Extraordinarily Stable Hairpin-Based Biosensors for Rapid Detection of DNA Ligases.

DNA ligases are essential enzymes involved in DNA replication and repair processes in all organisms. These enzymes seal DNA breaks by catalyzing the formation of phosphodiester bonds between juxtaposed 5' phosphate and 3' hydroxyl termini in double-stranded DNA. In addition to their critical roles in maintaining genomic integrity, DNA ligases have been recently identified as diagnostic biomarkers for several types of cancers and recognized as potential drug targets for the treatment of various diseases. Although DNA ligases are significant in basic research and medical applications, developing strategies for efficiently detecting and precisely quantifying these crucial enzymes is still challenging. Here, we report our design and fabrication of a highly sensitive and specific biosensor in which a stable DNA hairpin is utilized to stimulate the generation of fluorescence signals. This probe is verified to be stable under a wide range of experimental conditions and exhibits promising performance in detecting DNA ligases. We anticipate that this hairpin-based biosensor will significantly benefit the development of new targeting strategies and diagnostic tools for certain diseases.

Synergistic Contribution of Oligo(ethylene glycol) and Fluorine Substitution of Conjugated Polymer Photocatalysts toward Solar Driven Sacrificial Hydrogen Evolution.

To separately explore the importance of hydrophilicity and backbone planarity of polymer photocatalyst, a series of benzothiadiazole-based donor-acceptor alternating copolymers incorporating alkoxy, linear oligo(ethylene glycol) (OEG) side chain, and backbone fluorine substituents is presented. The OEG side chains in the polymer backbone increase the surface energy of the polymer nanoparticles, thereby improving the interaction with water and facilitating electron transfer to water. Moreover, the OEG-attached copolymers exhibit enhanced intermolecular packing compared to polymers with alkoxy side chains, which is possibly attributed to the self-assembly properties of the side chains. Fluorine substituents on the polymer backbone produce highly ordered lamellar stacks with distinct π-π stacking features; subsequently, the long-lived polarons toward hydrogen evolution are observed by transient absorption spectroscopy. In addition, a new nanoparticle synthesis strategy using a methanol/water mixed solvent is first adopted, thereby avoiding the screening effect of surfactants between the nanoparticles and water. Finally, hydrogen evolution rate of 26 000 µmol g-1  h-1 is obtained for the copolymer incorporated with both OEG side chains and fluorine substituents under visible-light irradiation (λ > 420 nm). This study demonstrates how the glycol side chain strategy can be further optimized for polymer photocatalysts by controlling the backbone planarity.

Thiazole Imide-Based All-Acceptor Homopolymer with Branched Ethylene Glycol Side Chains for Organic Thermoelectrics.

n-Type semiconducting polymers with high thermoelectric performance remain challenging due to the scarcity of molecular design strategy, limiting their applications in organic thermoelectric (OTE) devices. Herein, we provide a new approach to enhance the OTE performance of n-doped polymers by introducing acceptor-acceptor (A-A) type backbone bearing branched ethylene glycol (EG) side chains. When doped with 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI), the A-A homopolymer PDTzTI-TEG exhibits n-type electrical conductivity (σ) up to 34 S cm-1 and power factor value of 15.7 µW m-1 K-2 . The OTE performance of PDTzTI-TEG is far greater than that of homopolymer PBTI-TEG (σ=0.27 S cm-1 ), indicating that introducing electron-deficient thiazole units in the backbone further improves the n-doping efficiency. These results demonstrate that developing A-A type polymers with EG side chains is an effective strategy to enhance n-type OTE performance.

Reduced Nonradiative Recombination Energy Loss Enabled Efficient Polymer Solar Cells via Tuning Alkyl Chain Positions on Pendent Benzene Units of Polymers.

Nonradiative recombination energy loss (ΔE3) plays a key role in enhancing device efficiencies for polymer solar cells (PSCs). Until now, there is no clear resolution for reducing ΔE3 via molecular design. Herein, we report two conjugated polymers, PBDB-P-p and PBDB-P-m, which are integrated from benzo[1,2-b:4,5-b']dithiophene with alkylthio chain substituted at para- or meta-position on pendent benzene and benzo[1,2-c:4,5-c']dithiophene-4,8-dione. Both the polymers have different temperature-dependent aggregation properties but similar molecular energy levels. When BO-4Cl was used as an acceptor to fabricate PSCs, the device of PBDB-P-p:BO-4Cl displayed a maximal power conversion efficiency (PCE) of 13.83%, while the best device of PBDB-P-m:BO-4Cl exhibited a higher PCE of 14.12%. The close JSCs and fill factors in both PSCs are attributed to their formation of effective nanoscale phase separation as confirmed by atomic force microscopy measurements. We find that the PBDB-P-m-based device has 1 order of magnitude higher electroluminescence quantum efficiency (EQEEL) than in the PBDB-P-p-based one, which could arise from the relatively weak aggregation in the PBDB-P-m-based film. Thus, the PBDB-P-m-based device has a remarkably enhanced VOC of 0.86 V in contrast to 0.80 V in the PBDB-P-p-based device. This study offers a feasible structural optimization way on the alkylthio side chain substitute position on the conjugated polymer to enhance VOC by reducing nonradiative recombination energy loss in the resulting PSCs.