Heterocyclic effect boosted peroxidase-like activity of MIL(Fe) metal-organic framework for colorimetric assay and dye removal.

Metal-organic frameworks (MOFs) have emerged as promising candidates for enzyme mimics due to their abundant pore structures and adjustable active sites. The catalytic activity particularly depends on the electronic character of the organic ligand. In this study, we report an iron-based MOF nanozyme FeTDC, created by replacing the 1,4-dicarboxybenzene ligand with five-membered 2,5-thiophenedicarboxylic acid (H2TDC). In comparison with the phenyl analogue, the sulfur-based heterocyclic ligand demonstrates high electron delocalization, and a low pKa value, which are beneficial for enhancing the metal/ligand interactions. Accordingly, FeTDC can facilitate the oxidation of the benzidine substrate in the presence of H2O2, thereby exhibiting remarkable peroxidase-like activity. The generation of hydroxyl radical (•OH) at the Fe active sites contributes to the catalytic process. Furthermore, the smartphone-assisted colorimetric assay of pyrophosphate was developed with high sensitivity, based on its inhibitory effect. When FeTDC was utilized for the removal of benzidine dye under high-salt condition, a 90 % of removal rate was achieved due to the synergistic effect of enzyme catalysis and physical adsorption. This work presents a novel perspective of heterocyclic effect on the design of MOF nanozymes, thereby expanding their applicability in the control of pollutants.

Specific detection of fungicide thiophanate-methyl: A smartphone colorimetric sensor based on target-regulated oxidase-like activity of copper-doped carbon nanozyme.

Nanozyme-based colorimetric assays have shown great potential in the rapid and sensitive determination of pesticide residue in environment. However, the non-specific enzyme inhibition makes the assays generally lack of selectivity. In this study, we proposed a colorimetric sensing platform for the specific detection of the agricultural fungicide thiophanate-methyl (TM) based on its distinctive inhibitory effect on the nanozyme activity. Since TM contains the symmetric ethylenediamine- and bisthiourea-like groups, it displays strong affinity to the metal site, leading to a loss of the catalytic activity. Accordingly, a Cu-doped carbon nanozyme with excellent oxidase-like properties was designed, and the oxidation process of chromogenic substrate is promoted by Cu-induced generation of reactive oxygen species. Interestingly, the nanozyme activity can be directly and strongly restrained by TM, rather than other probably coexistent pesticides. Consequently, the as-proposed analytical method exhibits specific response toward TM and good linear relationship in the range of 0.2-15 µg mL-1 with a low limit of detection of 0.04 µg mL-1 (S/N = 3). Besides, a smartphone-assisted rapid detection was achieved through identifying the RGB value of the chromogenic system. This work provides a new nanozyme inhibition strategy for the specific detection of TM in environmental sample.

Visual evaluation of acetylcholinesterase inhibition by an easy-to-operate assay based on N-doped carbon nanozyme with high stability and oxidase-like activity.

Acetylcholinesterase (AChE) is the key enzyme associated with neurotransmission, and thus many drugs have been explored for their inhibitory effect on AChE, such as donepezil for Alzheimer's disease and organophosphorus pesticides (OPs). Compared with clinical trials, in vitro screening bioassays for AChE inhibitors are preferable in terms of operability and cost. Herein, we developed an easy-to-operate nanozyme-based colorimetric assay for the evaluation of AChE inhibitory strength with excellent anti-interference ability and low dependence on professional equipment. The metal-free carbon nanozyme NC900 played an important role in the signal output due to its features of efficient oxidase-like activity, excellent water dispersibility, high stability and low color interference. Employing various AChE-targeted or non-targeted pesticides as examples, the as-proposed assay exhibited excellent distinguishing ability for different chemicals. The higher absorption intensity at 652 nm represents a stronger inhibitory effect, as well as blue color. In addition, this method was used to study the influence of pH on the degradation of prodrugs, and the efficiency of mixed pesticides. This work provides a simple and reliable assay to screen AChE inhibitors, which is promising for the preliminary evaluation of a large number of potential candidates.

CeO2@NC nanozyme with robust dephosphorylation ability of phosphotriester: A simple colorimetric assay for rapid and selective detection of paraoxon.

