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.

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.

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.

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.

Co and postseismic fault slip models of the 2022 M_(W)6.7 Menyuan earthquake reveal conjugated faulting tectonics at the central section of the Lenglongling fault

The 2022 M_(W)6.7 Menyuan earthquake ruptured the western end of the Tianzhu seismic gap,providing an opportunity to study the regional seismogenic characteristics and seismic hazards.Here we use interferometric synthetic aperture radar(InSAR)and seismic data to study the mainshock rupture,early afterslip and the second largest aftershock of the 2022 Menyuan earthquake sequences.Our modeling results show that the mainshock ruptured the Lenglongling fault and the Tuolaishan fault with a maximum slip of~3 m.Rapid postseismic transient deformation occurred at the center of the Lenglongling fault.Our afterslip modeling reveals that the majority of afterslip occurred in the deeper part of the Lenglongling fault.A high-angle conjugated faulting event is found at the middle section of the Lenglongling fault.We use the stress inversion to investigate the possible triggering mechanism of the conjugated rupture event.The results indicate the maximum principal stress direction is in~222°,forming a~22°angle between the conjugated fault of second largest aftershock and the mainshock.The calculated normal stress changes indicate the region is within a pull-apart stress field,which favors such a conjugated rupturing event.Our study will help understand the rupture behavior of such kind of conjugated fault in other regions.

phytoestrogens/insoluble fibers and colonic estrogen receptor β: randomized, double-blind, placebo-controlled study

AIM:To assess the safety and effect of the supplementation of a patented blend of dietary phytoestrogens and insoluble fibers on estrogen receptor (ER)-β and biological parameters in sporadic colonic adenomas. METHODS:A randomized, double-blind placebo-controlled trial was performed. Patients scheduled to undergo surveillance colonoscopy for previous sporadic colonic adenomas were identified, and 60 eligible patients were randomized to placebo or active dietary intervention (ADI) twice a day, for 60 d before surveillance colonoscopy. ADI was a mixture of 175 mg milk thistle extract, 20 mg secoisolariciresinol and 750 mg oat fiber extract. ER-β and ER-α expression, apoptosis and proliferation (Ki-67 LI) were assessed in colon samples. RESULTS:No adverse event related to ADI was recorded. ADI administration showed a significant increases in ER-β protein (0.822 ± 0.08 vs 0.768 ± 0.10, P = 0.04) and a general trend to an increase in ER-β LI (39.222 ± 2.69vs 37.708 ± 5.31,P = 0.06), ER-β/ER-α LI ratio (6.564 ± 10.04 vs 2.437 ± 1.53, P = 0.06), terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling (35.592 ± 14.97 vs 31.541 ± 11.54, P = 0.07) and Ki-67 (53.923 ± 20.91 vs 44.833 ± 10.38, P = 0.07) approximating statistical significance. A significant increase of ER-β protein (0.805 ± 0.13 vs 0.773 ± 0.13,P = 0.04), mRNA (2.278 ± 1.19vs 1.105 ± 1.07, P < 0.02) and LI (47.533 ± 15.47 vs 34.875 ± 16.67,P < 0.05) and a decrease of ER-α protein (0.423 ± 0.06vs 0.532 ± 0.11,P < 0.02) as well as a trend to increase of ER-β/ER-α protein in ADI vs placebo group were observed in patients without polyps (1.734 ± 0.20 vs 1.571 ± 0.42, P = 0.07). CONCLUSION:The role of ER-β on the control of apoptosis, and its amenability to dietary intervention, are supported in our study.

Effect of Technetium-99 Conjugated with Methylene Diphosphonate on IgM-RF,IgG-RF and IgA-RF

