NIR light-driven pure organic Janus-like nanoparticles for thermophoresis-enhanced photothermal therapy.

Photothermal therapy (PTT) represents a promising noninvasive tumor therapeutic modality, but the current strategies for enhancing photothermal effect have been mainly based on promoting thermal relaxation or suppressing radiative dissipation process of excited energy, leaving little room for further improvement in photothermal effect. Herein, as a proof of concept, we report the thermophoresis-enhanced photothermal effect with pure organic Janus-like nanoparticles (Janus-like NPs) for PTT. The Janus-like NPs are eccentrically loaded with compactly J-aggregated photothermal molecules (DMA-BDTO), which show red-shifted absorption wavelength and inhibited radiative decay as compared to individual molecules. Under NIR irradiation, the asymmetric heat generation at particle surface endows Janus-like NPs the active thermophoresis, which further increases collisions and converts kinetic energy into thermal energy, and Janus-like NPs exhibit significantly elevated temperature as compared to conventional NPs with homogenously distributed DMA-BDTO. Both in vitro and in vivo results confirm such thermophoresis-enhanced photothermal effect for improved PTT. Our new strategy of thermophoresis-enhanced photothermal effect shall open new insights for improving photothermal-related tumor therapy.

Thermal oxidation of degradation products from thermoplastic polyvinyl alcohol: Determination on oxidation temperature and residence time.

The degradable protective articles made of thermoplastic polyvinyl alcohol (TPVA) are widely used in nuclear power plants, and they are thermally decomposed after use to reduce solid waste. However, in the real decomposition of TPVA, the temperature in the oxidation reactor is not self-sustaining; as a result, the degradation products contain a lot of CO, resulting in more pollution and energy waste. In this paper, jet stirred reactor (JSR) and Chemkin software were used to study the reaction kinetics characteristics of the oxidation process of degradation products from TPVA in the range of 550 °C-700 °C. Both experiments and kinetic simulation show that a higher average temperature of the oxidation reactor is needed to achieve lower CO emissions. When using 5% or 10% TPVA degradation solution, the average temperature should not befall below 625 °C or 675 °C. The corresponding residence time should be greater than 6 s and 5 s respectively. The combination of research findings and engineering practice provides great help to the optimization of the actual work process.

Synthesis of Uniform Polymer Encapsulated Organic Nanocrystals through Ouzo Nanocrystallization.

Nanocrystals (NCs) are widely used in optoelectronics, photocatalysis, and bioimaging. As the surface area to volume ratio increases with a decrease in the size of NCs, strategies to control the size of NCs are highly valuable for many applications. Given the importance of photoluminescent dyes, especially those with aggregation-induced emission, the transformation from an amorphous to a crystalline state can yield a drastic enhancement in their optical properties, which is of significance for biomedical applications. Till now, there is no general method available for the synthesis of small NCs with accurate control over the size and uniformity. Herein, a simple and general approach of ouzo nanocrystallization is presented for the synthesis of small (<100 nm) and highly uniform (polydispersity index~0.1) NCs with good control over the size. The process of nanoprecipitation is used to synthesize uniform nanoparticles (NPs) with different size, which is followed by solvent addition to form swollen NPs. Further, the amorphous core of swollen NPs is converted into NCs within polymer shell under Ouzo zone, which restricts NCs to grow above certain size. To demonstrate the general applicability of ouzo nanocrystallization, two different classes of luminescent materials are used as examples to fabricate small and highly uniform NCs.

"Internal and External Combined" Nonradiative Decay-Based Nanoagents for Photoacoustic Image-Guided Highly Efficient Photothermal Therapy.