Enzyme-mediated dephosphorylation reaction is the important approach to realize the inactivation and detection of hazardous phosphate chemicals. To date, many phosphatases-like nanozymes (e.g., CeO2) have demonstrated the catalytic hydrolysis ability of the phosphomonoesters, rather than phosphotriester, and the CeO2 nanozyme only work under relatively harsh conditions of high temperature, and large dosage. Thus, exploration of efficient nanozymes for the rapid dephosphorylation of phosphotriester under mild conditions remains a challenge. Here, a novel CeO2@NC nanozyme is developed with excellent phosphatases-like activity based on substrate synergistic effect, in which, CeO2 nanoparticles embedded in N-doped carbon (NC) material. Taking paraoxon as the model substrate, such CeO2@NC nanozyme can drive rapid dephosphorylation of phosphotriester over a broad temperature range, which not only significantly outperforms natural phosphatases and neat CeO2, but also can preserve >80% of the optimal activity after exposure of harsh conditions, such as strong acidic/basic medium, high temperature of up to 80 °C. The excellent catalytic performance could be due to that Ce(IV)/Ce(III) species act as the active sites to realize the polarization and hydrolysis of P-O bond while NC template works as the synergistic group to adsorb the substrate. Furthermore, a simple colorimetric assay is developed for the rapid and selective detection of paraoxon. Overall, this work not only develops a highly efficient phosphatases-like nanozyme via substrate synergetic strategy, but also opens an interesting avenue for the rapid detection of organophosphorus pesticides.

Conjugated Polyelectrolyte/Silver Bromide Nanocomposites: Highly Durable and Robust Antibacterial Materials.

We report the in situ synthesis of silver bromide nanoparticles (AgBr NPs) in a cationic conjugated polyelectrolyte (CPE) matrix. It is interesting that the obtained CPE/AgBr nanocomposite materials exhibit robust and long-term antimicrobial activity against both Gram-negative bacteria and Gram-positive bacteria by producing a large amount of biologically active Ag+. Meanwhile, it is demonstrated that the antimicrobial activity of CPE/AgBr nanocomposites is also related to the size of the AgBr NPs. Smaller particles show a faster AgBr release rate and hence higher antimicrobial activity than big particles. However, the relatively large-sized nanocomposites are beneficial to obtain long-term antimicrobial activity by substantially producing bioactive Ag+. Consequently, the antimicrobial property of the CPE/AgBr nanocomposites can be manipulated by controlling the dimensions of embedded AgBr NPs. The CPE/AgBr nanocomposites can cause a rapid initial drop of bacterial counts in solution, which makes it a potential candidate for antimicrobial therapy in emergency cases. In addition, the sustained release of Ag+ from large-sized nanocomposites makes them suitable for long-term use.

Nitrogen-Enriched Conjugated Polymer Enabled Metal-Free Carbon Nanozymes with Efficient Oxidase-Like Activity.

Metal-free carbon nanozymes could be promising with the unique features of intrinsic catalytic ability, structure diversity, and strong tolerance to acidic/alkaline media. However, to date, the study of metal-free carbon nanozymes fell far behind metal-based nanomaterials, in which, the majority reported much more peroxidase-like activity than other enzyme-mimicking behavior (e.g., oxidase). Thus, the exploit of high-performance carbon nanozymes is of importance but challenging. In this work, the nitrogen-rich conjugated polymer (Aza-CPs) with rigid network structure is utilized as precursor to yield N-doped carbon material QAU-Z1 in high yield via a direct pyrolysis method. Surprisingly, QAU-Z1 stood out in oxidase-like behavior, which significantly outperformed the control materials GNC-900 and QAU-Z2 with nucleobase or conjugated small molecule as precursor, respectively. More importantly, it is a crucial revelation that the catalytic performance is closely related to the change of zeta potential for carbon nanozyme during the substrate 3,3',5,5'-tetramethylbenzidine oxidation process, as well as its catalytical capacity to O2 , which could be insightful to understand the inherent mechanism. This work not only presents the potential of conjugated polymers in constructing highly efficient carbon nanozyme, but also reveals the vital role of interaction mode between the nanozyme and substrate in the catalytic performance.

Biofuel Cell-Driven Robust Electrochemiluminescence Biosensing Platform.

Electrochemiluminescence (ECL) is one powerful tool in the sensing field, in which the electrochemical workstation is necessary to achieve the electrical/optical signal conversion in the presence of luminescent agents. By contrast, biofuel cells (BFCs) can also provide electricity from renewable biofuels under moderate conditions. More importantly, BFCs with the features of adjustable voltage output and excellent compatibility would well meet the requirement of working voltages for different ECL devices. However, to the best of our knowledge, the BFC-driven luminous system has not been reported. In this work, we constructed, for the first time, a BFC-driven ECL system with fast and stable signal outputs. To demonstrate the proof-of-concept of the BFC-ECL system, the sensitive and selective detection of histidine was achieved, exhibiting great potential among point-of-care diagnoses in remote regions. Overall, this work not only paves a new way for the conversion of chemical energy, electrical energy, and luminous system but also explores the new application of BFC.

Rational Design of Low Band Gap Polymers for Efficient Solar Cells with High Open-Circuit Voltage: The Profound Effect of Me and Cl Substituents with a Similar van Der Waals Radius.