To explore the effect of technetium-99 conjugated with methylene diphosphonate ( 99 Tc-MDP) on IgM-RF, IgG-RF and IgA-RF (RFs), 47 cases were selected for study, including 33 patients with rheumatoid arthritis (RA) and 15 patients with joint pain/arthritis. After 99 Tc-MDP for drips model being given to the patients by intravenous drip 0.2 g daily for 5 days, the injection A and B models of 99 Tc-MDP were used to the patients by intravenous injection one set daily for 10 days, that was one course of treatment. The next course started after 10 days. Each case used it from 2 to 4 courses of treatment. The RFs in serum were determined by the method of enzyme-linked immunoabsorption assay (ELISA) before and after 2 and 4 courses of treatment. In the patients with RA, the concentrations of IgM-RF were 296.2±108.4 IU/ml, 189.5±92.3 IU/ml and 107.8±72.5 IU/ml; the concentrations of IgG-RF were 325.6±126.2 IU/ml, 209.7±98.2 IU/ml and 160.2±80.8 IU/ml; the concentrations of IgA-RF were 330.4±136.3 IU/ml, 210.7±89.2 IU/ml and 148.8±72.2 IU/ml before and after 2 and 4 courses of treatment, respectively. The concentrations of the above RFs were significantly lower after 2 and 4 courses than those before treatment ( P <0.05 and P <0.01). There was no significant difference in RFs concentrations in the patients with joint pain/arthritis before and after use of 99 Tc-MDP. In the patients with positive RFs before treatment, the RFs concentrations were decreased significantly after 2 and 4 courses of treatment ( P <0.05 and P <0.01). There was no obvious change of RFs concentrations in the patients with negative RFs after treatment of 99 Tc-MDP. It was concluded that 99 Tc-MDP could obviously reduce the abnormally high concentrations of RFs, but not influence the normal RFs, which indicated that 99 Tc-MDP has an important effect on controlling the activities of RA.

Protective effects of estrogens and caloric restriction during aging on various rat testis parameters

Aim： To investigate the effects of 17β-estradiol （E2）, Peganum harmala extract （PHE） and caloric restriction （CR） on various testis parameters during aging. Methods： Twelve-month-old male rats were treated for 6 months with either E2 or PHE, or submitted to CR （40%）. Results： Our results show that estrogens and CR are able to protect the male gonad by preventing the decrease of testosterone and E2 levels as well as the decrease of aromatase and estrogen receptor gene expressions. Indeed, E2, PHE and CR treatments induced an increase in the superoxide dismutase activities and decreased the activity of testicular enzymes： gamma-glutamyl transferase, alkaline phosphatase, lactate deshydrogenase as well as the aspartate and lactate transaminases in aged animals. In addition, the testicular catalase and gluthatione peroxidase activities were enhanced in E2, PHE and CR-treated rats compared to untreated animals at 18 months of age. Moreover, the positive effects of estradiol, PHE and CR were further supported by a lower level of lipid peroxidation. Recovery of spermatogenesis was recorded in treated rats. Conclusion： Besides a low caloric diet which is beneficial for spermatogenesis, a protective antioxydant role of estrogens is suggested. Estrogens delay testicular cell damage, which leads to functional senescence and, therefore, estrogens are helpful in protecting the reproductive functions from the adverse effects exerted by reactive oxygen species （ROS） produced in large quanti- ties in the aged testis.

Synthesis of CuAPTPP-TDI-TiO2 Conjugated Microspheres and its Photocatalytic Activity

The metal complex 5-（4-aminophenyl）-10,15,20-triphenylporphyrin copper （CuAPTPP） was covalently linked on the surface of TiO2 microspheres by using toluene disocyanate （TDI） as a bridging bond unit. The hydroxyl group （-OH） of TiO2 microspheres surface and the amino group （-NH2） of CuAPTPP reacted respectively with the active -NCO groups of TDI to form a surface conjugated microsphere CuAPTPP-TDI-TiO2 that was confirmed by FT-IR spectra. The CuAPTPP-TDI-TiO2 microspheres were characterized with UV-visible, elemental analysis, XRD, SEM, and UV-Vis diffuse reflectance spectra. The effect of amounts of linked TDI on the performance of photocatalytic microspheres was discussed, and the optimal molar ratio of TDI：TiO2 was established. The photocatalytic activity of CuAPTPP- TDI-TiO2 was evaluated using the photocatalytic degradation of methylene blue （MB） under visible-light irradiation. The results showed that, TDI, as a bond unit, was used to form a steady chemical brigdging bond linking CuAPTPP and the surface of TiO2 microspheres, and the prepared catalyst exhibited higher photocatalytic activity under visible-light irradiation for MB degradation. The degradation rate of 20 mg/L MB could reach 98.7% under Xe- lamp （150 W） irradiation in 120 rain. The degradation of MB followed the first-order reaction model under visible light irradiation, and the rate constant of 5.1× 10^-2 min-1 and the half- life of 11.3 min were achieved. And the new photocatalyst can be recycled for 4 times, remaining 90.0% MB degradation rate.

