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Twelve arrays containing porphyrin, chlorin, and/or perylene-imide units were synthesized to investigate panchromatic absorption integrated with charge separation.
We report a facile synthetic approach to create stable radical block copolymers containing a secondary fluorinated block via anionic polymerization using a bulky, sterically hindered countercation composed of a sodium ion and di-benzo-18-crown-6 complex. The synthetic conditions described in this report allowed for controlled molecular weights and dispersity (<1.3) of both homopolymers: poly(2,2,6,6-tetramethyl-1-piperidinyloxy-methacrylate) (PTMA) and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) as well as their block copolymers (PTMA-b-PTFEMA). The stable radical concentration of the polymers was determined by electron spin resonance (ESR) and showed radical content above 70%. An analysis of the microphase morphologies in PTMA-b-PTFEMA thin films via atomic force microscopy (AFM) and grazing incidence small angle X-ray scattering (GISAXS) showed clear evidence of long-range ordering of lamellar and cylindrical morphologies with 32 and 36 nm spacing, respectively. The long-range ordering of the morphologies was developed with the aid of two separate neutral layers: PTMA-ran-PTFEMA-ran-poly(hydroxyl ethyl methacrylate) (PHEMA) and poly(isobutyl methacrylate) (PiBMA)-ran-PTFEMA-ran-PHEMA, which helped us corroborate, along with the Zisman method, the surface energy estimation of PTMA to be 30.1 mJ m -2 .
Considerable attention has been given to polymeric membranes either containing, or built from, ionic liquids (ILs) in gas separation processes due to their selective separation of CO 2 molecules. Achieving high-performance CO 2 separation membranes with enhanced permeability and selectivity relies mainly on rationally designing the molecular substructure and molecular composition of the polymer matrix. In this work, we have exclusively explored a facile synthetic route to incorporate aromatic amide linkages onto an ionene backbone derived from imidazolium-mediated Tröger's base moieties, yielding a novel rigid polyamide-ionene material (“Im-TB-PA ionene”). We have optimized two novel Im-TB-PA ionene polymers via Menshutkin reactions between N,N'-(1,4-phenylene)bis(4-(chloromethyl)benzamide) and equimolar amounts of two isomeric diimidazole-functionalized Tröger's base monomers with ‘ortho’ or ‘para’ regiochemistry. The two resulting Im-TB(o&p)-PA ionenes exhibited high molecular weights and excellent solubilities in polar organic solvents, serving homogeneous and mechanically stable blend membranes with “free” ILs. The structural and physical properties, as well as the gas separation behaviors of both the Im-TB(o&p)-PA ionenes and their IL composite counterparts ([Im-TB(o&p)-PA] + [IL]), were further extensively investigated. The membrane with an optimal composition and polymer architecture ([Im-TB(o)-PA] + [IL]) exhibited outstanding permselectivites for CO 2 /CH 4 (46.73), CO 2 /N 2 (51.74), and CO 2 /H 2 (4.38) gas pairs together with the best CO 2 permeability of 47.2 barrer. Altogether, this study provides a promising strategy to explore the benefits of Im-TB-PA ionenes to separate CO 2 from flue gas, natural gas, and syngas streams, while opening new possibilities in polymer design with strong candidate materials for other practical applications.
Under anaerobic conditions, ferrous iron reacts with sulfide producing FeS, which can then undergo a temperature, redox potential, and pH dependent maturation process resulting in the formation of oxidized mineral phases, such as greigite or pyrite. A greater understanding of this maturation process holds promise for the development of iron-sulfide catalysts, which are known to promote diverse chemical reactions, such as H + , CO 2 and NO 3 - reduction processes. Hampering the full realization of the catalytic potential of FeS, however, is an incomplete knowledge of the molecular and redox processess ocurring between mineral and nanoparticulate phases. Here, we investigated the chemical properties of iron-sulfide by cyclic voltammetry, Raman and X-ray absorption spectroscopic techniques. Tracing oxidative maturation pathways by varying electrode potential, nanoparticulate n(Fe 2+ S 2- ) (s) was found to oxidize to a Fe 3+ containing FeS phase at -0.5 V vs. Ag/AgCl (pH = 7). In a subsequent oxidation, polysulfides are proposed to give a material that is composed of Fe 2+ , Fe 3+ , S 2- and polysulfide (S n 2- ) species, with its composition described as Fe 2+ 1-3x Fe 3+ 2x S 2- 1-y (S n 2- ) y . Thermodynamic properties of model compounds calculated by density functional theory indicate that ligand oxidation occurs in conjunction with structural rearrangements, whereas metal oxidation may occur prior to structural rearrangement. These findings together point to the existence of a metastable FeS phase located at the junction of a metal-based oxidation path between FeS and greigite (Fe 2+ Fe 3+ 2 S 2- 4 ) and a ligand-based oxidation path between FeS and pyrite (Fe 2+ (S 2 ) 2- ).