Generally, low band gap material-based photovoltaic devices have reduced open circuit voltage (VOC), and realizing the trade-off between the low band gap (Eg < 1.6 eV) and high VOC (>0.9 V) could be critical to give efficient polymer solar cells, especially for high-performance semitransparent PSCs and tandem solar cells. Although lots of efforts have been made to address the issue, most results have not been gratifying. In this work, the polymer PTBTz-Cl based on the chlorination method and efficient thiazole-induced strategy was designed and synthesized, aiming at the deep HOMO energy level, and the enhanced backbone planarity caused by the weak noncovalent Cl···S interaction. In addition, the methyl-substituted polymer PTBTz-Me was constructed as the reference due to the similar van der Waals radius of the side chain (CH3: 0.20 nm vs Cl: 0.18 nm). Encouragingly, in comparison with that of PTBTz-2, the newly synthesized polymers exhibit the red-shifted absorption spectra ranging from 300 to 770 nm, with an obviously reduced Eg of ∼1.6 eV. However, the function of Cl and Me substituents is different. Compared to the polymer PTBTz-Me, PTBTz-Cl exhibits a lower HOMO value, stronger crystallinity, and more compact intramolecular interactions. Consequently, the polymer PTBTz-Cl exhibits excellent photovoltaic performance with a notable VOC of 0.94 V and a power conversion efficiency of 10.35%, which is ∼11% higher than the 9.12% efficiency based on PTBTz-Me, and is also one of the highest values among polymer/fullerene solar cells. Moreover, a smaller photo energy loss (Eloss) of 0.64 eV is achieved, which is rare among the current high-performance polymer systems.

Chlorinated Polymers for Efficient Solar Cells with High Open Circuit Voltage: The Influence of Different Thiazole Numbers.

The chlorination strategy has gradually become a promising approach to improve the open circuit voltage (VOC ) in polymer solar cells. In this work, by using an efficient thiazole-induced strategy in a polymer backbone, three thieno[3,4-b]thiophene (TT)-based polymers-PBClTTz-0, PBClTTz-1, and PBClTTz-2-are designed and synthesized with a Cl-substituted benzodithiophene (BDT) moiety and a thiazole unit as a π spacer. As expected, all of the polymers show a desirable open circuit voltage (VOC ) of >0.94 V in the solar cells; specifically, the voltage can reach 1.01 V for polymer PBClTTz-2 with two thiazole moieties. In addition, due to the excellent surface morphology and weak recombination of the active layer, photovoltaic devices based on PBClTTz-1 with one thiazole unit exhibit the highest power conversion efficiency (PCE) of 8.42%, which is noticeably superior to the fluorinated analogue PBClTTz-0 (6.85%). This work reveals the influence of the thiazole unit in a quinoid polymer backbone and confirms that the Donor-Acceptor(π)-Quinoid strategy is a promising construction method in molecular design.

Regulating Molecular Aggregations of Polymers via Ternary Copolymerization Strategy for Efficient Solar Cells.

For many high-performance photovoltaic materials in polymer solar cells (PSCs), the active layers usually need to be spin-coated at high temperature due to the strong intermolecular aggregation of donor polymers, which is unfavorable in device repeatability and large-scale PSC printing. In this work, we adopted a ternary copolymerization strategy to regulate polymer solubility and molecular aggregation. A series of D-A1-D-A2 random polymers based on different acceptors, strong electron-withdrawing unit ester substituted thieno[3,4-b]thiophene (TT-E), and highly planar dithiazole linked TT-E (DTzTT) were constructed to realize the regulation of molecular aggregation and simplification of device fabrication. The results showed that as the relative proportion of TT-E segment in the backbone increased, the absorption evidently red-shifted with a gradually decreased aggregation in solution, eventually leading to the active layers that can be fabricated at low temperature. Furthermore, due to the excellent phase separation and low recombination, the optimized solar cells based on the terpolymer P1 containing 30% of TT-E segment exhibit high power conversion efficiency (PCE) of 9.09% with a significantly enhanced fill factor up to 72.86%. Encouragingly, the photovoltaic performance is insensitive to the fabrication temperature of the active layer, and it still could maintain high PCE of 8.82%, even at room temperature. This work not only develops the highly efficient photovoltaic materials for low temperature processed PSCs through ternary copolymerization strategy but also preliminarily constructs the relationship between aggregation and photovoltaic performance.

Compact Layer Free Perovskite Solar Cells with a High-Mobility Hole-Transporting Layer.

A high-mobility diketopyrrolopyrrole-based copolymer (P) was employed in compact layer free CH3NH3PbI3 perovskite solar cells as a hole-transporting layer (HTL). By using the P-HTL, the 6.62% device efficiency with conventional poly-3-hexylthiophene was increased to 10.80% in the simple device configuration (ITO/CH3NH3PbI3/HTL/MoO3/Ag). With improved short circuit current density, open circuit voltage, and fill factor, the higher power conversion efficiency of P-HTL device is ascribed to the higher carrier mobility, more suitable energy level, and lower interfacial charge recombination. Advantages of applying P-HTL to perovskite solar cells, such as low cost, low-temperature processing, and excellent performance with simple cell structure, exhibit a possibility for commercial applications.