Xenoestrogens challenge 17β-estradiol protective effects in colon cancer

Several epidemiological,cellular,and molecular studies demonstrate the role of environmental chemicals with endocrine disrupting activities,typical of Westernized societies,in the pathogenesis of numerous diseases including cancer.Nonetheless this information,the design and execution of studies on endocrine disruptors are not yet cognizant that the specific actions of individual hormones often change with development and ageing,they may be different in males and females and may be mediated by different receptors isoforms expressed in different tissues or at different life stages.These statements are particularly true when assessing the hazard of endocrine disruptors against 17β-estradiol(E2)actions in that this hormone is crucial determinant of sexrelated differences in anatomical,physiological,and behavioral traits which characterize male and female physiology.Moreover,E2 is also involved in carcinogenesis.The oncogenic effects of E2 have been investigated extensively in breast and ovarian cancers where hormone-receptor modulators are now an integral part of targeted treatment.Little is known about the E2preventive signalling in colorectal cancer,although this disease is more common in men than women,the difference being more striking amongst pre-menopausal women and age-matched men.This review aims to dissect the role and action mechanisms of E2 in colorectal cancer evaluating the ability of estrogen disruptors(i.e.,xenoestrogens)in impair these E2 actions.Data discussed here lead to define the possible role of xenoestrogens in the impairment and/or activation of E2signals important for colorectal cancer prevention.

Estrogens and the pathophysiology of the biliary tree

The scientific framework concerning estrogen effects on different tissues has expanded enormously during the last decades, when estrogen receptor （ER） subtypes were identified. Estrogens are not only essential for the female reproductive system, but they also control fundamental functions in other tissues including the cardiovascular system, bone, brain and liver. Recently, estrogens have been shown to target the biliary tree, where they modulate the proliferative and secretory activities of cholangiocytes, the epithelial cells lining bile ducts. By acting on both estrogen receptors （ER-α） and （ER-β） subtypes, and by activating either genomic or non-genomic pathways, estrogens play a key role in the complex loop of growth factors and cytokines, which modulates the proliferative response of cholangiocytes to damage. Specifically, estrogens activate intracellular signalling cascades JERK1/2 （extracellular regulated kinases 1/2, PI3-kinase/AKT （phosphatidylinositol-3＇ kinase/AKT）] typical of growth factors such as insulin like growth factor （IGF1）, nerve growth factor （NGF） and vascular endothelial growth factor （VEGF）, thus potentiating their action. In addition, estrogens stimulate the secretion of different growth factors in proliferating cholangiocytes. This review specifically deals with the recent advances related to the role and mechanisms by which estrogens modulate cholangiocyte functions in normal and pathological conditions.

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.

Estrogens and the regulation of glucose metabolism

The main estrogens:estradiol,estrone,and their acyl-esters have been studied essentially related to their classical estrogenic and pharmacologic functions.However,their main effect in the body is probably the sustained control of core energy metabolism.Estrogen nuclear and membrane receptors show an extraordinary flexibility in the modulation of metabolic responses,and largely explain gender and age differences in energy metabolism:part of these mechanisms is already sufficiently known to justify both.With regard to energy,the estrogen molecular species act essentially through four key functions:(1)Facilitation of insulin secretion and control of glucose availability;(2)Modulation of energy partition,favoring the use of lipid as the main energy substrate when more available than carbohydrates;(3)Functional protection through antioxidant mechanisms;and(4)Central effects(largely through neural modulation)on whole body energy management.Analyzing the different actions of estrone,estradiol and their acyl esters,a tentative classification based on structure/effects has been postulated.Either separately or as a group,estrogens provide a comprehensive explanation that not all their quite diverse actions are related solely to specific molecules.As a group,they constitute a powerful synergic action complex.In consequence,estrogens may be considered wardens of energy homeostasis.

Inhibitory Effect of Estrogens,Phytoestrogens,and Caloric Restriction on Oxidative Stress and Hepato-toxicity in Aged Rats

