Bioinspired Passive Tactile Sensors Enabled by Reversible Polarization of Conjugated Polymers

Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors consume less power,but lack the capability to resolve static stimuli.Here,we address this issue by utilizing the unique polarization chemistry of conjugated polymers for the first time and propose a new type of bioinspired,passive,and bio-friendly tactile sensors for resolving both static and dynamic stimuli.Specifically,to emulate the polarization process of natural sensory cells,conjugated polymers(including poly(3,4-ethylenedioxythiophen e):poly(styrenesulfonate),polyaniline,or polypyrrole)are controllably polarized into two opposite states to create artificial potential differences.The controllable and reversible polarization process of the conjugated polymers is fully in situ characterized.Then,a micro-structured ionic electrolyte is employed to imitate the natural ion channels and to encode external touch stimulations into the variation in potential difference outputs.Compared with the currently existing tactile sensing devices,the developed tactile sensors feature distinct characteristics including fully organic composition,high sensitivity(up to 773 mV N^(−1)),ultralow power consumption(nW),as well as superior bio-friendliness.As demonstrations,both single point tactile perception(surface texture perception and material property perception)and two-dimensional tactile recognitions(shape or profile perception)with high accuracy are successfully realized using self-defined machine learning algorithms.This tactile sensing concept innovation based on the polarization chemistry of conjugated polymers opens up a new path to create robotic tactile sensors and prosthetic electronic skins.

Recent advances and innovations in the design and fabrication of wearable flexible biosensors and human health monitoring systems based on conjugated polymers

Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing wearable biosensors have accelerated the development of point-of-care sensing platforms and implantable biomedical devices in human health care.Among numerous potential materials,conjugated polymers(CPs)are emerging as ideal choices for constructing high-performance wearable biosensors because of their outstanding conductive and mechanical properties.Recently,CPs have been extensively incorporated into various wearable biosensors to monitor a range of target biomolecules.However,fabricating highly reliable CP-based wearable biosensors for practical applications remains a significant challenge,necessitating novel developmental strategies for enhancing the viability of such biosensors.Accordingly,this review aims to provide consolidated scientific evidence by summarizing and evaluating recent studies focused on designing and fabricating CP-based wearable biosensors,thereby facilitating future research.Emphasizing the superior properties and benefits of CPs,this review aims to clarify their potential applicability within this field.Furthermore,the fundamentals and main components of CP-based wearable biosensors and their sensing mechanisms are discussed in detail.The recent advancements in CP nanostructures and hybridizations for improved sensing performance,along with recent innovations in next-generation wearable biosensors are highlighted.CPbased wearable biosensors have been—and will continue to be—an ideal platform for developing effective and user-friendly diagnostic technologies for human health monitoring.

Conjugated microporous polymers-scaffolded enzyme cascade systems with enhanced catalytic activity

Enhancing catalytic activity of multi-enzyme in vitro through substrate channeling effect is promis-ing yet challenging.Herein,conjugated microporous polymers(CMPs)-scaffolded integrated en-zyme cascade systems(I-ECSs)are constructed through co-entrapping glucose oxidase(GOx)and horseradish peroxidase(HRP),in which hydrogen peroxide(H_(2)O_(2)) is the intermediate product.The interplay of low-resistance mass transfer pathway and appropriate pore wall-H_(2)O_(2) interactions facilitates the directed transfer of H_(2)O_(2),resulting in 2.4-fold and 5.0-fold elevation in catalytic activ-ity compared to free ECSs and separated ECSs,respectively.The substrate channeling effect could be regulated by altering the mass ratio of GOx to HRP.Besides,I-ECSs demonstrate excellent stabili-ties in harsh environments and multiple recycling.

Tuning Acceptor Length in Photocatalytic Donor-Acceptor Conjugated Polymers for Efficient Solar-to-Hydrogen Energy Conversion

The development of conjugated polymer photocatalysts for efficient solar-to-hydrogen energy conversion is highly desirable for the sustainability of our society.Although the construction of donor-acceptor(D-A)structure in conjugated polymer photocatalysts for solar-to-hydrogen energy conversion has been well documented,less attention has been paid on how large D and how large A units combined together could achieve the best performance.Herein,a series of D-A copolymers P(BDT-DBTSOx)(x=7,19,39,and 79)composed of a benzodithiophene(BDT)donor unit and an oligomeric dibenzo[b,d]thiophene sulfone(DBTSO)acceptor segment were synthesized and studied.It was found that the polymer photocatalytic stabilities under full-arc irradiation improved upon shortening the length of the acceptor segment.Under visible light irradiation and in the presence of 3 wt%Pt cocatalyst,P(BDT-DBTSO79)displayed the best performance with an optimal hydrogen evolution rate of 119.3±5.8 mmol·g^(-1)·h^(-1).This is 1.4-fold as that of DBTSO homopolymer and 22.5-fold as that of BDT/DBTSO alternative copolymer,highlighting the importance of acceptor length in D-A structure for achieving high photocatalytic performance.

