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A diazirine-based four-armed cross-linker (4CNN) with a tetrahedron geometry is presented for efficient patterning of polymeric semiconductors by photo-induced carbene insertion. After blending of 4CNN with no more than 3 % (w/w), photo-patterning of p-, n-, and ambipolar semiconducting polymers with side alkyl chains was achieved; regular patterns with size as small as 5 μm were prepared with appropriate photomasks after 365 nm irradiation for just 40 s. The interchain packing order and the thin film morphology were nearly unaltered after the cross-linking and the semiconducting properties of the patterned thin films were mostly retained. A complementary-like inverter with a gain value of 112 was constructed easily by two steps of photo-patterning of the p-type and n-type semiconducting polymers. The results show that 4CNN is a new generation of cross-linker for the photo-patterning of polymeric semiconductors for all-solution-processible flexible electronic devices.

Diketopyrrolopyrrole (DPP) and its derivatives are commercially used dyes that have drawn great attention in recent years for applications in organic electronic/optical materials. These material studies cannot progress without further developments in the syntheses of the DPP family of molecules. In this review, recent progress in the syntheses of DPP derivatives is summarized in detail as well as the structure–property relationships of the derivatives, including the syntheses of DPP cores, N-functionalization reactions, and π-extensions on and along the DPP cores. Finally, existing problems and future perspectives of DPP-based derivatives are also discussed.

The diallene-containing compound dACl-1 was unexpectedly obtained by the unconventional transformation of two carbonyl groups in 4,4′,5,5′-tetrachloro-10H,10′H-[9,9′-bianthracenylidene]-10,10′-dion...

Optically tunable field-effect transistors (FETs) with near infra-red (NIR) light show promising applications in various areas. Now, arylazopyrazole groups are incorporated in the side chains of a semiconducting donor-acceptor (D-A) polymer. The cis-trans interconversion of the arylazopyrazole can be controlled by 980 nm and 808 nm NIR light irradiation, by utilizing NaYF4 :Yb,Tm upconversion nanoparticles and the photothermal effect of conjugated D-A polymers, respectively. This reversible transformation affects the interchain packing of the polymer thin film, which in turn reversibly tunes the semiconducting properties of the FETs by the successive 980 nm and 808 nm light irradiation. The resultant FETs display fast response to NIR light, good resistance to photofatigue, and stability in storage for up to 120 days. These unique features will be useful in future memory and bioelectronic wearable devices.

Tuning autophagy in a controlled manner could facilitate cancer therapy but it remains challenging. Pyridinium-substituted tetraphenylethylene salts (PTPE 1-3), able to target mitochondria and disrupt autophagy after forming complexes with albumin, are reported. Mitochondrion affinity and autophagy-inducing activity are improved by prolonging the length of alkyl chains in PTPE 1-3. PTPE 1-3 demonstrate proautophagic activity and a mitophagy blockage effect. Failure of autophagosome-lysosome fusion in downstream autophagy flux results in cancer cell death. Moreover, fast formation of complexes of PTPE 1-3 with albumin in blood can facilitate biomimetic delivery and deep tumor penetration. Efficient tumor accumulation and effective tumor suppression are successfully demonstrated with in vitro and in vivo studies. PTPE 1-3 salts exhibit dual functionality: they target and image mitochondria because of aggregation-induced emission effects and they are promising for cancer therapy.

Multi-stimuli-responsive field-effect transistors (FETs) with organic/polymeric semiconductors have received increasing attention. Herein, we report a novel strategy for fabricating multi-stimuli-r...

Polycyclic aromatic hydrocarbons with hexagons/pentagons or hexagons/heptagons have been intensively investigated in recent years, but those with simultaneous presence of hexagons, pentagons and heptagons remain rare. In this paper, we report dicyclohepta[ijkl,uvwx]rubicene (DHR), a non-benzenoid isomer of dibenzo[bc,kl]coronene with two pentagons and two heptagons. We developed an efficient and scalable synthetic method for DHR by using Scholl reaction and dehydrogenation. Crystal structure of DHR shows that the benzenoid rings, two pentagons and two heptagons are coplanar. The bond lengths analysis and the ICSS(1)zz and LOL-π calculations indicate that the incorporation of two formal azulene moieties has an effect on the conjugated structure. The π-electrons of benzenoid and pentagon rings are more delocalized. Cyclic voltammetry studies indicate that DHR shows multiple oxidation and reduction potentials. Interestingly, DHR exhibits unusual S0 to S2 absorption and abnormal anti-Kasha S2 to S0 emission. Moreover, crystals of DHR exhibit semiconducting behaviour with hole mobility up to 0.082 cm2 V-1 s-1 .