Rational manipulation of nonradiative decay channels is of crucial significance to improve photothermal conversion efficiency (PCE) and design photothermal agents. We first used the "internal and external combined" nonradiative decay strategy to enhance PCE. Specifically, organic IR-Y6 NPs with strong NIR absorption and high molar extinction coefficient were prepared and characterized. By means of TD-DFT calculations and fs-TA spectroscopy, the dual nonradiative decay channels composed of the free rotor (external strategy) and ultrafast dark excited states (DESs) between S0 and S1 states (internal strategy) were proved, which significantly enhanced PCE, up to 66%. IR-Y6 NPs were applied to a mice tumor model for photoacoustic image-guided photothermal therapy, showing complete tumor ablation ability and good biocompatibility for the normal organs. This work is of significance to deeply understand the nonradiation decay mechanism and rational design of high-performance PTT agents.

Mechanical single-molecule potentiometers with large switching factors from ortho-pentaphenylene foldamers.

Molecular potentiometers that can indicate displacement-conductance relationship, and predict and control molecular conductance are of significant importance but rarely developed. Herein, single-molecule potentiometers are designed based on ortho-pentaphenylene. The ortho-pentaphenylene derivatives with anchoring groups adopt multiple folded conformers and undergo conformational interconversion in solutions. Solvent-sensitive multiple conductance originating from different conformers is recorded by scanning tunneling microscopy break junction technique. These pseudo-elastic folded molecules can be stretched and compressed by mechanical force along with a variable conductance by up to two orders of magnitude, providing an impressively higher switching factor (114) than the reported values (ca. 1~25). The multichannel conductance governed by through-space and through-bond conducting pathways is rationalized as the charge transport mechanism for the folded ortho-pentaphenylene derivatives. These findings shed light on exploring robust single-molecule potentiometers based on helical structures, and are conducive to fundamental understanding of charge transport in higher-order helical molecules.

Gram-Scale Synthesis of 41% Efficient Single-Component White-Light-Emissive Carbonized Polymer Dots with Hybrid Fluorescence/Phosphorescence for White Light-Emitting Diodes.

Fluorescent carbon dots (CDs) are compelling optical emitters to construct white light-emitting diodes (WLEDs). However, it remains a challenge to achieve large-scale and highly efficient single-component white-light-emissive CDs suitable for WLED applications. Herein, a low cost, fast processable, environmentally friendly, and one-step synthetic approach is developed for the preparation of gram-scale and highly efficient single-component white-light-emissive carbonized polymer dots (SW-CPDs). It is revealed that hybrid fluorescence/phosphorescence components cooperatively contribute to the emergence of white light emission. The SW-CPDs exhibit a record quantum yield (QY) of ≈41% for the white light emission observed in solid-state CD systems, while the QY of the phosphorescence is ≈23% under ambient conditions. Heavy doping of N and P elements as well as presence of covalently cross-linked polymer frameworks is suggested to account for the emergence of hybrid fluorescence/phosphorescence, which is supported by the experimental results and theoretical calculations. A WLED is fabricated by applying the SW-CPDs on an UV-LED chip, showing favorable white-light-emitting characteristics with a high luminous efficacy of 18.7 lm W-1 that is comparable to that of state-of-the-art WLEDs reported before.

Nanococktail Based on AIEgens and Semiconducting Polymers: A Single Laser Excited Image-Guided Dual Photothermal Therapy.

Semiconducting polymers (SPs)-based dual photothermal therapy (PTT) obtained better therapeutic effect than single PTT due to its higher photothermal conversion efficiency. However, most dual PTT need to use two lasers for heat generation, which brings about inconvenience and limitation to the experimental operations. Herein, we report the development of "nanococktail" nanomaterials (DTPR) with 808 nm-activated image-guided dual photothermal properties for optimized cancer therapy. Methods: In this work, we co-encapsulated AIEgens (TPA-BDTO, T) and SPs (PDPPP, P) by using maleimide terminated amphiphilic polymer (DSPE-PEG2000-Mal, D), then further conjugated the targeting ligands (RGD, R) through "click" reaction. Finally, such dual PTT nanococktail (termed as DTPR) was constructed. Results: Once DTPR upon irradiation with 808 nm laser, near-infrared fluorescence from T could be partially converted into thermal energy through fluorescence resonance energy transfer (FRET) between T and P, coupling with the original heat energy generated by the photothermal agent P itself, thus resulting in image-guided dual PTT. The photothermal conversion efficiency of DTPR reached 60.3% (dual PTT), much higher as compared to its inherent photothermal effect of only 31.5% (single PTT), which was further proved by the more severe photothermal ablation in vitro and in vivo upon 808 nm laser irradiation. Conclusion: Such smart "nanococktail" nanomaterials could be recognized as a promising photothermal nanotheranostics for image-guided cancer treatment.

