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.

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.

Numerical Investigations on the Resonance Errors of Multiscale Discontinuous Galerkin Methods for One-Dimensional Stationary Schrödinger Equation

In this paper,numerical experiments are carried out to investigate the impact of penalty parameters in the numerical traces on the resonance errors of high-order multiscale discontinuous Galerkin(DG)methods(Dong et al.in J Sci Comput 66:321–345,2016;Dong and Wang in J Comput Appl Math 380:1–11,2020)for a one-dimensional stationary Schrödinger equation.Previous work showed that penalty parameters were required to be positive in error analysis,but the methods with zero penalty parameters worked fine in numerical simulations on coarse meshes.In this work,by performing extensive numerical experiments,we discover that zero penalty parameters lead to resonance errors in the multiscale DG methods,and taking positive penalty parameters can effectively reduce resonance errors and make the matrix in the global linear system have better condition numbers.

Prediction of one-dimensional CrN nanostructure as a promising ferromagnetic half-metal

Searching for one-dimensional(1D)nanostructure with ferromagnetic(FM)half-metallicity is of significance for the development of miniature spintronic devices.Here,based on the first-principles calculations,we propose that the 1D CrN nanostructure is a FM half-metal,which can generate the fully spin-polarized current.The ab initio molecular dynamic simulation and the phonon spectrum calculation demonstrate that the 1D CrN nanostructure is thermodynamically stable.The partially occupied Cr-d orbitals endow the nanostructure with FM half-metallicity,in which the half-metallic gap(?s)reaches up to 1.58 eV.The ferromagnetism in the nanostructure is attributed to the superexchange interaction between the magnetic Cr atoms,and a sizable magnetocrystalline anisotropy energy(MAE)is obtained.Moreover,the transverse stretching of nanostructure can effectively modulate?s and MAE,accompanied by the preservation of half-metallicity.A nanocable is designed by encapsulating the CrN nanostructure with a BN nanotube,and the intriguing magnetic and electronic properties of the nanostructure are retained.These novel characteristics render the 1D CrN nanostructure as a compelling candidate for exploiting high-performance spintronic devices.

When insulating polymers meet conjugated polymers:the noncovalent bonding does matter

Insulating polymers are characterized by a predominantlyσ-covalent structure,which localize electrons in the atoms and exhibit dielectricity.Insulating polymers typically adopt a more linear and extended conformation,as the repeating units are connected by single covalent bonds,resulting in a relatively straight and extended chain structure.For most insulating polymers,the contour length(L_(c))is significantly larger than their persistence length(Lp)due to the rotation of C−C single bonds(Fig.1(a)).Consequently,this leads to a flexible,random-coil chain conformation.This structural feature contributes to the great mechanical durability and resistance to crack initiation during stretching or bending processes.In contrast,conjugated polymers possess aπ-conjugated molecular structure,allowing electron mobility along the main chain,called delocalization,which imparts semiconducting properties[1,2].The presence of rigid,alternating single and multiple bonds results in comparable Lc and Lp,thereby yielding a stiff or semi-flexible conformation(Fig.1(b))[3,4].As a consequence,most conjugated polymers are prone to fracture under low strain levels(<10%)[5−7].

Classification of Hallux Valgus Using Conjugated Deformity

Hallux valgus is a complex deformity of the forefoot. It is the result of multiple effects of endogenous and exogenous etiological factors with different degrees of influence. The degree of hallux valgus deformity was assessed by radiological values of hallux valgus (HVA) and intermetatarsal (IMA) angle. Thus, each hallux valgus deformity corresponds to a pair (HVA, IMA) of hallux valgus angle (HVA) and intermetatarsal angle (IMA) values in the plane of the deformity. The intensity of the point position vector S (HVA, IMA) in the deformation plane determined by the relation represents the absolute (conjugate) value of the power deformities. The goal of the article is to explain the advantage of the definition of the degree of hallux valgus deformity using its absolute (conjugate) value, and then to show that the degree of deformity defined in this way enables a better classification of deformities for all values of the HVA and IMA angles. Furthermore, in this article, applying the definition of conjugate deformity, analytical expressions were constructed for the assessment of the average value of deformity correction after operative treatment, as well as the error assessment of deformity correction after operative treatment. All obtained results were checked on a sample of 396 operatively treated feet.

