Highly Conductive and Solution-Processable n-Doped Transparent Organic Conductor.

Transparent conductors (TCs) play a vital role in displays, solar cells, and emerging printed electronics. Here, we report a solution-processable n-doped organic conductor from copper-catalyzed cascade reactions in the air, which involves oxidative polymerization and reductive doping in one pot. The formed polymer ink is shelf-stable over 20 days and can endure storage temperatures from -20 to 65 °C. The optimized n-doped thin-film TC exhibits a low sheet resistance of 45 Ω/sq and a high transmittance (T550 > 80%), which can rival indium tin oxide. The transparent organic conductor exhibits excellent durability under accelerated weathering tests (85 °C/85% RH). Furthermore, the n-doped polymer film can also function as an electrode material with a high volumetric capacity. When it is paired with p-doped PEDOT:PSS, a record-high coloration efficiency is obtained in a dual-polymer electrochromic device.

Bioinspired Dynamic Camouflage from Colloidal Nanocrystals Embedded Electrochromics.

Camouflage is often seen in animals, and it presents in both passive and active forms. For instance, the wings of Closterocerus coffeellae exhibit distinct appearances against different backgrounds, while the chameleon actively changes its skin colors to morph into the environment. Herein, we report an artificial skin-like optoelectronic device that enables actively changing appearances and passively morphing into the environment by manipulating light-matter interactions with electrochromic polymers and photonic colloid nanocrystals. To construct the new electrochromic device, highly reflective, yet transmissive photonic nanocrystals are introduced into the gel electrolyte and sandwiched between the layers of electrochromic polymers and ion storage materials. Through voltage-controlled color switching of electrochromic polymers from colored state to bleached state, the degree of light absorbance, transmittance, and reflectance can be finely balanced and precisely modulated with the device. A broad synthesized color gamut and angle-dependent visual effects can be realized on this electronic skin-like device.

Ambient Oxygen-Doped Conjugated Polymer for pH-Activatable Aggregation-Enhanced Photoacoustic Imaging in the Second Near-Infrared Window.

Photoacoustic (PA) probes absorbing in the second near-infrared (NIR-II: 1000-1700 nm) window hold great promise for deep-tissue diagnosis and treatment. Currently, NIR-II PA probes typically involve complex synthesis and surfactant adjuvant for processing and delivery. Furthermore, these NIR-II PA probes are "always-on," leading to inadequate signal-to-background ratio and low specificity. To address these challenges, this study reports a pH-activatable and aggregation-enhanced NIR-II PA probe. Without using any toxic or exotic oxidants, the selected polymer (PPE) is readily doped by oxygen in an ambient environment and simultaneously red-shifts its absorption profile from visible to NIR-II region. By virtue of the carboxyl groups on the side chains, oxygen-doped PPE is readily water-soluble at a physiological pH but tends to aggregate in an acidic environment. The pH-induced aggregation results in a significant PA enhancement and thus allows specific PA imaging of acidic tumor microenvironment in vivo. Our study provides a facile and surfactant-free strategy for achieving water-soluble and pH-responsive NIR-II PA probes, which could be applied for diagnoses of cancer and other diseases associated with changes in pH. It paves the way for the development of new activatable NIR-II imaging probes and also could facilitate the investigation of biological and pathological processes in deep tissue.

Integrated analysis of potential pathways by which aloe-emodin induces the apoptosis of colon cancer cells.