The experimental investigation of side-chain effects on intramolecular charge transport in π-conjugated molecules is essential but remains challenging. Herein, the dependence of intra-molecular conductance on the nature of branching alkyl chains is investigated through a combination of the scanning tunneling microscope break junction (STM-BJ) technique and density functional theory. Three thiophene-flanked diketopyrrolopyrrole (DPP) derivatives with different branching alkyl chains (isopentane, 3-methylheptane, and 9-methylnonadecane) are used with phenylthiomethyl groups as the anchoring groups. The results of single-molecule conductance measurements show that as the alkyl chain becomes longer, the torsional angles between the aromatic rings increase due to steric crowding, and therefore, the molecular conductance of DPP decreases due to reduction in conjugation. Both theoretical simulations and 1 H NMR spectra demonstrate that the planarity of the DPPs is directly reduced after introducing longer branching alkyl chains, which leads to a reduced conductance. This work indicates that the effect of the insulating side chain on the single-molecule conductance cannot be neglected, which should be considered for the design of future organic semiconducting materials.

Photodynamic therapy (PDT) has emerged as an attractive alternative in cancer therapy, but therapeutic effects suffer from low photosensitizing efficiency and poor retention of photosensitizes in cancer cells. This paper reports the photosensitizers which show absorption and emission in the long-wavelength region and high photosensitizing efficiency can be formed in situ in cells from 4,6-dibromothieno[3,4-b]thiophene derivative (TT-5-P) after white light irradiation. The self-oligomerization of TT-5-P is uptaken in cells upon light irradiation-induced cell apoptosis simultaneously and efficiently. In addition, the formation of oligomers (TT-5-Ps) enhances the retention time in cells remarkably, which is advantageous for boosting the photodynamic therapy efficiency. Moreover, the selectivity toward tumor cells of TT-5-P can be improved obviously via the formation of complex of TT-5-P with albumin. This in situ photoinduced self-oligomerization strategy can be utilized to design effective biomaterials for long-term imaging and improved therapy.

Conjugated molecules with low lying LUMO levels are demanding for the development of air stable n-type organic semiconductors. In this paper, we report a new A-D-A'-D-A conjugated molecule (DAPDCV) entailing diazapentalene (DAP) and dicyanovinylene groups as electron accepting units. Both theoretical and electrochemical studies manifest that the incorporation of DAP unit in the conjugated molecule can effectively lower the LUMO energy level. Accordingly, thin film of DAPDCV shows n-type semiconducting behavior with electron mobility up to 0.16 cm2 ⋅V-1 ⋅s-1 after thermal annealing under N2 atmosphere. Moreover, thin film of DAPDCV also shows stable n-type transporting property in air with mobility reaching 0.078 cm2 ⋅V-1 ⋅s-1 .

A highly selective and red emissive fluorescent probe (HCyNB) for penicillin G amidase (PGA) has been prepared in a simple two-step process. After enzymatic reaction, HCyNB showed a fast response to PGA and afforded a light-up red fluorescence assay of PGA with a detection limit of 0.067 U L−1, without interference from other biologically-relevant species and enzymes, including ROS. The easy synthesis, fast response, good sensitivity, remarkable selectivity and pH independence render HCyNB an outstanding tool for bioimaging of endogenous PGA in penicillinase-producing Bacillus subtilis.

A systematic combination strategy is proposed for overcoming cisplatin resistance using near-infrared (NIR)-light-triggered hyperthermia. A new photothermal polymer DAP-F is complexed with a reduction-sensitive amphiphilic polymer P1 to form F-NPs with photothermal effect. Subsequently, to build the final nanosystem F-Pt-NPs, F-NPs are combined with Pt-NPs, which are obtained by encapsulating a Pt(IV) prodrug with P1. Mild hyperthermia (43 °C), generated from F-Pt-NPs induced by an 808 nm NIR laser, have various effects such as: i) enhancing the cellular membrane permeability to promote the uptake of drugs; ii) activating cisplatin by accelerating the glutathione consumption; iii) increasing the Pt-DNA adducts formation and possibly the formation of a portion of irreparable Pt-DNA interstrand crosslinks, thereby inhibiting the repair of DNA. In vitro, it is found that even on cisplatin-resistant A549DDP cells, the IC50 of F-Pt-NPs (43 °C) is only 7.0 × 10-6 m Pt mL-1 . In vivo, on a patient-derived xenograft model of multidrug resistant lung cancer, the efficacy of the F-Pt-NPs (43 °C) treatment group shows a tumor inhibition rate of 94%. Taken together, here, an important perspective of resolving cascade drug resistance with the assistance of mild hyperthermia triggered by NIR light is presented, which can be of great significance for clinic translation.