Drug delivery micelles with efficient near-infrared photosensitizer for combined image-guided photodynamic therapy and chemotherapy of drug-resistant cancer.

The combination of photodynamic therapy (PDT) and chemotherapy (CT) offers a promising approach for the tumor eradication for overcoming multidrug resistance (MDR), which is a major obstacle to effective cancer treatment. However, for PDT, simultaneously achieving near-infrared (NIR) emission and efficient reactive oxygen species (ROS) generation with low dark toxicity is urgently needed but remains challenging. Herein, a series of novel fluorophores with strong NIR emission, hybridized local and charge transfer characteristics, good two-photon absorption, high photostability, low dark cytotoxicity and excellent ROS generation ability are developed. By encapsulating the NIR fluorophore (DEB-BDTO) as a photosensitizer along with a drug resistance inhibitor tariquidar (TQR) within a polymeric prodrug (PMP), a reduction-sensitive drug co-delivery system (DEB/TQR@PMP micelles) is constructed. The DEB/TQR@PMP micelles exhibit a prominent synergistic lethal effect of PDT and CT on SKOV-3 cells and SKOV-3/MDR cells, and can apparently enhance the inhibition of tumor growth compared with sole PDT or CT in the tumor-bearing mouse model. Both in vitro and in vivo experiments prove that the new NIR fluorophores are excellent photosensitizers and can furnish an efficient combination therapy of image-guided PDT and CT within drug delivery micelles, which is particularly useful for eradicating multidrug resistance cancer.

New Aggregation-Induced Delayed Fluorescence Luminogens With Through-Space Charge Transfer for Efficient Non-doped OLEDs.

In this work, two tailor-made luminogens comprising of electron donors (acridine and phenoxazine) and acceptor (triazine) bridged by the through-space conjugated hexaphenylbenzene (HPB) are synthesized and characterized. Their thermal stability, electrochemical behaviors, crystal, and electronic structures, and photophysical properties are systematically investigated. The crystal and electronic structures reveal that the peripheral phenyls in HPB are closely aligned in a propeller-like fashion, rendering efficient through-space charge transfer between donor and electron moieties. These molecules display weak fluorescence with negligible delayed component in solutions but strong fluorescence with greatly increased delayed component upon aggregate formation, namely aggregation-induced delayed fluorescence (AIDF). Their neat films exhibit high photoluminescence quantum yields (PLQY), and prominent delayed fluorescence. The non-doped organic light-emitting diodes (OLEDs) based on these new luminogens exhibit excellent performance with maximum external quantum efficiency of 12.7% and very small efficiency roll-off of 2.7% at 1,000 cd m-2. Designing AIDF molecules with through-space charge transfer could be a promising strategy to explore robust luminescent materials for efficient non-doped OLEDs.

A high therapeutic efficacy of polymeric prodrug nano-assembly for a combination of photodynamic therapy and chemotherapy.

Combination of photodynamic therapy and chemotherapy has been emerging as a new strategy for cancer treatment. Conventional photosensitizer tends to aggregate in aqueous media, which causes fluorescence quenching, reduces reactive oxygen species (ROS) production, and limits its clinical application to photodynamic therapy. Traditional nanoparticle drug delivery system for chemotherapy also has its disadvantages, such as low drug loading content, drug leakage, and off-target toxicity for normal tissues. Here, we developed a reduction-sensitive co-delivery micelles TB@PMP for combinational therapy, which composed of entrapping a red aggregation-induced emission fluorogen (AIEgen) for photodynamic therapy and PMP that contains a reduction-sensitive paclitaxel polymeric prodrug for chemotherapy. AIEgen photosensitizer illustrates a much improved photostability and ROS production efficiency in aggregate state and PMP loads a high dose of paclitaxel and carries a smart stimuli-triggered drug release property. This co-delivery system provides a better option that replaces AIEgen photosensitizer for cancer diagnosis and therapy.