Embedding pyridine units in acceptors to construct donor-acceptor conjugated polymers

The development of donor-acceptor(D-A) conjugated polymers greatly promotes the device performance in organic electronics. Recently, the strategy of embedding pyridine units into D-A conjugated polymer backbones has attracted much attention due to the resulted lowered LUMO levels. In addition, the possible non-bonding interactions resulted from the nitrogen atoms also improve the coplanarity of the polymer backbones. All these factors have great contribution to enhance the device performance. In this review, we summarized the recent development of pyridine-embedded D-A conjugated polymers and their applications in organic field-effect transistors(OFETs).

Dithienocarbazole- and benzothiadiazole-based donor-acceptor conjugated polymers for bulk heterojunction polymer solar cells

Donor-acceptor （D-A）-conjugated polymers P（BT-C1） and P（BT-C2）, with dithieno[2,3-b;7,6-b]carbazole （C1） or dithi- eno[3,2-b;6,7-b]carbazole （C2） as D-unit and benzothiadiazole （BT） as A-unit, were synthesized. The optical bandgaps of the polymers are similar （1.84 and 1.88 eV, respectively）. The structures of donor units noticeably influence the energy levels and backbone curvature of the polymers. P（BT-C1） shows a large backbone curvature; its highest occupied molecular orbital （HOMO） energy level is -5.18 eV, whereas P（BT-C2） displays a pseudo-straight backbone and has a HOMO energy level of -5.37 eV. The hole mobilities of the polymers without thermal annealing are 1.9×10^-3 and 2.7×10^-3 cm^2 V-1 s^-1 for P（BT-C1） and P（BT-C2）, respectively, as measured by organic thin-film transistors （OTFTs）. Polymer solar cells using P（BT-C1） and P（BT-C2） as the donor and phenyl-Cyl-butyric acid methyl ester （PCyLBM） as the acceptor were fabricated. Power conversion efficiencies （PCEs） of 4.9% and 5.0% were achieved for P（BT-C1） and P（BT-C2）, respectively. The devices based on P（BT-C2） exhibited a higher Voc due to the deeper HOMO level of the polymer, which led to a slightly higher PCE.

A Stable Open-Shell Conjugated Diradical Polymer with Ultra-High Photothermal Conversion Efficiency for NIR-Ⅱ Photo-Immunotherapy of Metastatic Tumor

Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.

Effect of electron-electron interaction on polarization process of exciton and biexciton in conjugated polymer

By using one-dimensional tight-binding model modified to include electron-electric field interaction and electron-electron interaction,we theoretically explore the polarization process of exciton and biexciton in cis-polyacetylene.The dynamical simulation is performed by adopting the non-adiabatic evolution approach.The results show that under the effect of moderate electric field,when the strength of electron-electron interaction is weak,the singlet exciton is stable but its polarization presents obvious oscillation.With the enhancement of interaction,it is dissociated into polaron pairs,the spin-flip of which can be observed through modulating the interaction strength.For the triplet exciton,the strong electron-electron interaction restrains its normal polarization,but it is still stable.In the case of biexciton,the strong electron-electron interaction not only dissociate it,but also flip its charge distribution.The yield of the possible states formed after the dissociation of exciton and biexciton is also calculated.

High-Performance Na-Ion Storage of S-Doped Porous Carbon Derived from Conjugated Microporous Polymers

Na-ion batteries(NIBs)have attracted considerable attention in recent years owing to the high abundance and low cost of Na.It is well known that S doping can improve the electrochemical performance of carbon materials for NIBs.However,the current methods for S doping in carbons normally involve toxic precursors or rigorous conditions.In this work,we report a creative and facile strategy for preparing S-doped porous carbons(SCs)via the pyrolysis of conjugated microporous polymers(CMPs).Briefly,thiophene-based CMPs served as the precursors and doping sources simultaneously.Simple direct carbonization of CMPs produced S-doped carbon materials with highly porous structures.When used as an anode for NIBs,the SCs exhibited a high reversible capacity of 440 mAh g?1 at 50 mA g?1 after 100 cycles,superior rate capability,and excellent cycling stability(297 mAh g?1 after 1000 cycles at 500 mA g?1),outperforming most S-doped carbon materials reported thus far.The excellent performance of the SCs is attributed to the expanded lattice distance after S doping.Furthermore,we employed ex situ X-ray photoelectron spectroscopy to investigate the electrochemical reaction mechanism of the SCs during sodiation-desodiation,which can highlight the role of doped S for Na-ion storage.