Diketopyrrolopyrrole (DPP) as a building block has been intensively investigated for organic semiconductors and light emitting materials. The synthesis of N-aryl DPPs remains challenging. Herein, we firstly report a new easily handled synthetic method toward N-aryl DPPs through H-DPP with diaryliodonium salt in the presence of CuI, which shows broad reaction scope. Sixteen N-aryl DPPs, including phenyl, furan and thiophene as flanking aromatic groups, were synthesized with yields up to 78 %. These N-aryl DPPs are fluorescent in both solutions and solid states, with quantum yields up to 96 % and 40 %, respectively. Moreover, we show that the reaction between H-DPP and diaryliodonium salt can lead to π-expanded DPPs by using Pd(OAc)2 as catalyst. Nine π-expanded DPPs were obtained in 27-61 % yields. These π-expanded DPPs exhibit good semiconducting properties with hole mobility of 0.71 cm2 V-1 s-1 , demonstrating that they are useful building blocks for high performance organic semiconductors.

Rigid and planar conjugated molecules have substantial significance due to their potential applications in organic electronics. Herein we report two highly fused ladder type conjugated molecules, TTCTTC and TTTCTTTC, with up to 10 fused rings in which the fused-thiophene rings are fused to the chromeno[6,5,4-def]chromene unit. Both molecules show high HOMO levels and accordingly they can be oxidized into their radical cations with absorptions extending to 1300 nm in the presence of trifluoroacetic acid. Thin films of TTCTTC and TTTCTTTC exhibit p-type semiconductor properties with hole mobilities up to 0.39 cm2 V−1 s−1. Moreover, TTCTTC shows a high fluorescence quantum yield of up to 16.5% in the solid state.

Two new ambipolar thiazole-flanked diketopyrrolopyrrole-based polymers pDPPTz2T-1 and pDPPTz2T-2 with urea-containing linear side-chains were prepared. The formation of hydrogen bonding enhanced th...

Peptides with modular structure provide a tailorable platform for constructing responsive supramolecular assemblies, which are attractive as functional biomaterials and smart sensors. In this work, the feasibility of regulating small peptides assembly with molecular design and metal ion recognition was demonstrated. Tripeptides were designed and found to have diverse response and self-assembly behavior to Hg2+. The incorporation of an aggregation-induced emission fluorophore TPE enabled the visualization of Hg2+ recognition and the assembly phenomenon. A structural analogue (Pep2) to γ-glutathione was identified with high specificity and nanomolar response to Hg2+ both in buffer solution and living cells. Driven by the coordination force and noncovalent intramolecular stacking, assembling of twisted nanofibers from Pep2-TPE and Hg2+ were observed. Benefiting from its biocompatibility, fast and switchable fluorescence response, Pep2-TPE was applied for imaging and monitoring Hg2+ distribution in living cel...

Imaging-guided photodynamic therapy (PDT) has been regarded as a promising strategy for precise cancer treatment. Because of their excellent modifiability and drug-loading capacity, nanoparticles have played an important role in PDT. Nonetheless, when traditional photosensitizers are made into nanoparticles, both their fluorescence and reactive oxygen species generation efficacy decrease due to a phenomenon known as aggregation-caused quenching. Fortunately, in recent years, several kinds of organic dyes with “abnormal” properties (termed aggregation-induced emission, AIE) were developed. With enhanced fluorescence emission in the nanoaggregation state, the traditional obstacles mentioned above may be overcome by AIE luminogens. Herein, we provide a better combination of photosensitizers and nanoparticles, namely, dual-function AIE nanoparticles capable of producing reactive oxygen species, to implement targeted and imaging-guided in vivo PDT. Good contrast of in vivo imaging and obvious therapeutic efficacy were observed at a low dose of AIE nanoparticles and low irradiance of light, thus resulting in negligible side effects. Our work shows that AIE nanoparticles may play a promising role in imaging-guided clinical PDT for cancer in the near future.