The combination of block copolymer (BCP) thin film self-assembly and selective infiltration synthesis of inorganic materials into one BCP block provides access to various organic–inorganic hybrids. Here, we apply sequential infiltration synthesis, a vapor-phase hybridization technique, to selectively introduce ZnO into the organic microdomains of silicon-containing rod-coil diblock copolymers and a triblock terpolymer, polydimethylsiloxane (PDMS)-b-poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene} (PDMS-b-PMPCS) and PDMS-b-polystyrene-b-PMPCS (PDMS-b-PS-b-PMPCS), in which the PMPCS rod block is a liquid crystalline polymer. The in-plane cylindrical PDMS-b-PMPCS and core–shell cylindrical and hexagonally perforated lamellar PDMS-b-PS-b-PMPCS films were infiltrated with ZnO with high selectivity to the PMPCS. The etching contrast between PDMS, PS and the ZnO-infused PMPCS enables the fabrication of ZnO/SiO x binary composites by plasma etching and reveals the core–shell morphology of the triblock terpolymer.
This perspective deviates from exclusively focusing on structural features of actinide-containing metal-organic frameworks and pivots towards their prospect as avant-garde materials with an emphasis on their physicochemical properties.
Highly stretchable PAN/ILs fibers were fabricated through melt-spinning with ionic liquids containing cyano-based anions.
We report a [3+2] cycloaddition using 3,6-bis-propargyloxy-1,2,4,5-tetrazine and azides to synthesize energetic polymers containing 1,2,4,5-tetrazine within the scaffold.
An efficient, column chromatography-free route for scale-up preparation of protected carbonyl containing biomass molecules is established. Then the protection group effect is investigated in multiple systems especially under a reducing atmosphere.
A new quaternary 3D chalcogenide, Na 2 Si 6 B 12 Se 18 , was synthesized via solid-state methods and features a unique framework containing the rare icosahedral [B 12 ] 10+ cation. The tunnels in this 3D framework structure are occupied by Na + ions.
Conjugated ladder polymers (CLPs) are difficult yet captivating synthetic targets due to their fully unsaturated fused backbones. Inherent challenges associated with their synthesis often lead to low yields, structural defects, and insoluble products. Here a new method to form CLPs is demonstrated, utilizing a high-yielding dimerization of annulated zirconacyclopentadienes to form cyclooctatetraene (COT) monomer units. The resulting COT-containing polymers form rapidly in a single ladderization step from the bis-zirconacyclopentadiene precursors and display M n up to 29.7 kg mol -1 . The polymers represent rare examples of CLPs with negatively curved rings, resulting in the observation of unusual properties. The rigid tub-shaped COT units embedded in the backbone imbue the polymers with microporosity, exhibiting BET surface areas up to 555 m 2 g -1 . Additionally, the remarkable solubility of these CLPs in organic solvents enables the fabrication of thin films showcasing high dielectric performance with a discharged energy density as high as 6.54 J cm -3 at 650 MV m -1 .
The development of elastomer-containing photoactive block copolymers with regulated rigid-block lengths results in organic solar cells with high power conversion efficiency (17.3%) and mechanical robustness (toughness = 1.8 MJ m −3 ).
Chemical recycling of condensation polymers is often rationalized on the basis of the intrinsic reactivity of ester and carbonate functional groups. However, under heterogeneous conditions relevant to plastic waste processing and environmental degradation, bulk depolymerization rates often diverge from trends predicted by homogeneous chemistry. Here, we investigate how polymer–solvent compatibility, catalyst strength, and phase behavior govern the heterogeneous glycolysis of carbonyl-containing polymers. Using poly(ethylene terephthalate) (PET), glycol-modified PET (PETG), and bisphenol-A polycarbonate (PC) as model systems, we examine depolymerization kinetics at 180 °C with ethylene glycol and bisphenol A as diols under both amphoteric organosalt (TBD : MSA) and strong base (TBD) catalysis. Despite substantial differences in crystallinity and glycol uptake, PET and PETG depolymerize at comparable rates under organosalt catalysis, while PC depolymerizes significantly more slowly under identical conditions. Time-resolved molecular weight analysis and thermal characterization demonstrate that these rate differences do not arise from crystallinity, swelling, or inherent carbonyl reactivity, but instead reflect solubility-limited kinetics that constrain the transition from heterogeneous to homogeneous reaction regimes. When polymer solubility is low, depolymerization remains heterogeneous and slow; when solubility is enhanced—either through increased polymer–diol compatibility or stronger base catalysis—rapid homogeneous depolymerization is observed, reversing apparent reactivity trends. These results establish solubility and phase behavior as primary determinants of depolymerization kinetics in heterogeneous polymer recycling systems. By demonstrating how catalyst selection and solvent compatibility can expose or overcome solubility limitations, this work provides mechanistic insight to design more energy-efficient and selective chemical recycling processes. More broadly, these findings suggest that polymers with limited solvent or water compatibility may resist chemical degradation in the environment, favoring fragmentation and persistence as micro- and nanoplastics. Understanding solubility-controlled depolymerization offers a pathway toward more sustainable polymer design and end-of-life chemical recovery.