Aromatic Heterocycle 1,3,4-Oxadiazole-Substituted Thieno[3,4-b]thiophene to Build Low-Bandgap Polymer for Photovoltaic Application.

Electron-deficient heterocycle 1,3,4-oxadiazole is first introduced to the 2-position of thieno[3,4-b]thiophene (TT) to construct a new building block 2-(thieno[3,4-b]thiophen-2-yl)-5-(alkylthio)-1,3,4-oxadiazole (TTSO) with alkylthio chain. The polymer PBDT-TTSO based on TTSO and benzodithiophene (BDT) exhibits a deep lying highest occupied molecular orbital (HOMO) energy level of -5.32 eV and low-bandgap of 1.62 eV. The power conversion efficiency (PCE) of 5.86% is obtained with a relatively high V OC of 0.74 V, a J SC of 13.1 mA cm(-2), and FF of 60.5%. Furthermore, as S atom in thioether can be oxidized easily, the optoelectronic properties of PBDT-TTSO treated with different oxidants are preliminary investigated. Interestingly, the oxidation products still maintain high PCE with reduction less than 30%. This work demonstrates a new method to regulate HOMO energy levels by introducing electron-deficient aromatic heterocyclic moiety.

Intra- and Intermolecular Steric Hindrance Effects Induced Higher Open-Circuit Voltage and Power Conversion Efficiency.

A pair of donor-acceptor polymers PBDThDTBT and PBDTchDTBT are synthesized, which share the same conjugated backbone, but are designed with hexyl and cyclohexyl side chains, respectively. The stronger steric hindrance of cyclohexyl endows PBDTchDTBT a deeper lying HOMO energy level of -5.39 eV compared to -5.22 eV for PBDThDTBT. However, PBDThDTBT and PBDTchDTBT exhibit a similar optical bandgap around 1.72 eV and a hole mobility around 10-5 cm2 V-1 s-1. Interestingly, the PBDTchDTBT/PC71BM blends exhibited higher hole mobility than PBDThDTBT/PC71BM after DIO was added. The higher hole mobility and fibrillar network in the active layer endows PBDTchDTBT higher power conversion efficiency of 7.9%, together with simultaneously improved open-circuit voltage of 0.80 V, short-circuit current density of 13.50 mA cm-2, and fill factor of 72.74% after a systemic study of their solar cell devices.

Development of new two-dimensional small molecules based on benzodifuran for efficient organic solar cells.

A new organic small molecule, DCA3TBDF, with a 2D benzo[1,2-b:4,5-b']difuran (BDF) moiety as the central core and octyl cyanoacetate units as the end-capped blocks, was designed and synthesized for solution-processed bulk heterojunction solar cells. DCA3TBDF possesses good solubility in common organic solvents such as toluene, CH2Cl2, chlorobenzene, and CHCl3 and good thermal stability with an onset decomposition temperature with 5% weight-loss occurring at 361 °C. The DCA3TBDF thin film showed a broad absorption at λ=320-700 nm and high crystallinity. Small-molecule organic solar cells based on DCA3TBDF and [6,6]-phenyl-C61-butyric acid methyl ester demonstrated promising power conversion efficiency with a high fill factor under the illumination of AM 1.5G (100 mW cm(-2)).

Novel donor-acceptor polymer containing 4,7-bis(thiophen-2-yl)benzo[c][1,2,5]thiadiazole for polymer solar cells with power conversion efficiency of 6.21%.

In order to improve the solution processability of 4,7-bis(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (DTBT)-based polymers, novel donor-acceptor polymer PTOBDTDTBT containing DTBT and benzo[1,2-b:4,5-b']dithiophene (BDT) with conjugated side chain is designed and synthesized with narrow band gap 1.67 eV and low lying HOMO energy level -5.4 eV. The blend film of PTOBDTDTBT and PC71 BM exhibits uniform and smooth film with root-mean-square (RMS) surface roughness 1.15 nm because of the excellent solubility of PTOBDTDTBT when six octyloxy side chains are introduced. The hole mobility of the blend film is measured to be 4.4 × 10(-5) cm(2) V(-1) s(-1) by the space-charge-limited current (SCLC) model. The optimized polymer solar cells (PSCs) based on PTOBDTDTBT/PC71 BM exhibits an improved PCE of 6.21% with Voc = 0.80 V, Jsc = 11.94 mA cm(-2) and FF = 65.10%, one of the highest PCE in DTBT containing polymers.