A supramolecular system (1@CB[7]) formed between an AIE-active molecule and cucurbit[7]uril (CB[7]) was used to construct selective fluorescent probe for spermine. 1@CB[7] displayed high selectivity toward spermine with a linear range of 0–12 μM and a detection limit of 1.0 μM spermine, which well covered the concentration range required for early diagnosis of cancer (1–10 μM for urinary spermine). The design strategy based on supramolecular chemistry avoided tedious and time-consuming synthetic and purification procedures. A selective fluorescent probe for 1-adamantanamine (AD) was also fabricated using the same approach based on the supramolecular structure of AIE-active molecule 1 and cucurbit[8]uril (CB[8]). This design strategy is crucial for the early diagnosis of malignant tumour and may provide some guideline for the development of new fluorescent probes for important biological species. Elsevier B.V. All rights reserved

We demonstrate a simple, but efficient, approach for improving the semiconducting performances of DPP-based conjugated D-A polymers. This approach involves the replacement of one bulky branching alkyl chain with the linear one at each DPP unit in regular polymer PDPPSe-10 and PDPPSe-12. The UV–vis absorption, Raman spectra, PDS data, and theoretical calculations support that the replacement of bulky branching chains with linear ones can weaken the steric hindrance, and accordingly conjugated backbones become more planar and rigid. GIWAXS data show that the incorporation of linear alkyl chains as in PDPPSe-10 and PDPPSe-12 is beneficial for side-chain interdigitation and interchain dense packing, leading to improvement of interchain packing order and thin film crystallinity by comparing with PDPPSe, which contains branching alkyl chains. On the basis of field-effect transistor (FET) studies, charge mobilities of PDPPSe-10 and PDPPSe-12 are remarkably enhanced. Hole mobilities of PDPPSe-10 and PDPPSe-12 in ...

The selective and sensitive detection of α-ketoglutaric acid ( KA ) is of great importance not only for biological studies but also for early diagnosis of cancers. In comparison with other assays, fluorescence detection is advantageous. However, the fluorescence turn-on detection of KA remains rare. In this paper, we disclose a new fluorescence detection of KA with the ensemble of silole-A and n -octanohydrazide by utilizing the aggregation induced emission feature of silole compounds and the chemical reaction between KA and n -octanohydrazide. The ensemble displays reasonably good sensitivity and selectivity toward KA , and KA with concentration as low as 1.5 μM can be detected.

Polymer adsorption and desorption are fundamental in many industrial and biomedical applications. Here, we introduce a new method to monitor the polymer desorption kinetics in situ based on the behavior of aggregation-induced emission. Poly(ethylene oxide) and colloidal silica (SiO2) were used as a model system. It was found that the aggregation-induced emission method could be successfully used to determine the polymer desorption kinetics, and the polymer desorption followed the first-order kinetics. It was also found that the polymer desorption rate constant decreased with the increasing molecular weight, which could be described by a power law function kd ≈ M–0.28, close to that of the adsorption rate constant.

A tetraphenylethylene based aggregation induced emission (AIE) probe, TPENNO 2 , bearing a 2,4-dinitrobenzenesulfonyl pendant was designed and synthesized for light-up and discriminatory detection of Cys over Hcy and GSH in PBS. The 2,4-dinitrobenzenesulfonyl group quenched the fluorescence of TPENNO 2 . While after thiol group promoted nucleophilic aromatic substitution reaction, TPENNO 2 can be converted to fluorescent TPENH 2 . The discriminatory detection of Cys over Hcy and GSH comes from the different reaction kinetic profiles of TPENNO 2 with the thiol residues of Cys, Hcy and GSH. Moreover, TPENNO 2 can be used to image biothiols in living HeLa cells.

Singlet fission (SF), in which one singlet exciton (S₁) splits into two triplets (T₁) on adjacent molecules through a correlated triplet-pair ¹(TT) state, requires precise but difficult tuning of exciton energetics and intermolecular electronic couplings in the solid state. Here we demonstrate anti-aromatic 4nπ dibenzopentalenes (DPs) as a new class of single-chromophore based intramolecular SF materials, which exhibit optically allowed S2 state with E(S₂) > 2E(T₁) and optically forbidden S₁ state. Ultrafast population transfer from high-lying S₂ state to ¹(TT) state was observed in monomeric solution of styryl-substituted DP (SDP) on sub-picosecond timescale. More importantly, we provide compelling evidence of exciton diffusion (ED) of ¹(TT) state to yield two individual long-lived triplets in SDP thin film. The overall triplet yield via iSF and subsequent triplet-pair diffusion can be as high as 142±10% in thin-film.

The rational design of multifunctional materials with both emissive and semiconducting properties remains a challenge. A multifunctional cruciform donor–acceptor (D–A) molecule, 2,2′-(((4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl)bis(thiophene-5,2-diyl))bis(methanylylidene))dimalononitrile (BDTTM), which contains a benzodithiophene as the central core, has been synthesized and, based on the output and transfer characteristics of the corresponding FETs, thin films of BDTTM exhibited ambipolar semiconducting behavior. Notably, FETs with thin films of BDTTM showed a photoresponse in both p- and n-channels, and drain-source-current enhancement under white-light irradiation could be detected, even at a low light intensity of 0.1 mW cm−2. Furthermore, BDTTM exhibited red-light emission both in solution and as a crystalline solid. A microplate of BDTTM with red-light emission displayed typical optical waveguiding behavior.