Size effect on light propagation modulation near band edges in one-dimensional periodic structures

Periodic photonic structures can provide rich modulation in propagation of light due to well-defined band structures.Especially near band edges,light localization and the effect of near-zero refractive index have attracted wide attention.However,the practically fabricated structures can only have finite size,i.e.,limited numbers of periods,leading to changes of the light propagation modulation compared with infinite structures.Here,we study the size effect on light localization and near-zero refractive-index propagation near band edges in one-dimensional periodic structures.Near edges of the band gap,as the structure's size shrinks,the broadening of the band gap and the weakening of the light localization are discovered.When the size is small,an added layer on the surface will perform large modulation in the group velocity.Near the degenerate point with Dirac-like dispersion,the zero-refractive-index effects like the zero-phase difference and near-unity transmittance retain as the size changes,while absolute group velocity fluctuates when the size shrinks.

A Dugdale-Barenblatt model for elliptical orifice problem with asymmetric cracks in one-dimensional orthorhombic quasicrystals

By means of Muskhelishvili’s method and the technique of generalized conformal mapping,the physical plane problems are transformed into regular mathematical problems in quasicrystals(QCs).The analytical solution to an elliptical orifice problem with asymmetric cracks in one-dimensional(1D)orthorhombic QCs is obtained.By using the Dugdale-Barenblatt model,the plastic simulation at the crack tip of the elliptical orifice with asymmetric cracks in 1D orthorhombic QCs is performed.Finally,the size of the atomic cohesive force zone is determined precisely,and the size of the atomic cohesive force zone around the crack tip of an elliptical orifice with a single crack or two symmetric cracks is obtained.

Robust Damage Detection and Localization Under Complex Environmental Conditions Using Singular Value Decomposition-based Feature Extraction and One-dimensional Convolutional Neural Network

Ultrasonic guided wave is an attractive monitoring technique for large-scale structures but is vulnerable to changes in environmental and operational conditions(EOC),which are inevitable in the normal inspection of civil and mechanical structures.This paper thus presents a robust guided wave-based method for damage detection and localization under complex environmental conditions by singular value decomposition-based feature extraction and one-dimensional convolutional neural network(1D-CNN).After singular value decomposition-based feature extraction processing,a temporal robust damage index(TRDI)is extracted,and the effect of EOCs is well removed.Hence,even for the signals with a very large temperature-varying range and low signal-to-noise ratios(SNRs),the final damage detection and localization accuracy retain perfect 100%.Verifications are conducted on two different experimental datasets.The first dataset consists of guided wave signals collected from a thin aluminum plate with artificial noises,and the second is a publicly available experimental dataset of guided wave signals acquired on a composite plate with a temperature ranging from 20℃to 60℃.It is demonstrated that the proposed method can detect and localize the damage accurately and rapidly,showing great potential for application in complex and unknown EOC.

Gas‐phase fluorination of conjugated microporous polymer microspheres for effective interfacial stabilization in lithium metal anodes

Lithium(Li)metal anodes have attracted extensive attention due to their ultrahigh theoretical capacity and low potential.However,the uneven deposition of Li near the unstable electrode/electrolyte interfaces leads to the growth of Li dendrites and the degradation of active electrodes.Herein,we directly fluorinate alkyne-containing conjugated microporous polymers(ACMPs)microspheres with fluorine gas(F_(2))to introduce a novel fluorinated interlayer as an interfacial stabilizer in lithium metal batteries.Using density functional theory methods,it is found that as-prepared fluorinated ACMP(FACMP)has abundant partially ionic C–F bonds.The C–F bonds with electrochemical lability yield remarkable lithiophilicity during cycling.The in situ reactions between the active C–F bonds and Li ions enable transfer of lithium fluoride microcrystals to the solid electrolyte interphase(SEI)layers,guaranteeing effective ionic distribution and smooth Li deposition.Consequently,Li metal electrodes with the fluorinated interlayers demonstrate excellent cycling performances in both half-batteries and full cells with a lithium bis(trifluoromethanesulfonyl)imide electrolyte as well as a nonfluorinated lithium bis(oxalate)borate electrolyte system.This strategy is highly significant in customizable SEI layers to stabilize electrode interfaces and ensure high utilization of Li metal anodes,especially in a nonfluorinated electrolyte.