In this work, the syntheses of bidentate and tripodal phosphine ligands containing aryl chlorides were achieved in 4 and 7 steps respectively, starting from diethyl malonate.
We have developed a system for rapid reduction of radioactive contamination and capture and recycling of contaminated wash waters called Integrated Wash-Aid, Treatment, and Emergency Reuse System (IWATERS). IWATERS prescribes the use of wash waters containing salt additives to enhance the removal of radionuclides from various surfaces and solid sorbents to remove the radionuclides selectively. One possible additive to the wash water is Ca2+ . However, the concentration of this ion can have a very strong detrimental effect on the ability of sequestration agents to sorb strontium effectively. A literature review, batch tests, and surface complexation modeling revealed a few sorbent options for Sr2+ in the presence of Ca2+. Engineered silicotitanate sorbents exhibited superior Kd values in the presence of Ca2+ but have significant drawbacks in cost and availability.
The physics of vibrational kinetics in nitrogen-containing plasma produced by collisions with electrons is studied on the basis of recently derived cross sections and rate coefficients for the resonant vibrational-excitation by electron-impact. The temporal relaxation of the vibrational energy and of the vibrational distribution function is analyzed in a state-to-state approach. The electron and vibrational temperatures are varied in the range [0-50 000] K. Conclusions are drawn with respect to the derivation of reduced models and to the accuracy of a relaxation time formalism. An analytical fit of the vibrational relaxation time is given.
It is shown that the frequencies of Trivelpiece-Gould (TG) modes in non-neutral plasma can get into the low-frequency range due to the Doppler shift caused by plasma rotation in crossed fields. TG modes interact with the ion modes that leads to plasma instability. In paper the frequency spectrum of 'cold' electron plasma completely filling a waveguide and containing small density fraction of ions of background gas is determined numerically. For ions the kinetic description is used. Oscillations having azimuthal number m= 2 are considered. In this case both low- and upper-hybrid TG modes get into the low-frequency range. The spectrum consists of families of 'modified' ion cyclotron (MIC) modes and electron TG modes with the frequencies equal to hybrid frequencies with the Doppler shift. The growth rates of upper-hybrid modes are much faster than the growth rates of low-hybrid and MIC modes.
In this paper, the dispersive properties of three-dimensional (3D) magnetized plasma photonic crystals (MPPCs) composed of anisotropic dielectric (the uniaxial material) spheres immersed in homogeneous magnetized plasma background with face-centered-cubic (fcc) lattices are theoretically investigated by the plane wave expansion method, as the Voigt effects of magnetized plasma are considered. The equations for calculating the anisotropic photonic band gaps (PBGs) in the first irreducible Brillouin zone are theoretically deduced. The anisotropic PBGs and two flatbands regions can be obtained. The effects of the ordinary-refractive index, extraordinary-refractive index, filling factor, plasma frequency, and external magnetic field on the dispersive properties of the 3D MPPCs are investigated in detail, respectively, and some corresponding physical explanations are also given. The numerical results show that the anisotropy can open partial band gaps in 3D MPPCs with fcc lattices and the complete PBGs can be found compared to the conventional 3D MPPCs doped by the isotropic material. The bandwidths of PBGs can be tuned by introducing the magnetized plasma into 3D PCs containing the uniaxial material. It is also shown that the anisotropic PBGs can be manipulated by the ordinary-refractive index, extraordinary-refractive index, filling factor, plasma frequency, and external magnetic field, respectively. The locations of flatbands regions cannot be manipulated by any parameters except for the plasma frequency and external magnetic field. Introducing the uniaxial material can obtain the complete PBGs as the 3D MPPCs with high symmetry and also provides a way to design the tunable devices.