Apart from sensing and imaging, luminogens with aggregation-induced emission (AIE) are also interesting for photosensitizing. The photosensitizing behavior and bacteria-killing performance of a pyridinium-substituted tetraphenylethylene with an alkyne group (TPE-A-Py+ ) is reported herein. Interestingly, TPE-A-Py+ exhibits higher photosensitizing efficiency than TPE-Py+ (without alkyne group) when I- was used as a counteranion. This is well explained by the fact that the ΔEST between the excited singlet state (S1 ) and triplet state (T1 ) was lower for TPE-A-Py+ than for TPE-Py+ , according to theoretical calculations. Moreover, replacement of I- with other anions (PF6- , N(SO2 CF3 )2- and BPh4- ) led to a decrease of photosensitizing efficiency for TPE-A-Py+ . Notably, TPE-A-Py+ could be used as an efficient photosensitizer to photo-inactivate ampicillin-resistant (ampr ) E. coli at low concentration under white-light irradiation very quickly.

Biphenyl, as the elementary unit of organic functional materials, has been widely used in electronic and optoelectronic devices. However, over decades little has been fundamentally understood regarding how the intramolecular conformation of biphenyl dynamically affects its transport properties at the single-molecule level. Here, we establish the stereoelectronic effect of biphenyl on its electrical conductance based on the platform of graphene-molecule single-molecule junctions, where a specifically designed hexaphenyl aromatic chain molecule is covalently sandwiched between nanogapped graphene point contacts to create stable single-molecule junctions. Both theoretical and temperature-dependent experimental results consistently demonstrate that phenyl twisting in the aromatic chain molecule produces different microstates with different degrees of conjugation, thus leading to stochastic switching between high- and low-conductance states. These investigations offer new molecular design insights into building functional single-molecule electrical devices.

Based on one single AIE-doped photonic-structured polyionic liquid sphere, a novel customizable virtual sensor array system was developed., By simultaneously exploiting the unique properties of ionic liquids and aggregation-induced emission (AIE) luminogens, as well as photonic structures, a novel customizable sensing system for multi-analytes was developed based on a single AIE-doped poly(ionic liquid) photonic sphere. It was found that due to the extraordinary multiple intermolecular interactions involved in the ionic liquid units, one single sphere could differentially interact with broader classes of analytes, thus generating response patterns with remarkable diversity. Moreover, the optical properties of both the AIE luminogen and photonic structure integrated in the poly(ionic liquid) sphere provide multidimensional signal channels for transducing the involved recognition process in a complementary manner and the acquisition of abundant and sufficient sensing information could be easily achieved on only one sphere sensor element. More importantly, the sensing performance of our poly(ionic liquid) photonic sphere is designable and customizable through a simple ion-exchange reaction and target-oriented multi-analyte sensing can be conveniently realized using a selective receptor species, such as counterions, showing great flexibility and extendibility. The power of our single sphere-based customizable sensing system was exemplified by the successful on-demand detection and discrimination of four multi-analyte challenge systems: all 20 natural amino acids, nine important phosphate derivatives, ten metal ions and three pairs of enantiomers. To further demonstrate the potential of our spheres for real-life application, 20 amino acids in human urine and their 26 unprecedented complex mixtures were also discriminated between by the single sphere-based array.

A new selective and sensitive fluorescence turn-on detection of ClO- is reported by taking advantage of the specific reaction between a 1-methyl-1,2-dihydropyridine-2-thione unit and ClO- and the aggregation induced-emission (AIE) behavior of the tetraphenylethylene unit.

Conjugated D–A polymers with high charge mobilities have received increasing attention in recent years. In this paper, we report a simple, but efficient approach to improve the charge mobilities of conjugated polymers by partial replacement of branching alkyl chains with linear ones. With this strategy in mind, we designed and investigated three new DPP-quaterthiophene terpolymers PDPP4T-1, PDPP4T-2 and PDPP4T-3 containing both linear (n-dodecane) and branching (2-decyltetradecyl) alkyl chains with different ratios. On the basis of GIWAXS data, interchain packing order is improved for terpolymers PDPP4T-1, PDPP4T-2 and PDPP4T-3, in comparison with PDPP4T with only branching alkyl chains. The incorporation of linear alkyl chains can affect the interchain packing mode, and PDPP4T-3 with more linear alkyl chains among the three terpolymers adopts the edge-on chain arrangement on the substrate. Field effect transistor measurements indicate that PDPP4T-1, PDPP4T-2 and PDPP4T-3 exhibit higher hole mobilities than PDPP4T. Moreover, the hole mobilities increase in the following order: PDPP4T-1 < PDPP4T-2 < PDPP4T-3 by increasing the content of linear alkyl chains in these terpolymers. The thin film mobility of PDPP4T-3 can reach 6.1 cm2 V−1 s−1, which can be further increased to 9.1 cm2 V−1 s−1 after incorporating NMe4I.