Analysis of Dynamical Behavior of One-Dimensional Real Maps: An Executable Dynamical Programming Software Approach

The dynamical behavior of real-world phenomena is implausible graphically due to the complexity of mathematical coding. The present article has mainly focused on some one-dimensional real maps’ dynamical behavior irrespective of using coding. In continuation, linear, quadratic, cubic, higher-order, exponential, logarithmic, and absolute value maps have been used to scrutinize their dynamical behavior, including the characteristics of the orbit of points. Dynamical programming software (DPS.exe) will be proposed as a new technique to ascertain the dynamical behavior of said maps. Thus, a mathematician can automatically determine one-dimensional real maps’ dynamical behavior apart from complicated programming code and analytical solutions.

Activating coordinative conjugated polymer via interfacial electron transfer for efficient CO_(2) electroreduction

With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).

Thermal-induced interfacial behavior of a thin one-dimensional hexagonal quasicrystal film

In this paper,we investigate the interfacial behavior of a thin one-dimensional(1D)hexagonal quasicrystal(QC)film bonded on an elastic substrate subjected to a mismatch strain due to thermal variation.The contact interface is assumed to be nonslipping,with both perfectly bonded and debonded boundary conditions.The Fourier transform technique is adopted to establish the integral equations in terms of interfacial shear stress,which are solved as a linear algebraic system by approximating the unknown phonon interfacial shear stress via the series expansion of the Chebyshev polynomials.The expressions are explicitly obtained for the phonon interfacial shear stress,internal normal stress,and stress intensity factors(SIFs).Finally,based on numerical calculations,we briefly discuss the effects of the material mismatch,the geometry of the QC film,and the debonded length and location on stresses and SIFs.

Cobalt phthalocyanine-based conjugated polymer as efficient and exclusive electrocatalyst for CO_(2) reduction to ethanol

Electrocatalytic conversion of carbon dioxide to high value-added chemicals is a promising method for solving the energy crisis and global warming.Electrochemical active metal-containing conjugated polymers have been widely studied for heterogeneous carbon dioxide reduction.In the present contribution,we designed and synthesized a stable cobalt phthalocyanine-based conjugated polymer,named CoPPc-TFPPy-CP,and also explored its electro-catalytic application in carbon dioxide reduction to liquid products in an aqueous solution.In the catalyst,cobalt phthalocyanine acts as building blocks connected with 1,3,6,8-tetrakis(4-formyl phenyl)pyrenes via imine-linkages,leading to mesoporous formation polymers with the pore size centered at 4.1nm.And the central co-balt atoms shifted to a higher oxidation state after condensation.With these chemical and structural natures,the catalyst displayed a remarkable electrocatalytic CO_(2) reduction performance with an ethanol Faradaic efficiency of 43.25%at-1.0V vs RHE.While at the same time,the electrochemical reduction process catalyzed by cobalt phthalocyanine produced only carbon monoxide and hydrogen.To the best of our knowledge,CoPPc-TFPPy-CP is the first example among organic polymers and metal-organic frameworks that produces ethanol from CO_(2) with a remarkable selectivity.

Design of pH-responsive antimicrobial peptide melittin analog-camptothecin conjugates for tumor therapy

Melittin,a classical antimicrobial peptide,is a highly potent antitumor agent.However,its significant toxicity seriously hampers its application in tumor therapy.In this study,we developed novel melittin analogs with pH-responsive,cell-penetrating and membranelytic activities by replacing arginine and lysine with histidine.After conjugation with camptothecin(CPT),CPT-AAM-1 and CPT-AAM-2 were capable of killing tumor cells by releasing CPT at low concentrations and disrupting cell membranes at high concentrations under acidic conditions.Notably,we found that the C-terminus of the melittin analogs was more suitable for drug conjugation than the N-terminus.CPT-AAM-1 significantly suppressed melanoma growth in vivo with relatively low toxicity.Collectively,the present study demonstrates that the development of antitumor drugs based on pH-responsive antimicrobial peptide-drug conjugates is a promising strategy.