BACKGROUND: Colon cancer is a malignant gastrointestinal tumour with high incidence, mortality and metastasis rates worldwide. Aloe-emodin is a monomer compound derived from hydroxyanthraquinone. Aloe-emodin produces a wide range of antitumour effects and is produced by rhubarb, aloe and other herbs. However, the mechanism by which aloe-emodin influences colon cancer is still unclear. We hope these findings will lead to the development of a new therapeutic strategy for the treatment of colon cancer in the clinic. METHODS: We identified the overlapping targets of aloe-emodin and colon cancer and performed protein-protein interaction (PPI), Gene Ontology (GO), and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analyses. In addition, we selected apoptosis pathways for experimental verification with cell viability, cell proliferation, caspase-3 activity, DAPI staining, cell cycle and western blotting analyses to evaluate the apoptotic effect of aloe-emodin on colon cancer cells. RESULTS: The MTT assay and cell colony formation assay showed that aloe-emodin inhibited cell proliferation. DAPI staining confirmed that aloe-emodin induced apoptosis. Aloe-emodin upregulated the protein level of Bax and decreased the expression of Bcl-2, which activates caspase-3 and caspase-9. Furthermore, the protein expression level of cytochrome C increased in a time-dependent manner in the cytoplasm but decreased in a time-dependent manner in the mitochondria. CONCLUSION: These results indicate that aloe-emodin may induce the apoptosis of human colon cancer cells through mitochondria-related pathways.

Polymer Electrochromism Driven by Metabolic Activity Facilitates Rapid and Facile Bacterial Detection and Susceptibility Evaluation.

The electrochromism of a water-soluble naturally oxidized electrochromic polymer, ox-PPE, is harnessed for rapid and facile bacterial detection, discrimination, and susceptibility testing. The ox-PPE solution shows distinct colorimetric and spectroscopic changes within 30 min when mixed with live bacteria. For the underlying mechanism, it is found that ox-PPE responds to the reducing species (e.g. cysteine and glutathione) released by metabolically active bacteria. This reduction reaction is ubiquitous among various bacterial strains, with a noticeable difference that enables discrimination of Gram-negative and Gram-positive bacterial strains. Combining ox-PPE with antibiotics, methicillin-susceptible and -resistant S. aureus can be differentiated within 2.5 h. Proof-of-concept demonstration of ox-PPE for antimicrobial susceptibility testing is carried out by incubating E. coli with various antibiotics. The obtained minimum inhibition concentrations are consistent with the conventional culture-based methods, but with the procedure time significantly shortened to 3 h.

Functionalized NIR-II Semiconducting Polymer Nanoparticles for Single-cell to Whole-Organ Imaging of PSMA-Positive Prostate Cancer.

Development of molecular probes holds great promise for early diagnosis of aggressive prostate cancer. Here, 2-[3-(1,3-dicarboxypropyl) ureido] pentanedioic acid (DUPA)-conjugated ligand and bis-isoindigo-based polymer (BTII) are synthesized to formulate semiconducting polymer nanoparticles (BTII-DUPA SPN) as a prostate-specific membrane antigen (PSMA)-targeted probe for prostate cancer imaging in the NIR-II window. Insights into the interaction of the imaging probes with the biological targets from single cell to whole organ are obtained by transient absorption (TA) microscopy and photoacoustic (PA) tomography. At single-cell level, TA microscopy reveals the targeting efficiency, kinetics, and specificity of BTII-DUPA SPN to PSMA-positive prostate cancer. At organ level, PA tomographic imaging of BTII-DUPA SPN in the NIR-II window demonstrates superior imaging depth and contrast. By intravenous administration, BTII-DUPA SPN demonstrates selective accumulation and retention in the PSMA-positive tumor, allowing noninvasive PA detection of PSMA overexpressing prostate tumors in vivo. The distribution of nanoparticles inside the tumor tissue is further analyzed through TA microscopy. These results collectively demonstrate BTII-DUPA SPN as a promising probe for prostate cancer diagnosis by PA tomography.

Chiroptical Switching of Electrochromic Polymer Thin Films.

The interaction between light and chiroptical polymers plays a crucial role in chiroptics, spintronics, and chiral-spin selectivity. Despite considerable successes in creating dissymmetric polymer films, the elucidation of chiroptical activities under electrochemical switching remains unexplored. Here homogeneous chiral electrochromics is reported using chiral assembly of conjugated polymers through a transient solidification process with molecular chiral templates. In their neutral state, the chiral electrochromic polymers directly produce a remarkably dissymmetric polarization-dependent transmittance. The circular dichroism (CD) and dissymmetric transmission can be tuned by adjusting the doping level of the electrochemically active polymer films. Under high levels of oxidation, the chiroptical activities are reversed with strong bleaching in the visible, leading to formation of monosignate CD spectra over the infrared region. The matching between circular polarization handedness and chirality of chiroptical polymers makes a distinct impact on optical contrast and color switching dynamics due to the flipped chiroptical activities through polymer redox reactions. The differential circularly polarized transmission in the chiral see-through display can make a well-resolved color change in human eyes, demonstrating proof-of-concept devices for 3D imaging and information encryption. This work serves as a foundation to develop advanced on-chip fabrication of circular polarization-multiplexed display in flexible and highly integrated platforms.