In this work, a conjugated polymer PNV is developed, linking naphthalene diimide with a vinyl linkage. Owing to the C–H⋯O hydrogen bond between the carbonyl and the vinyl, PNV exhibits a high red emission with a quantum yield of 33.4% in the solid state while it shows n-type properties with an electron mobility up to 1.5 × 10−3 cm2 V−1 s−1 in organic field effect transistors, simultaneously.

A fast and sensitive method was established for an in-solution selection of cancer cell-targeting peptides at "single-residue resolution" by using the switchable fluorescence of tetraphenylethylene. The selected peptides have potential for biomarker tracing and can be used for targeted delivery of different cargos into living cancer cells.

Two-photon excited fluorescence microscopy and nanoparticle-assisted photodynamic therapy (PDT) are two important areas in biomedical research, and their combination can be more beneficial. A type of red emissive photosensitizer (PS) with aggregation-induced emission (AIE) features, which is called tetraphenylethylene (TPE-red), was synthesized and further encapsulated with poly(styrene-co-maleic anhydride) (PSMA) to form nanoparticles. Two-photon fluorescence, as well as two-photon excited reactive oxygen species (ROS) generation by TPE-red–PSMA nanoparticles, was characterized. A large two-photon absorption cross-section was observed at 1040 nm with a femtosecond (fs) laser. PDT via two-photon excitation was well realized on tumor cells, using TPE-red–PSMA nanoparticles as PSs under 1040 nm fs laser excitation. Based on our study, we believe that two-photon excited PDT with AIE-active PSs has great potential applications in deep tissue imaging-guided therapy.

n-Type organic/polymeric semiconductors with high electron mobilities are highly demanded for future flexible organic circuits. Except for developing a new conjugated backbone, recent studies show that side-chain engineering also plays an indispensable role in boosting the charge-transporting property. In this paper, we report a new polymer PNDI2T-DTD with a representative n-type naphthalene diimide (NDI)-bithiophene backbone for high-performance n-type flexible thin-film transistors through branching/linear side-chain engineering strategy. Serving as the flexible side chains, the linear/branching side-chain pattern is found to be effective in tuning the preaggregation behavior in solution and the packing ordering of polymeric chains, resulting in the improvement of thin-film crystallinity. The electron mobility of the thin film of PNDI2T-DTD on flexible substrates can reach 1.52 cm2 V-1 s-1, which is approximately five times higher than that of PNDI2T-DT with the same conjugated backbone and only branching alkyl chains.

A new design strategy for photoresponsive semiconducting polymer with tri-stable semiconducting states is reported by simultaneous incorporation of tetra-ortho-methoxy-substituted azobenzene (mAzo) and arylazopyrazole (pAzo) in the side chains. The trans-to-cis transformations for mAzo and pAzo groups can sequentially occur within the polymer thin film after sequential 560 and 365 nm light irradiation. Remarkably, the trans-cis isomerization of mAzo and pAzo groups can modulate the thin film crystallinity. Accordingly, the performances of the resulting field-effect transistors (FETs) can be reversibly modulated, leading to tri-stable semiconducting states after sequential 560, 365, and 470 nm light irradiation. Therefore, the device performance can be logically controlled by light irradiation at three different wavelengths. In addition, with light irradiation and device current as the input and output signals, the three-value logic gate by using single FET device can be successfully mimicked.

A tetraphenylethylene based aggregation induced emission (AIE) probe, TPEPyE, bearing a positively charged pyridinium pendant was designed and synthesized. The positively charged TPEPyE can efficiently bind to the negatively charged lipopolysaccharide (LPS) through electrostatic interactions between the two oppositely charged species. As a result, upon the addition of LPS into the PBS solution of TPEPyE, this probe aggregated immediately onto the surface of LPS and resulted over 22-fold of fluorescence enhancement. TPEPyE exhibited good selectivity and high sensitivity toward LPS in PBS buffer solution and the detection limit was calculated to be 370 pM (3.7ng/mL). More notably, TPEPyE also retained good sensitivity and selectivity in artificial urine system (with much higher ionic strength) with the detection limit down to nanomolar. Moreover, this probe can also make a distinction between gram-positive bacteria Staphylococcus aureus (S. aureus) and gram-negative bacteria Escherichia coli (E. coli), making it a promising sensor for clinical monitoring of urinary tract infections.

