Stable Structure and Fast Ion Diffusion: A Flexible MoO2@Carbon Hollow Nanofiber Film as a Binder-Free Anode for Sodium-Ion Batteries with Superior Kinetics and Excellent Rate Capability.

Designing innovative anode materials that exhibit excellent ion diffusion kinetics, enhanced structural stability, and superior electrical conductivity is imperative for advancing the rapid charge-discharge performance and widespread application of sodium-ion batteries. Hollow-structured materials have received significant attention in electrode design due to their rapid ion diffusion kinetics. Building upon this, we present a high-performance, free-standing MoO2@hollow carbon nanofiber (MoO2@HCNF) electrode, fabricated through facile coaxial electrospinning and subsequent heat treatment. In comparison to MoO2@carbon nanofibers (MoO2@CNFs), the MoO2@HCNF electrode demonstrates superior rate capability, attributed to its larger specific surface area, its higher pseudocapacitance contribution, and the enhanced diffusion kinetics of sodium ions. The discharge capacities of the MoO2@HCNF (MoO2@CNF) electrode at current densities of 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0 A g-1 are 195.55 (155.49), 180.98 (135.20), 163.81 (109.71), 144.05 (90.46), 121.16 (71.21) and 88.90 (44.68) mAh g-1, respectively. Additionally, the diffusion coefficients of sodium ions in the MoO2@HCNFs are 8.74 × 10-12 to 1.37 × 10-12 cm2 s-1, which surpass those of the MoO2@CNFs (6.49 × 10-12 to 9.30 × 10-13 cm2 s-1) during the discharging process. In addition, these prepared electrode materials exhibit outstanding flexibility, which is crucial to the power storage industry and smart wearable devices.

An electrochemical sensor based on synergistic enhancement effects between nitrogen-doped carbon nanotubes and copper ions for ultrasensitive determination of anti-diabetic metformin.

Metformin (MET) is the primary medicine for type II diabetes, which produces carcinogenic byproducts during chlorine disinfection, so the detection of MET in aqueous environment is crucial. In this work, an electrochemical sensor based on nitrogen-doped carbon nanotubes (NCNT) has been constructed for ultrasensitive determination of MET in the presence of Cu(II) ions. The excellent conductivity and rich π-conjugated structure of NCNT facilitate the electron transfer rate of fabricated sensor and benefit the adsorption of cation ions. Cu(II) ions can chelate with MET to form MET-Cu(II) complex, which are easily accumulated on the surface of NCNT through cation-π interaction. Attributing to the synergistic enhancement effects of NCNT and Cu(II) ions, the fabricated sensor exhibits excellent analytical performances with a low detection limit of 9.6 nmol L-1, high sensitivity of 64.97 A mol-1 cm-2 and wide linear range of 0.3-10 µmol L-1. The sensing system has been successfully applied for rapid (20 s) and selective determination of MET in real water samples with satisfactory recoveries (90.2 %-108.8 %). This study provides a robust strategy for MET detection in aqueous environment and holds great promise for rapid risk assessment and early warning of MET.

Benzobis(Thiazole)-Based Conjugated Polymer with Varying Alkylthio Side-Chain Positions for Efficient Fullerene-Free Organic Solar Cells.