Transparent Electrochromic Polymers with High Optical Contrast and Contrast Ratio.

Colored-to-transmissive electrochromic polymers, known for their wide selection of colors and solution processability, have gained great attraction in thin film electrochromic devices that have entered the market. However, their adoption in the real world is limited due to their limited optical transparency and contrast. This study introduces a new molecular design strategy to overcome these issues. This strategy involves using meta-conjugated linkers (MCLs) and aromatic moieties along polymer backbones, which enable transparent-to-colored electrochromic switching. The MCL interrupts charge delocalization, increasing the band gap in the neutral state and ensuring transparency in the visible region. This innovative approach achieves nearly 100% transmittance in the neutral state and a high absorption in the oxidized state, overcoming residue absorption issues in conventional electrochromic polymers. Simultaneously, the MCL and aromatic moieties enable low oxidation potential, facilitating stable transparent-to-color switching. Polymers developed using this approach exhibit wide color tunability, optical contrast exceeding 93%, and cycling stability over 5000 cycles with less than 3% contrast decay. Our research represents a major advancement in overcoming existing challenges, enabling polymer-based electrochromic devices for visual comfort and energy conservation.

Mechanism of action of the Banxia-Xiakucao herb pair in sleep deprivation: New comprehensive evidence from network pharmacology, transcriptomics and molecular biology experiments.

ETHNOPHARMACOLOGICAL RELEVANCE: Chinese herb pairs are the most basic and compressed examples of Chinese herbal combinations and can be used to effectively explain the fundamental concepts of traditional Chinese medicine prescriptions. These pairings have gained significant interest due to their subtle therapeutic benefits, minimal side effects, and efficacy in treating complicated chronic conditions. The Banxia-Xiakucao Chinese herb pair (BXHP) consists of Pinellia ternata (Thunb.) Breit. (Banxia) and Prunella vulgaris L. (Xiakucao). This formula was documented in The Medical Classic of the Yellow Emperor approximately 2000 years ago，and clinical research has demonstrated that BXHP effectively treats insomnia. AIM OF THE STUDY: This study aimed to evaluate the efficacy and therapeutic mechanism of the BXHP through a comprehensive strategy involving network pharmacology, molecular docking, transcriptomics, and molecular biology experimental validation. MATERIALS AND METHODS: The composition of BXHP was characterized using the UPLC-Q-TOF-MS. The active compounds were screened to find drug-likeness compounds by analyzing the ADME data. To predict the molecular mechanism of BXHP in sleep deprivation (SD) by network pharmacology and molecular docking. We established a rat model of SD and the in vivo efficacy of BXHP was verified through the pentobarbital sodium righting reflex test, behavioral assays, enzyme-linked immunosorbent assay, transmission electron microscopy, HE staining, and Nissl staining, and the underlying molecular mechanism of BXHP in SD was revealed through transcriptomic and bioinformatic analyses in conjunction with quantitative real-time PCR, Western blot, and immunofluorescence staining. RESULTS: In the present study, we showed for the first time that BXHP reduced sleep latency, prolongs sleep duration, and improves anxiety; lowered serum CORT, IL6, TNF-α and MDA levels; decreased hypothalamic Glu levels; and elevated hypothalamic GABA and 5-HT levels in SD rats. We found 16 active compounds that acted on 583 targets, 145 of which are related to SD. By modularly dissecting the PPI network, we discovered three critical targets, Akt1, CREB1, and PRKACA, all of which play important roles in the effects of BXHP on SD. Molecular docking resulted in the identification of 16 active compounds that strongly bind to key targets. The results of GO and KEGG enrichment analyses of network pharmacology and transcriptomics focused on both the regulation of circadian rhythm and the cAMP signaling pathway, which strongly demonstrated that BXHP affects SD via the cAMP-PKA-CREB-Circadian rhythm pathway. Molecular biology experiments verified this hypothesis. Following BXHP administration, PKA and CREB phosphorylation levels were elevated in SD rats, the cAMP-PKA-CREB signaling pathway was activated, the expression levels of the biological clock genes CLOCK, p-BMAL1/BMAL1, and PER3 were increased, and the rhythmicity of the biological clock was improved. CONCLUSIONS: The active compounds in BXHP can activate the cAMP-PKA-CREB-Circadian rhythm pathway, improve the rhythmicity of the biological clock, promote sleep and ameliorate anxiety, which suggests that BXHP improves SD through a multicomponent, multitarget, multipathway mechanism. This study is important for the development of herbal medicines and clinical therapies for improving sleep deprivation.