Synthesis,Conductivity and Photosensitivity of 2-D Conjugated Polymers of Metal-porphyrazine with Sulfur Bridges

The title polymers PMS 8Pz,M=Mn Ⅱ,Fe Ⅱ,Co Ⅱ,Ni Ⅱ,Cu Ⅱ,Zn Ⅱ,were synthesized by teaction of 2,3,5,6 tetracyano 1,4 dithiin with corresponding metal salts ,respectively.The styucture and properties of these polyers were characterized by elemental analysis,transmission electron microscope,DTA,IR, UV Vis,fluorescence and EPR spectra. It has been found that these conjugated polymers have the property of intrinsic semiconductor. The conductivity σ 298K of these polymers is in the range of 10 -9 ￣10 -3 S · cm -1 under pressure 10.63 MPa and incremental in the metal orderMn < Co<Fe<Zn<Cu<Ni.\ The photosensitivity of the MS 8Pz to the CdS PVA films is incremental in the metal order Zn < Mn < Co < Fe < Cu < Ni.

Effects of polarons on static polarizabilities and second order hyperpolarizabilities of conjugated polymers

According to the one-dimensional tight-binding Su-Schrieffer-Heeger model, we have investigated the effects of charged polarons on the static polarizability, axx, and the second order hyperpolarizabilities, γxxxx, of conjugated polymers. Our results are consistent qualitatively with previous ab initio and semi-empirical calculations. The origin of the universal growth is discussed using a local-view formalism that is based on the local atomic charge derivatives. Furthermore, combining the Su Schrieffer-Heeger model and the extended Hubbard model, we have investigated systematically the effects of electron-electron interactions on αxx and γxxxx of charged polymer chains. For a fixed value of the nearest-neighbour interaction V, the values of αxx and γxxxx increase as the on-site Coulomb interaction U increases for U 〈 Uc and decrease with U for U 〉 Uc, where Uc is a critical value of U at which the static polarizability or the second order hypcrpolarizability reaches a maximal value of αxx or γxxxx. It is found that the effect of the e-e interaction on the value of αxx is dependent on the ratio between U and V for either a short or a long charged polymer. Whereas, that effect on the value of γxxxx is sensitive both to the ratio of U to V and to the size of the molecule.

Two-step dissociation of a polaron in conjugated polymers

We have studied the electric-field-driven motion of a polaron by solving the time-dependent SchrSdinger equation nonadiabatically and the lattice equation of motion simultaneously. It is found that the polaron may experience two sequent transitions under high fields; one is the transition from the subsonic to the supersonic state, and the other from the supersonic to dissociated state. The acoustic mode is decoupled from the charge when the polaron moves at a speed faster than the sound speed, and then the optical mode is decoupled at the second transition to make the polaron dissociate completely.

The short wave near-infrared fluorescence properties of two p-azaquinodimethane (p-AQM)-based conjugated polymers

The absorption,scattering,and autofluorescence of biological tissues in short-wave infrared re-gion(SWIR,900-1700 nm)are relatively low,so SWIR fluorescence usually has deeper pene-tration into living tissues,and can show a higher signal-to-noise ratio when used for imaging in vivo.However,there are few types of organic SWIR fluorescent materials currently.In this work,p-azaquinodimethane(p-AQM)with a quinoid structure is used as the acceptor unit,and car-bazole or fluorene with sp3 hybridization are used as the donor units,two conjugated polymers were synthesized.The quinone structure is conducive to the redshift of absorption and fluores-cence spectra,and the sp3 hybridization structure is conducive to weakening the aggregation quenching of polymer fluorescence.PF and PCz exhibited absorption peaks of 492 nm and 508 nm,respectively.The emission peaks of the two polymers are 920 nm and 950 nm,respec-tively,both in the short-wave near infrared region.The quantum yield(QY)of PF and PCz is 0.4%and 0.3%,respectively.

Electropolymerizable Conjugated Polymers with High Contrast in Infrared Region

Two conjugated molecules have been designed and synthesized for preparing electrochromic thin film devices on the surface of electrodes through electropolymerization. These devices exhibit good contrast at around 80% in mid-infrared region and rapid response time, especially EP02 which could be switched between on and off state in around 1 s. The interesting electrochromic properties and easy processable properties open the door to electrochromic applications using large or flexible surfaces such as IR shutters and apertures.