Alkylthio groups can be used to modulate energy levels and molecular packing of organic semiconductors, which makes it important in the design of materials for organic solar cell. However, its effect has not been sufficiently exploited as most of the studies report introducing an alkylthio group to the donor unit and seldom to the acceptor unit of donor-acceptor conjugated polymers. In this report, two alkylthio-substituted polymers, namely, PBB-TSA and PBB-TSD, with benzo[1,2-d:4,5-d']bis(thiazole) (BBT) as the acceptor unit and benzo[1,2-b:4,5-b']dithiophene (BDT) as the donor unit, were rationally designed, synthesized, and applied in organic photovoltaics. An alkylthio side chain was substituted on the BBT-accepting unit for PBB-TSA, while for PBB-TSD, the alkylthio side chain was substituted on the BDT donor unit. PBB-TSA and PBB-TSD show upshifted and downshifted energy levels, respectively, compared to the nonsulfur-substituted material. Both polymers exhibit dominate face-on orientation, while PBB-TSD exhibits higher crystallinity compared to PBB-TSA. With the contribution of lower energy level and beneficial film morphology, the device based on PBB-TSD/IT-4F has much higher power conversion efficiency (PCE) of 14.6%, whereas the PBB-TSA blend had a lower PCE of 10.7%. 1,8-Diiodooctane can effectively optimize the blend film morphology, and the effect on device performance has also been demonstrated in detail. This result indicates that introducing an alkylthio side chain into the donor or acceptor moieties would result in materials with different energy levels and thus would be utilized to match with various acceptors, achieving optimized performance in organic solar cells.

Dithieno[3,2-b:2',3'-d]silole-based conjugated polymers for bioimaging in the short-wave infrared region.

The short-wave infrared window (SWIR, 900-1700 nm) fluorescence imaging has been demonstrated to have excellent imaging performance in signal/noise ratio and tissue penetration compared to the conventional NIR biological window (NIR-I, 700-900 nm). Conventional organic SWIR fluorescent materials still suffer from low fluorescence quantum efficiency. In this work, a donor unit with sp3 hybrid configuration and an acceptor unit with small hindered alkyl side chains are employed to construct donor-acceptor (D-A) type conjugated polymers P1 and P2, which were substituted with one or two fluorine atoms. These structural features can alleviate the aggregation-caused quenching (ACQ) and contribute to charge transfer, resulting in a significantly improved fluorescence quantum efficiency. The SWIR fluorescent quantum efficiencies of P1 and P2 nanoparticles are 3.4% and 4.4%, respectively, which are some of the highest for organic SWIR fluorophores reported so far. Excellent imaging quality has been demonstrated with P2 nanoparticles for SWIR imaging of the vascular system of nude mice. The results indicate that our design strategy of introducing sp3 hybrid configuration and small hindered alkyl side chains to fabricate conjugated polymers is efficient in improving the fluorescent quantum efficiency as SWIR fluorescent imaging agents for potential clinical practice.

D-A polymers for fluorescence/photoacoustic imaging and characterization of their photothermal properties.

NIR-II fluorescence imaging has great potential in diagnosis, but the quantum efficiency of contrast agents is an urgent problem to be solved. We synthesized two new multifunctional polymers, P-TT and P-DPP, with a tetrahedral C (sp3) and branched alkyl chains in the main chain, which were beneficial to obtain high quantum efficiency. P-TT and P-DPP showed absorption peaks of 686 nm and 763 nm, respectively, and fluorescence emission peaks of 1071 nm and 1066 nm, respectively. The photothermal effect of P-DPP can reach 52 °C, and the quantum yield reaches 1.5%, which was three times higher than that of nanotube fluorophores (quantum yield 0.4%). P-DPP is used for stable fluorescence imaging of blood vessels and photoacoustic imaging of nude mice, and successfully applied to phototherapy of nude mouse tumours.

Probing effects of molecular conformation on the electronic and charge transport properties in two- and three-dimensional small molecule hole-transporting materials: a theoretical investigation.

Thiophene/benzene-fused π-conjugated systems are normally employed as the core units of two- and three-dimensionally expanded small molecule hole-transporting materials (HTMs) to improve their electronic and charge transport properties, whereas comparison studies between two-dimensional and three-dimensional core conformations are less reported. To further find useful clues for the design of highly-efficient small molecule HTMs and to find new core units, in this work, four HTM molecules are designed by employing triphenylene, benzotrithiophene, triptycene, and thiophenetriptycene as the core units, and simulated with density functional theory combined with the Marcus hopping model. Our results show that all the considered HTMs display appropriate molecular energy levels, less optical absorption in the visible light region and large Stokes shifts, and high hole mobilities (9.80 × 10-2 cm2 V-1 s-1). Compared with the two-dimensional core structures, the three-dimensional cores exhibit evident superiorities with the same chemical components. Meanwhile, we also find that the quasi-degenerate HOMO energy levels will be helpful to enlarge the transfer integrals between adjacent molecules, and further to promote the hole transport in HTMs. By considering the various elements simultaneously, these investigated HTMs (S-1-S-4) with thiophene- and benzene-fused cores can be expected as potential promising candidates to help create more efficient solar cells.