Synthesis and Reduction of Nitrogen-Substituted Diaryl Dihydrophenazine Diradical Dications.

A one-pot synthetic approach to form core-extended N,N'-disubstituted diaryl dihydrophenazine (DADHP) diradical dications (DRDCs) via chemical oxidation from aryl-substituted ortho-phenyldiamines is reported. The isolated N,N'-disubstituted DADHP DRDCs were reduced to their neutral counterparts with hydrazine. The model system featuring an unsubstituted fluorene aryl group, 2a, was tested as a photocatalyst for the polymerization of methyl methacrylate using organocatalyzed atom transfer polymerization (O-ATRP), which yielded a polymer with a controlled molecular weight and narrow polydispersity.

Printing dynamic color palettes and layered textures through modeling-guided stacking of electrochromic polymers.

In printable electrochromic polymer (ECP) displays, a wide color gamut, precise patterning, and controllable color switching are important. However, it is a significant challenge to achieve such features synergistically. Here, we present a solution-processable ECP stacking scheme, where a crosslinker is co-processed with three primary ECPs (ECP-Cyan, ECP-Magenta, and ECP-Yellow), which endows the primary ECPs with solvent-resistant properties and allows them to be sequentially deposited. Via varying the film thickness of each ECP layer, a full-color palette can be constructed. The ECP stacking strategy is further integrated with photolithography. Delicate multilayer patterns with overhang and undercut textures can be generated, allowing information displays with spatial dimensionality. In addition, via modulating the stacking sequence, the electrochemical onset potentials of the ECP components can be synchronized to reduce unwanted intermediate colors that are often found in co-processed ECPs. Should specific color properties be desired, COMSOL modeling could be applied to guide the stacking. We believe that this ECP stacking strategy opens a new avenue for electrochromic printing and displays.

Integrating pharmacological evaluation and computational identification for deciphering the action mechanism of Yunpi-Huoxue-Sanjie formula alleviates diabetic cardiomyopathy.

Background: Yunpi-Huoxue-Sanjie (YP-SJ) formula is a Chinese herbal formula with unique advantages for the treatment of diabetic cardiovascular complications, such as Diabetic cardiomyopathy (DCM). However, potential targets and molecular mechanisms remain unclear. Therefore, our research was designed to evaluate rat myocardial morphology, fat metabolism and oxidative stress to verify myocardial protective effect of YP-SJ formula in vivo. And then to explore and validate its probable mechanism through network pharmacology and experiments in vitro and in vivo. Methods: In this study, DCM rats were randomly divided into five groups: control group, model group, and three YP-SJ formula groups (low-dose, middle-dose, and high-dose groups). Experimental rats were treated with 6 g/kg/d, 12 g/kg/d and 24 g/kg/d YP-SJ formula by gavage for 10 weeks, respectively. Cardiac function of rats was measured by high-resolution small-animal imaging system. The cells were divided into control group, high glucose group, high glucose + control serum group, high glucose + dosed serum group, high glucose + NC-siRNA group, high glucose + siRNA-FoxO1 group. The extent of autophagy was measured by flow cytometry, immunofluorescence, and western blotting. Results: It was found that YP-SJ formula could effectively improve cardiac systolic function in DCM rats. We identified 46 major candidate YP-SJ formula targets that are closely related to the progression of DCM. Enrichment analysis revealed key targets of YP-SJ formula related to environmental information processing, organic systems, and the metabolic occurrence of reactive oxygen species. Meanwhile, we verified that YP-SJ formula can increase the expression of forkhead box protein O1 (FoxO1), autophagy-related protein 7 (Atg7), Beclin 1, and light chain 3 (LC3), and decrease the expression of phosphorylated FoxO1 in vitro and in vivo. The results showed that YP-SJ formula could activate the FoxO1 signaling pathway associated with DCM rats. Further experiments showed that YP-SJ formula could improve cardiac function by regulating autophagy. Conclusion: YP-SJ formula treats DCM by modulating targets that play a key role in autophagy, improving myocardial function through a multi-component, multi-level, multi-target, multi-pathway, and multi-mechanism approach.