The fluorescence detection of nitroreductase (NTR) and evaluation of the hypoxia status of tumor cells are vital, not only for clinical diagnoses and therapy, but also for biomedical research. Herein, we report the synthesis and application of a new fluorometric "turn-on" probe for the detection of NTR (TPE-NO2 ) that takes advantage of the aggregation-induced emission of tetraphenylethylene. TPE-NO2 can detect NTR at concentrations as low as 5 ng mL-1 in aqueous solution. The detection mechanism relied on the aggregation and deaggregation of tetraphenylethylene molecules. Moreover, this fluorescent probe can be used to monitor the hypoxia status of tumor cells through the detection of endogenous NTR.

We present four conjugated donor–acceptor (D–A) polymers PBPDT-Si, PBPDSe-Si, PBPDT, and PBPDSe entailing a new electron acceptor Pechmann dye framework, i.e., bipyrrolylidene-2,2′(1H,1′H)-dione (BPD), and thiophene and selenophene as the respective electron donors. PBPDT-Si and PBPDSe-Si contain siloxane-terminated side chains, while PBPDT and PBPDSe bear branching alkyl chains. The respective HOMO energies of PBPDT-Si and PBPDSe-Si are slightly higher than those of PBPDT and PBPDSe, whereas the respective LUMO energies of PBPDT-Si and PBPDSe-Si are slightly lower than those of PBPDT and PBPDSe. The results reveal that (i) thin films of all four polymers show ambipolar semiconducting performances under a nitrogen atmosphere, (ii) hole and electron mobilities are more balanced for PBPDT-Si and PBPDSe-Si, and (iii) the employment of siloxane-terminated side chains is beneficial for improving charge transporting compared to branching alkyl side chains. Thin film hole and electron mobilities of PBPDT-Si can ...

Solid state emissive materials with high quantum yields and tunable emissions are desirable for various applications. A new TPE derivative (1) with two carbazole moieties and two cyano groups is reported, which shows typical aggregation induced emission behavior. Four crystals 1a, 1b, 1c, and 1d are obtained after crystallization from N,N-dimethylformamid (DMF), trichloromethane (CHCl3 ), tetrahydrofuran (THF), and dichloromethane (CH2 Cl2 ), respectively. Crystal structural analyses reveal that (i) molecules of 1 co-crystallize with DMF, CHCl3 , THF, and CH2 Cl2 in 1a, 1b, 1c, and 1d, respectively, and (ii) conformations of 1 are different within 1a, 1b, 1c, and 1d, and compound 1 within crystal 1a adopts the most twisting conformation. Crystalline solids 1a, 1b, 1c, and 1d exhibit high emission quantum yields up to 0.65, but their emission colors are varied from blue to green. In comparison, the amorphous solid of 1 is yellow-emissive with emission maximum at 542 nm. Moreover, the blue- or green-emissive crystalline solids and the yellow-emissive amorphous solid can be inter-converted by the grinding of crystalline solids and exposure of the amorphous solid to vapors of appropriate solvents. It is also demonstrated that microrods of 1a, 1b, and 1d show typical optical waveguiding behavior.

The adsorption of polymer on colloidal particle has significant influence on colloid structure and dynamics. Here we introduce a new method to monitor the adsorption in situ, based on the different emission behavior of aggregation-induced emission (AIE) luminogen in different micro environments. Poly(vinyl alcohol) (PVA) and colloidal silica (CS) were used as a model system. It was found that AIE molecules exhibited extremely low fluorescence intensity in water and PVA solution, while their emission efficiency was enhanced when adsorbed on CS, and became significantly boosted when PVA was adsorbed on CS at the same time. The fluorescence intensity increases with the amount of added PVA and reaches a saturation point, which is earlier than that obtained by the well-established solvent relaxation NMR method, due to their different sensitivities for adsorption segments in specific conformation. This new method is advantageous in quick response, where the measurement can be finished within 2 min, while others usually take hours. Therefore, it is expected that this new method may be used to monitor the dynamical adsorption process of polymer on colloidal particles.

An AIE based tetraphenylethylene derivative (MOTIPS-TPE) with a pyridinium pendant was synthesized for light-up sensing of F− in aqueous solution without additives. The fluoride ion promoted cleavage reaction gave MOTIPS-TPE high selectivity toward F− over other common anions. Moreover, MOTIPS-TPE can be used to monitor F− in living HeLa cells.