Relationship between ATPase activity and conjugated polyamines in mito-chondrial membrane from wheat seedling roots under osmotic stress

The effects of osmotic stress on the ATPase activity, the contents of —SH group and conjugated polyamines in mitochondrial membrane from wheat seedling [Triticum aestivum L. cv. Yumai No.18(drought-tolerant) and cv. Yumai No.9(drought-sensitive)] roots were investigated. The results showed that ATPase activity and —SH group content decreased with polyethylene glycol(PEG) 6000(-0.55 MPa) treatment for 7 d, in concert with the decrease of the ratio of noncovalently conjugated spermidine(NCC-Spd)/noncovalently conjugated putrescine(NCC-Put) and increase of the covalently conjugated putrescine(CC-Put). Osmotic stress injury to Yangmai No.9 seedlings was alleviated greatly with 1 mmol/L exogenous spermidine(Spd), in concert with marked increases of the ratio of NCC-Spd/NCC-Put, —SH group contents and ATPase activity in mitochondrial membrane. Under osmotic stress, the concomitant treatment of Yumai No.18 seedlings with methylglyoxyl bis(guanylhydrazone) (MGBG), an inhibitor of S-adenosyl methionine decarboxylase(SAMDC), and phenanthrolin (o-Phen), an inhibitor of transglutaminase(TGase), caused a significant decrease of the ratio of NCC-Spd / NCC-Put, CC-Put contents, respectively, in concert with the marked decreases of ATPase activity, —SH group content and its tolerance to osmotic stress. All the results above suggested that osmotic stress tolerance of wheat seedlings was associated with the ATPase activity, the contents of —SH group, NCC-Spd and CC-Put in mitochondrial membrane.

The preparation and characterization of folate-conjugated human serum albumin magnetic cisplatin nanoparticles

Objective： Nanoparticles are becoming an important method of targeted drug delivery. To evaluate the importance of folate-conjugated human serum albumin （HSA） magnetic nanoparticles （Folate-CDDP/HSA MNP）, we prepared drug-loaded Folate-CDDP/HSA MNPs and characterized their features. Methods： First, folate was conjugated with HSA under the effect of a condensing agent, and the conjugating rate was evaluated by a colorimetric method using 2, 4, 6 - trinitrobenzene sulfonic acid. Second, under N., gas, Fe：~O1 magnetic nanomaterials were prepared and characterized by using transmission electron microscopy （TEM）, SEM-EDS and X-ray diffraction （XRD）. Finally, Folate-CDDP/HSA MNP was prepared by using a solvent evaporation technique. TEM was used to observe particle morphology. The particle size and distribution of the prepared complexes were determined by a Laser particle size analyzer. Drug loading volume and drug release were investigated by a high performance liquid chromatography method （HPLC） in vitro. Results： We successfully prepared folate-conjugated HSA and its conjugating rate was 27.26 μg/mg. Under TEM, Fe2O4 magnetic nanoparticles were highly electron density and had an even size distribution in the range of 10-20 nm. It was confirmed by SEM-EDS and XRD that Fe304 magnetic nanoparticles had been successfully prepared. Under TEM, drug-loaded magnetic nanoparticles were observed, which had a round shape, similar uniform size and smooth surface. Their average size was 79 nm which was determined by laser scattering, and they exhibited magnetic responsiveness. Encapsulation efficiency was 89.75% and effective drug loading was calculated to be 15.25%. The release results in vitro showed that the half release time （ta/2） of cisplatin in cisplatin Solution and Folate-CDDP/HSA MNP was 65 min and 24 h respectively, which indicated that microspheres had an obvious effect of sustained-release. Conclusion： Folate-CDDP/HSA MNPs were prepared successfully. The preparation process and related characteristics data provided a foundation for further study, including the mechanism of the nanoparticles distribution in vivo and their intake by tumor cells.

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

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

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.