Conjugated-Polymer-Based Nanoparticles with Efficient NIR-II Fluorescent, Photoacoustic and Photothermal Performance.

Fluorescence imaging (FI) and photoacoustic imaging (PA) play important roles in the real-time assessment of cell-based therapies. However, the limitations of conventional organic fluorescence contrast agents and the narrow range of the emission wavelength in the first near-infrared (NIR-I) window (750-900 nm) hamper applications of fluorescence imaging in living subjects. Herein, we report the design and synthesis of a short-wave infrared FI contrast agent and PA contrast agent based on a conjugated polymer-poly{2,5-bis[(5-thiophen-2-yl)methylene]-3,6-bis(2-octyldodecyl)-2,5-dihydropyrazine}-and its use to construct multifunctional nanoparticles to simplify photothermal therapy.

Photodegradation Pathways of Typical Phthalic Acid Esters Under UV, UV/TiO2, and UV-Vis/Bi2WO6 Systems.

Photolysis and photocatalysis of typical phthalic acid esters (dimethyl phthalate, DMP; diethyl phthalate, DEP; dibutyl phthalate, DBP) were carried out in UV, UV/TiO2, and UV-Vis/Bi2WO6 systems. All of the selected phthalic acid esters and their decomposition byproducts were subjected to qualitative and quantitative analysis through HPLC and GC-MS. The results of 300 min of photolysis and photodegradation reaction were that each system demonstrated different abilities to remove DMP, DEP, and DBP. The UV/TiO2 system showed the strongest degradation ability on selected PAEs, with removal efficiencies of up to 93.03, 92.64, and 92.50% for DMP, DEP, and DBP in 90 min, respectively. UV-Vis/Bi2WO6 had almost no ability to remove DMP and DEP. However, all of the systems had strong ability to degrade DBP. On the other hand, the different systems resulted in various byproducts and PAE degradation pathways. The UV system mainly attacked the carbon branch and produced o-hydroxybenzoates. No ring-opening byproducts were detected in the UV system. In the photocatalytic process, the hydroxyl radicals produced not only attacked the carbon branch but also the benzene ring. Therefore, hydroxylated compounds and ring-opening byproducts were detected by GC-MS in both the UV/TiO2 and UV-Vis/Bi2WO6 photocatalytic systems. However, there were fewer products due to direct hole oxidation in the UV-Vis/Bi2WO6 system compared with the UV/TiO2 system, which mainly reacted with the pollutants via hydroxyl radicals.

Recent Progress in Fluorescence Imaging of the Near-Infrared†II Window.

Near-infrared (NIR) fluorescent materials are considered to be the most promising labeling reagents for sensitive determination and biological imaging due to the advantages of lower background noise, deeper penetrating capacity, and less destructive effects on the biomatrix over those of UV and visible fluorophores. In the past decade, advances in biomedical fluorescence imaging in the NIR region have focused on the traditional NIR window (NIR-I; λ=700-900 nm), and have recently been extended to the second NIR window (NIR-II; λ=1000-1700 nm). In vivo NIR-II fluorescence imaging outperforms imaging in the NIR-I window as a result of further reduced absorption, tissue autofluorescence, and scattering. In this review, the applications of four types of NIR-II fluorescent materials, organic fluorophores, quantum dots, rare-earth compounds, and single-walled carbon nanotubes, are summarized and future trends are discussed. Some methods to enhance the NIR-II fluorescence quantum yield are also proposed.

Current status and future developments in preparation and application of nonspherical polymer particles.