Stabilizing Hybrid Electrochromic Devices through Pairing Electrochromic Polymers with Minimally Color-Changing Ion-Storage Materials Having Closely Matched Electroactive Voltage Windows.

Conjugated electrochromic polymers hold great promises for next-generation color-changing windows and displays. One of the major roadblocks in their solid-state electrochromic devices is the relatively poor cycling stability. Finding ion-storage materials as a charge-balancing component is critical in improving their electrochemical cycling stability. A key criterion for the selection of ion-storage materials is to match their electroactive voltage windows with the paired electrochromic polymers. Thus, we developed a nanostructured, amorphous vanadium oxide (VOx) ion-storage material that exhibits high transmissivity, minimal color interference, and excellent charge-balancing capability in a closely matched electroactive window with the paired electrochromic polymers. High-performance magenta-to-transmissive hybrid electrochromic devices constructed from pairing the polymer with the VOx can be reversibly switched for 50 000 cycles with an optical loss less than 5%.

Low-Temperature Thermally Annealed Niobium Oxide Thin Films as a Minimally Color Changing Ion Storage Layer in Solution-Processed Polymer Electrochromic Devices.

The limited availability of solution-processable ion storage materials, both inorganic and organic, hinders the adoption of roll-to-roll manufacturing for polymer electrochromic devices (ECDs). The n-type transition metal oxides are known for their ion storage properties. However, the fabrication methods of their amorphous metal oxide thin films typically involve sputtering, thermal deposition, electrical deposition, or sol-gel deposition followed by high-temperature thermal annealing (>300 °C), thus making them incompatible for low-cost roll-to-roll manufacturing on flexible substrates. In this study, we report the synthesis of amorphous niobium oxide(a-Nb2O5) thin films from sol-gel precursors through the combination of photoactivation and low-temperature thermal annealing (150 °C). Coupled with p-type electrochromic polymers (ECPs), solution-processed a-Nb2O5 thin films were evaluated as a minimally color changing counter electrode (MCC-CE) material for electrochromic devices. We found that ultraviolet ozone (UVO) treated and 150 °C thermally annealed (UVO-150 °C) a-Nb2O5 thin films show excellent electrochemical properties and cycling stability. Notably, a-Nb2O5/ECP-magenta ECD has a high optical contrast of ∼70% and a fast switching time (bleaching and coloring time of 1.6 and 0.5 s for reaching 95% of optical contrast). In addition, the ECD demonstrates a high coloration efficiency of ∼849.5 mC cm-2 and a long cycling stability without a noticeable decay up to 3000 cycles.

The complex influence of the oscillatory shear on the melt of linear diblock copolymers.

