and 2'- or 1'-positions on pyrene rings having a degree of polymerization of around 24.

Longan shell as novel biomacromolecular sorbent for highly selective removal of lead and mercury ions.

Strongly selective adsorbability of natural longan (Euphoria longan) shell as a biomacromolecular sorbent toward heavy metal ions from aqueous solutions has been discovered and successfully optimized by facilely controlling the shell dosage, sorption time, pH value, and ion concentration. The sorption well-fits the Langmuir isotherm and obeys the pseudo-second-order kinetics. The maximum adsorptivity of Pb(II) and Hg(II) is 99.

Interfacial synthesis and widely controllable conductivity of polythiophene microparticles.

Fine polythiophene (PTh) microparticles were successfully synthesized by a novel interfacial polymerization at a dynamic interface between two immiscible solvents, i.e., n-hexane and acetonitrile or nitromethane containing thiophene and oxidant, respectively.