Objective To investigate the protective effect of 17β-estradiol （E2）, peganum harmala extract （PHE） administration and calorie restriction （CR） treatment （60%） on oxidative stress and hepato-toxicity in aged rats. Methods Eighteen months old animals that were treated at the age of 12 months were divided into 4 groups： normal control group with free access to food, E2 treatment group, PHE treatment group and CR treatment group of the food given to control group. Six male rats at the age of 4 months were used as a reference group. Results Aging significantly decreased superoxide dismutase （SOD）, catalase （CAT） and glutathione peroxidase （GPX）, and increased lactate deshydrogenase （LDH）, gamma-glyiamyl transferase （GGT）, pbosphatase alkalines （PAL）, aspartate and lactate transaminase （AST and ALT） activities in the liver. Aging also induced an increased lipid peroxidation level, histological changes and a decreased E2 level. However, treatment with E2, PHE, and CR increased 17β-estradiol, and decreased hepatic dysfunction parameters and lipid peroxidation as well as histological changes in the liver of aged rats. Conclusion The antioxidant and hepatoprotective activity of PHE and CR is possibly attributed to its ability to increase E2 level, which as an antioxidant, acts as a scavenger of ROS. Further studies on the pharmaceutical functions of E2 in males may contribute to its clinical application.

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.

Novel Covalently Linked Self-Assembled Films from a Functional Hyperbranched Conjugated Poly (Phenylene Vinylene)

A new self-assembled films of a functional dendritic molecule, hyperbranched conjugated poly (phenylene vinylene), is obtained through covalent bond linkage. The highly ordered and homogenous molecular films are obtained;and characterized by UV-vis spectra, fluorescent spectra and atomic force microscopy.

Alkylation of Isobutane and Butene on BrФnsted-Lewis Conjugated Solid Superacids

A BrOnsted-Lewis (B-L) conjugated solid superacid HPW-SbF_5/SiO_2 wassynthesized by a two-step method. This B-L acid shows high acid strength, high activity, goodselectivity and moderate stability in alkylation of isobutane/butene due to strong interactionbetween the BrOnsted acid and the Lewis acid, as confirmed by the results of IR, NMR and XPS. Undera mild reaction condition (30℃, 15-35xl0~5 Pa), the conversion of butene was maintained at 100% for110 hours on stream and the main products were C_8 and TMP. The results of alkylation conductedunder various operating conditions indicated that the activity was improved by increasing theloading content of HPW and SbF_5. The selectivity of TMP in the products was enhanced when theisobutane/butene ratio in the feedstock was increased. The existence of some intermediates was alsoreported.

Simultaneous Determination of Four Estrogens in Compost Based on Ultrasonic Solvent Extraction, Solid-Phase Extraction Clean-Up and Analysis by UHPLC-MS/MS

A rapid, cost effective and reliable analytical method was developed and validated for the simultaneous determination of four estrogens (17 β-estradiol, 17 α-ethinylestradiol, estrone, and estriol) in compost samples from the biodegradation of biological infectious hazardous wastes. Ultrasonic solvent extraction, using methanol as extraction solvent, coupled with SPE clean-up, using cartridges HLB 60 mg - 6 ml Supelco® and acetonitrile for reconstitution of eluents, was used for the simultaneous extraction of the four estrogens. Mean recoveries in the range of 98% - 107% were obtained. All compounds were separated in a single gradient run by UHPLC KinetexTM 2.6 μm XB-C18 100 ÅLC (50 × 4.6 mm) column. Analytes were detected via multiple reaction monitoring (MRM) using an AB SCIEX API-5000TM triple quadrupole (Applied Biosystems/MDS SCIEX) with electrospray ionization in negative mode. Isocratic mobile phase of Water:ACN (50:50) resulted to be the optimum. Limits of detection and quantification were on the order of 0.66 ng·g-1 and 2 ng·g-1 for all the estrogens. These limits were lower than most of the values reported in the literature for similar matrices. Suitable level of linearity, good repeatability and reproducibility with coefficients of variation is lower than 11.7%, 6.8% and 8.3%, respectively.

Preparation of Conjugated Linoleic Acid of High Purity and Its Apparent Kinetic Characteristics During Formation

Conjugated linoleic acid (CLA) is a fatty acid with physiological activities and potential application prospect. This paper focuses on the method of synthesis of conjugated linoleic acid of high purity and the process line and conditions for its purification that can be used in large scale production. CLA of more than 95% purity was prepared by means of urea adduct purification and conjugation using safflower oil as material. The total recovery of the product adds up to more than 48%. The reactive kinetics about linoleic acid from sunflower oil converted into CLA was investigated, and its apparent kinetic model was also established, which can be used as a base for industrial designs.

Facile Synthesis of Chiral Conjugated Polymer Based on BINOL Skeleton

A new type of chiral conjugated polymers 6a-d has been synthesized by the reaction of (R)-2,2'-dihydroxy-1,1'-binaphthyl-6,6'-dicarbaldehyde 5 with corresponding diamine in the presence of acetic acid.