The phase morphologies of symmetric linear diblock copolymers subjected to the oscillatory shear are investigated with the aid of dissipative particle dynamics simulations. The frequency dependent reorientations of the lamellar phase (LAM) have been identified. We find that the parallel orientation of LAM (i.e., the lamellar normal is parallel to the velocity gradient) appears at high shear frequency, whereas the perpendicular orientation of LAM (the lamellar normal being perpendicular to the velocity gradient) takes place at low shear frequency. In both of the cases, the reorientations undergo similar processes: the original LAM phase prepared in equilibrium breaks down rapidly, and it takes a very long time for the perfectly oriented LAM being reformed. Moreover, the shear-induced isotropic to lamellar phase transitions are observed when the oscillatory shear amplitude is large enough. It indicates that the shear amplitude plays a dominant role in the order-disorder transition. The viscosity and the modulus of the melt are found to be dependent on the shear amplitude and the shear frequency in a complex way.

Highly Transparent Crosslinkable Radical Copolymer Thin Film as the Ion Storage Layer in Organic Electrochromic Devices.

A highly transparent crosslinkable thin film made of the radical polymer poly(2,2,6,6-tetramethyl-4-piperidinyloxy methacrylate)- co-(4-benzoylphenyl methacrylate) (PTMA- co-BP) has been developed as the ion storage layer in electrochromic devices (ECDs). After photo-crosslinking, the dissolution of PTMA- co-BP in electrolytes was mitigated, which results in an enhanced electrochemical stability compared with the homopolymer PTMA thin film. Moreover, the redox capacity of PTMA- co-BP increased because of the formation of a crosslinked network. By matching the redox capacity of the PTMA- co-BP thin film and bis(alkoxy)-substituted poly(propylenedioxythiophene), the ECD achieved an optical contrast of 72% in a small potential window of 2.55 V (i.e., switching between +1.2 and -1.35 V), and it was cycled up to 1800 cycles. The ECD showed an excellent optical memory as its transmittance decayed by less than 3% in both the colored and bleached states while operating for over 30 min under open-circuit conditions. Use of crosslinkable radical polymers as the transparent ion storage layer opens up a new venue for the fabrication of transmissive-mode organic ECDs.

Self-Bleaching Behaviors in Black-to-Transmissive Electrochromic Polymer Thin Films.

Polymer-based electrochromic smart windows are an emerging energy-saving technology. There are several technological hurdles in the development of organic electrochromics. In this article, the self-bleaching behaviors of a black electrochromic polymer (ECP-black) thin film were investigated. We found that the electrochemical break-in process led to a less dense morphology and the increased free volume facilitated ion permeation in the ECP-black thin films. The polarized interface between the polymer thin film and transparent indium-tin-oxide (ITO) electrode made charge transfer accessible, which caused the self-bleaching behaviors. Herein, we proposed two approaches to study and mitigate the self-bleaching phenomenon. First, a densely packed morphology was regenerated by increasing the cathodic polarization time under open-circuit conditions (Voff). The second involved the modification of the electrode (ITO) surface with a partial coverage of the octadecyltrichlorosilane layer. The combination of the two approaches rendered the ECP-black thin film capable of maintaining the colored state for up to 900 s. To extend the scope of our studies, self-bleaching of ECP-magenta and ECP-blue thin films were also tested and suppressed by using these two methods. Additionally, the cycling stability of the ECP-black has been improved from ∼600 cycles to up to 2300 cycles without a noticeable decay of optical contrast.

Semiconducting Polymer Nanoparticles for Centimeters-Deep Photoacoustic Imaging in the Second Near-Infrared Window.

Thienoisoindigo-based semiconducting polymer with a strong near-infrared absorbance is synthesized and its water-dispersed nanoparticles (TSPNs) are investigated as a contrast agent for photoacoustic (PA) imaging in the second near-infrared (NIR-II) window (1000-1350 nm). The TSPNs generate a strong PA signal in the NIR-II optical window, where background signals from endogenous contrast agents, including blood and lipid, are at the local minima. By embedding a TSPN-containing tube in chicken-breast tissue, an imaging depth of more than 5 cm at 1064 nm excitation is achieved with a contrast-agent concentration as low as 40 µg mL-1 . The TSPNs under the skin or in the tumor are clearly visualized at 1100 and 1300 nm, with negligible interference from the tissue background. TSPN as a PA contrast in the NIR-II window opens new opportunities for biomedical imaging of deep tissues with improved contrast.