Remarkable Multichannel Conductance of Novel Single-Molecule Wires Built on Through-Space Conjugated Hexaphenylbenzene.

Through-bond conjugated molecules are the major frameworks for traditional molecular wires, while through-space conjugated units are rarely utilized and studied although they have shown unique conducting potential. Herein, we present novel single-molecule wires built on through-space conjugated hexaphenylbenzene. Their conductance, measured by the scanning tunneling microscopy based break-junction technique, increases with the improvement of through-space conjugation and finally reaches a remarkable value (12.28 nS) which greatly exceeds that of conventional through-bond conjugated counterpart (2.45 nS). The multichannel conducting model by integrating through-space and through-bond conjugations could be a promising strategy for the further design of robust single-molecule wires with advanced conductance and stability.

Thiadiazolo[3,4-c]pyridine as an Acceptor toward Fast-Switching Green Donor-Acceptor-Type Electrochromic Polymer with Low Bandgap.

Thiadiazolo[3,4-c]pyridine (PT), an important analog of benzothiadiazole (BT), has most recently been explored as a novel electron acceptor. It exhibits more electron-accepting ability and other unique properties and potential advantages over BT, thus inspiring us to investigate PT-based donor-acceptor-type (D-A) conjugated polymer in electrochromics. Herein, PT was employed for the rational design of novel donor-acceptor-type systems to yield a neutral green electrochromic polymer poly(4,7-di(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-[1,2,5] thiadiazolo[3,4-c]pyridine) (PEPTE). PEPTE revealed a lower bandgap (Eg,ele=0.85 eV, Eg,opt=1.12 eV) than its BT analog and also favorable redox activity and stability. Furthermore, electrochromic kinetic studies demonstrated that PEPTE displayed higher coloration efficiency than BT analog, good optical memory, and very fast switching time (0.3 s at all three wavelengths), indicating that PT would probably be a promising choice for developing novel neutral green electrochromic polymers by matching with various donor units.

Poly(thieno[3,4-b]-1,4-oxathiane): medium effect on electropolymerization and electrochromic performance.

The asymmetrical sulfur analog of 3,4-ethylenedioxythiophene (EDOT), thieno[3,4-b]-1,4-oxathiane (EOTT), was synthesized, and its electropolymerization was comparatively investigated by employing different solvent-electrolyte systems (room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF6), CH2Cl2-Bu4NPF6, and CH2Cl2-BmimPF6). Further, the effect of solvents and supporting electrolytes on the structure, morphology, electrochemical, electronic, and optical properties and electrochromic performance of the obtained poly(thieno[3,4-b]-1,4-oxathiane) (PEOTT) films were minutely studied. PEOTT film with a band gap (Eg) of about 1.6 eV could be facilely electrodeposited in all the solvent-electrolytes and displayed excellent electroactivity, outstanding redox stability in a wide potential window, and improved thermal stability. Cyclic voltammetry showed that EOTT could be electropolymerized at a lower oxidation potential in BmimPF6 (∼1.0 V vs Ag/AgCl) due to several advantanges of RTIL BmimPF6 itself, such as high intrinsic conductivity and mild chemical conditions, etc., and the resulting PEOTT film exhibited compact morphology with better electroactivity and stability and higher electrical conductivity. On the other hand, PEOTT films from all the sovent-electrolytes also showed the electrochromic nature by color changing from gray blue to green, and further kinetic studies revealed that PEOTT had decent contrast ratios (36%), higher coloration efficiencies (212 cm(2)/C in BmimPF6), low switching voltages, moderate response time (1.2 s), excellent stability, and color persistence. From these results, PEOTT provides more plentiful electrochromic colors and holds promise for display applications.