Electron Correlation Effects in Polaron-Pair Recombination in Conjugated Polymers

Within a Su-Schriffer-Heeger model modified to include electron-electron interaction and an external electric field, we investigate the dynamics of oppositely charged polarons in a polymer chain in the presence of both electron-phonon and electron-electron interactions under the influence of an external electric field. We adopt a multi-configurational time-dependent Hartree-Fock method for the time-dependent Schrodinger equation and the Newtonian equation of motion for a lattice. Our results show that the on-site Coulomb interaction is of fundamental importance and favors the recombination between the pairs of polarons, and the yield of excitons depends crucially on the strength of the on-site Coulomb interaction U. Furthermore, the influence of the nearest neighbor interaction V is also discussed.

Synthesis and characterization of conjugated polymer containing azobenzene and oxadiazole units

A novel conjugated polymer containing azobenzene and oxadiazole units was synthesized through multi-step synthesis. The structures and properties of monomer and polymer were characterized and evaluated with IR, ^1H NMR, UV, TGA and GPC, respectively. Polymer with long side chain of alkoxy shows good solubility, thermal stability and photoisomerization property.

Synthesis and photocatalytic activity of TiO_2/conjugated polymer complex nanoparticles

A photocatalyst of nanometer TiO2/conjugated polymer complex was successfully synthesized and characterized by spectroscopic methods and photocatalytic experiments. The complex photocatalyst could be activated by absorbing both ultraviolet and visible light （λ = 190-800 nm）. Methylene blue （MB） could be degraded more efficiently on the complex photocatalyst than on the TiO2 under natural light. The conjugated polymer played a promoting role in the photocatalytic degradation of MB. The calcination temperature had an important effect in degradation of dye and could be summarized as 260℃ 〉 300 ℃ 〉 340 ℃ 〉 220 ℃ 〉 180 ℃.

Novel Bipolar Conjugated Polymer Containing Both Triphenylamine and Oxadizole Units

A novel bipolar conjugated polymer containing triphenylamine and 1, 3, 4-oxadiazole units was synthesized by Suzuki reaction. Its structure and properties were characterized by NMR, IR, UV-Vis, PL spectroscopy and electrochemical measurement. The photoluminescent spectroscopy and cyclic voltammograms measurement demonstrated that the resulting polymer shows blue emission (477 nm) and possesses both electron and hole-transporting property.

Confinement-induced nanocrystal alignment of conjugated polymer by the soft-stamped nanoimprint lithography

Soft-stamped nanoimprint lithography（NIL） is considered as one of the most effective processes of nanoscale patterning because of its low cost and high throughput. In this work, this method is used to emboss the poly（9, 9-dioctylfluorene）film. By reducing the linewidth of the nanogratings on the stamp, the orientations of nanocrystals are confined along the grating vector in the nanoimprint process, where the confinement linewidth is comparable to the geometrical size of the nanocrystal. When the linewidth is about 400 nm, the poly（9, 9-dioctylfluorene）（PFO） nanocrystals could be orderly arranged in the nanogratings, so that both pattern transfer and well-aligned nanocrystal arrangement could be achieved in a single step by the soft-stamped NIL. The relevant mechanism of the nanocrystalline alignment in these nanogratings is fully discussed. The modulation of nanocrystal alignment is of benefit to the charge mobilities and other performances of PFO-based devices for the future applications.

Anti-tumor Activity of Biodegradable Polymer-paclitaxel Conjugated Micelle Against Mice U14 Cervical Cancers

Two kinds of paclitaxel（PTX） conjugate micelles,of which one contained 25%（mass fraction） PTX [M（PTX）] and the other contained 22.5%（mass fraction） of PTX and 1.4%（mass fraction） of folate（FA）[FA-M（PTX）],were prepared for cell apoptosis and anti-tumor activity evaluation on U14 cervical cancer mouse models in comparison with 0.9%（mass fraction） saline（control） and equivalent Taxol.Seven days after tail intravenous injection of the drugs,the mice were sacrificed to measure the tumor masses.The average tumor masses were 4.26,2.89,2.63,and 2.17 g for the control,Taxol,M（PTX） and FA-M（PTX） groups,respectively.The inhibition rates of tumor growth calculated for the three drug groups were 32%,38% and 49%,respectively.Flow cytometry（FC） analysis and terminal deoxynucleotidyl transferase（TdT）-mediated deoxyuridine triphosphate（dUTP） nick end labeling（TUNEL） assay were conducted on the cancer tissues.The cell apoptosis rates based on the FC data and the TUNEL data were 20%,31%,37%,42%,and 10%,22%,26%,34%,respectively,both showing statistically significant differences（P〈0.05） between three drug groups and the control group,and between the FA-M（PTX） group and the other two drug groups.In conclusion,the composite FA-M（PTX） micelles can be used for U14 cervical cancer treatment.