Three conjugated D–A terpolymers PBPD1, PBPD2, and PBPD3 with the Pechmann dye-derived electron acceptor and dithienyl-diketopyrrolopyrrole as co-acceptors are presented. Their HOMO/LUMO energies and absorptions can be tuned by varying the ratios of two acceptors. Importantly, HOMO energies of these terpolymers are lowered by increasing the content of the Pechmann dye-derived electron acceptor in the conjugated backbones. The thin blend films of PBPD1, PBPD2, and PBPD3 with PC71BM have been tested as active layers for polymer solar cells. The blend of PBPD1:PC71BM shows a high power conversion efficiency of up to 5.21%, which is higher than that with the blend of the dithienyl-diketopyrrolopyrrole-based polymer without the Pechmann dye-derived electron acceptor and PC71BM. In addition, the neat thin films of PBPD1, PBPD2, and PBPD3 exhibit ambipolar semiconducting properties with hole and electron mobilities up to 0.604 cm2 V−1 s−1 and 0.225 cm2 V−1 s−1.

In order to demonstrate the influence of structural fine-tuning on bandgap and semiconductor performance of π-conjugated polymer materials, three new diketopyrrolopyrrole (DPP) based copolymers P1, P2 and P3 with monomers, i.e., 2-phenylpyridine, 2-(thiophen-2-yl)pyridine and 2-(thiophen-2-yl)thiazole, respectively, have been synthesized using a typical Suzuki cross-coupling polycondensation. The DFT calculations demonstrate that polymer P3 displays high backbone coplanarity in comparison to polymers P1 and P2. Absorption spectra results reveal that P3 exhibits a remarkable red-shifted absorption profile, narrow band gap and broad absorption. The thin film FET measurements show that P3 possesses the highest hole mobility (μh) up to 1.25 cm2 V−1 s−1 and on/off (Ion/off) ratio as high as 108. Those results demonstrate that the fine-tuning of the π-conjugated backbone can significantly affect the band gaps and coplanarities, and ultimately improve the semiconducting performances.

In this paper we report two n-type polymeric acceptors P1 and P2 based on imide/amide-derivatives (PDI, NDI and DPP). P1 and P2 exhibit very different optical properties which may be related to the different molecular configuration and polymeric crystallinity. All polymer solar cells were fabricated with conventional configuration based on polymeric donor PBDTTT-C-T and P1/P2. Results reveal that devices based on P1 show the best performance with a PCE of 2.01%, a V-OC of 0.68 V, a J(SC) of 7.06 mA cm 2 and a FF of 41.78%, which is attributed to the appropriate energy levels, relatively high electron mobility and preferable micro-phase separation. The poor performance for P2 ( PCE = 0.30%) was mainly ascribed to its extremely low J(SC) which was probably caused by the small HOMO energy level difference between donor and P2.

Chemotherapeutics specifically targeting cancer cells without damaging healthy cells is the long-awaited goal of cancer treatment. In this paper, a series of nanoparticles (NanoTPES 1–4) assembled from pyridinium-substituted tetraphenylethylene salts were synthesized and investigated both in vitro and in vivo for this purpose. By changing the counter anions, NanoTPES 1–4 exhibit tunable emission colors, sizes and surface charges. NanoTPES 2 and 3 with tetraphenyl borate and tetra(4-chlorophenyl) borate as the respective anions selectively imaged and targeted mitochondria in cancer cells. Accordingly, these two nanoparticles specifically kill cancer cells with minimal effect on normal cells. Such selective cytotoxicity was attributed to the change of membrane potential and inhibition of ATP synthesis in the mitochondria of cancer cells. Furthermore, both NanoTPES 2 and 3 exhibited efficient tumor accumulation and tumor growth inhibition in vivo, with negligible systemic toxicity.

Three new conjugated D–A terpolymers PADPP1, PADPP2 and PADPP3, which contain diketopyrrolopyrrole (DPP) as electron acceptors and thiophene/anthracene as electron donors, are described. In comparison with PDPP3T which contains just DPP and thiophene units, the DPP moieties are partially replaced with anthracene units in PADPP1, PADPP2 and PADPP3. The HOMO/LUMO levels of PADPP1, PADPP2 and PADPP3 are slightly enhanced in comparison with those of PDPP3T. Moreover, the incorporation of the anthracene units into the backbones leads to the formation of nanofibrils with an appropriate width within the blending thin films of PADPP2 with PC71BM. The short circuit currents (JSC) of the photovoltaic cells with blends of PADPP1, PADPP2 and PADPP3 with PC71BM are higher than those with the PDPP3T/PC71BM blend. As a result, PADPP1, PADPP2 and PADPP3 display better photovoltaic performances than PDPP3T after blending each polymer with PC71BM under the same conditions. The PCE of the photovoltaic cell of the PADPP2/PC71BM blending thin film at a weight ratio of 1 : 2 as the active layer can reach 6.24%.