Nonspherical polymer particles (NPPs) are nano/micro-particulates of macromolecules that are anisotropic in shape, and can be designed anisotropic in chemistry. Due to shape and surface anisotropies, NPPs bear many unique structures and fascinating properties which are distinctly different from those of spherical polymer particles (SPPs). In recent years, the research on NPPs has surprisingly blossomed in recent years, and many practical materials based on NPPs with potential applications in photonic device, material science and biomedical engineering have been generated. In this review, we give a systematic, balanced and comprehensive summary of the main aspects of NPPs related to their preparation and application, and propose perspectives for the future developments of NPPs.

Unsubstituted Benzodithiophene-Based Conjugated Polymers for High-Performance Organic Field-Effect Transistors and Organic Solar Cells.

Unsubstituted benzo[1,2-b:4,5-b']dithiophene (BDT) was used to construct a high-performance conjugated polymer with 5,6-difluoro-4,7-bis[4-(2-octyldodecyl)thiophene-2-yl]benzo[c][1,2,5] thiadiazole (DTFFBT), named PBDT-DTFFBT. The polymer shows the low-lying highest occupied molecular orbital (HOMO) energy level (-5.40 eV) and a broad absorption spectra with strong vibronic absorption peak. Pure polymer films exhibit good crystallinity and edge-on orientation, partially attributed to the BDT units without any side chains, and as a result, the corresponding thin-film transistor showed excellent hole mobility over 1 cm(2) V(-1) s(-1). Interestingly, a well-distributed nanofibrillar polymer aggregation with face-on orientation was obviously formed when blending with PC71BM, which was in favor of the charge transportation. Consequently, the bulk heterojunction polymer solar cells based on the blends showed high power conversion efficiency of 9.29% with large short-current density (14.56 mA cm(-2)) and high fill factor (0.751) without any process additives or thermal annealing.

Chloride ions promoted the catalytic wet peroxide oxidation of phenol over clay-based catalysts.

Catalytic wet peroxide oxidation (CWPO) of phenol over clay-based catalysts in the presence and absence of NaCl was investigated. Changes in the H2O2, Cl(-), and dissolved metal ion concentration, as well as solution pH during phenol oxidation, were also studied. Additionally, the intermediates formed during phenol oxidation were detected by liquid chromatography-mass spectroscopy and the chemical bonding information of the catalyst surfaces was analyzed by X-ray photoelectron spectroscopy (XPS). The results showed that the presence of Cl(-) increased the oxidation rate of phenol to 155%, and this phenomenon was ubiquitous during the oxidation of phenolic compounds by H2O2 over clay-based catalysts. Cl(-)-assisted oxidation of phenol was evidenced by several analytical techniques such as mass spectroscopy (MS) and XPS, and it was hypothesized that the rate-limiting step was accelerated in the presence of Cl(-). Based on the results of this study, the CWPO technology appears to be promising for applications in actual saline phenolic wastewater treatment.

The activity and selectivity of catalytic peroxide oxidation of chlorophenols over Cu-Al hydrotalcite/clay composite.

Liquid phase catalytic oxidation of chlorophenols (CPs) was carried out over Cu-Al hydrotalcite/clay composite at ambient temperature and pressure using hydrogen peroxide as oxidant. The results showed that the catalyst had high catalytic activity, with complete oxidation of 4-CP within 40 min at 40 °C. The content and position of chlorine on the aromatic ring had significantly different effects on the oxidation rate of CPs, with the rate sequence of phenol > monochlorophenol (MCP) > dichlorophenol (DCP) > trichlorophenol (TCP), 3-CP > 2-CP > 4-CP, and 3,5-DCP > 3,4-DCP > 2,5-DCP > 2,4-DCP > 2,6-DCP. This was ascribed to the interactions among σ-electron withdrawing conductive effect, π-electron donating conjugative effect, and steric hindrance effect of chlorine. It was evidenced that the catalytic peroxide oxidation of CPs in the first step was selective and rate-limiting, where chlorinated 1,4-benzoquinones formed.