Cross-linking Reaction Research Articles

Real-time tracking of curing process of an epoxy adhesive by X-ray photon correlation spectroscopy

Introduction: Cross-linkable polymers are in widespread use in a variety of industries because of their thermomechanical toughness, chemical resistance, and adhesive strength. But traditional methods to characterize these materials are insufficient for fully capturing the complex chemical and physical mechanisms of the crosslinking reaction. In this study, in situ X-ray photon correlation spectroscopy (XPCS) was used to investigate the crosslinking kinetics of a two-component epoxy resin adhesive.Materials and methods: With XPCS, we tracked the temporally resolved dynamics of silica filler particles, which served as probes of the internal dynamics of the thermoset network and allowed us to study the crosslinking process. The epoxy was cured isothermally at 40 °C and 80 °C to study the effects of curing temperature on the epoxy’s crosslinking reaction. XPCS results were compared to dielectric analysis (DEA) results, to demonstrate the similarities between a traditional technique and XPCS, and highlight the additional information gained with XPCS.Results and discussion: The epoxy resin was found to be highly sensitive to temperature. The epoxy samples exhibited different relaxation processes depending on isothermal cure temperature, indicating a complex relationship between applied temperature and the development of stress/relaxation conditions associated with formation of the thermoset network. Heating to the isothermal temperature setpoint at the start of curing promoted gelation, but the vitrification process was not completed during the isothermal curing stage. Instead, cooling the sample to room temperature facilitated the final vitrification process. This paper contextualizes this epoxy’s results within the broader field of thermoset study via XPCS, and advocates for XPCS as a fundamental technique for the study of complex polymers.

Pd nanocubes enclosed by {100} facets for activating electroless Cu deposition on liquid crystal polymer substrates with strong adhesion strength

In this study, we investigate the catalytic performance of palladium (Pd) nanocatalysts with different surface atomic structures for activating electroless copper (Cu) deposition on liquid crystal polymer (LCP) substrates. These nanocatalysts include Pd nanocubes featuring {100} facets of square atomic arrangement as their predominant surface structure and Pd spherical nanoparticles characterized by random atomic arrangements, synthesized using an aqueous method. Our electrochemical measurements reveal that the induction time for the growth of Cu films is significantly shorter when utilizing Pd nanocubes compared to Pd nanospheres. This shorter induction time signifies a quicker initiation of Cu growth, primarily due to the presence of Pd {100} facets. Furthermore, we also develop a surface modification approach involving a crosslinking reaction that utilizes the highly branched polyethylenimine and linear polyvinylpyrrolidone on the Pd nanocubes. This method not only facilitates the adsorption of Pd nanocubes onto the LCP substrates but also achieves a robust peel adhesion strength (630 gf/cm) of the resulting Cu films, exceeding the industrial adhesion goal of 500 gf/cm. Moreover, in-depth synchrotron X-ray photoelectron spectroscopy analysis provides valuable insights into the depth-dependent chemical changes within the Cu films and proves the removal of Cu oxides after the acid treatment.

A novel approach for the facile synthesis of zinc oxide/carbon hybrid systems from corn distillers soluble: Surface modification and characterization for sustainable remediation

Sustainable, efficient, and environmentally friendly ways to tailor the carbonaceous materials from bio sources with desired functionalities remain a challenge around the world. In this study, we represent a novel approach to synthesize carbon hybrid material based on Zinc Oxide/carbon (ZnO/C) hybrid systems by catalytic hydrothermal process via crosslinking reaction through nucleation and growth of ZnO particles at the functional groups of oxidized carbon material. This research explored the volarization of Condensed Corn Distillers Soluble (CDS) as a carbon precursor to synthesize biobased carbon spheres. Surface modification of the produced carbon spheres took place using zinc chloride (ZnCl2) during hydrothermal carbonization (HTC). Zinc chloride (ZnCl2) was used to function as a catalyst during HTC and functioned as a ZnO source to synthesize (ZnO/C) hybrid systems. Design Expert software v13 was used to design the hydrothermal carbonization (HTC) experiments and response surface methodology was used to find the optimized conditions for the preparation of carbon hybrid systems. The hydrothermal synthesis process introduced 3D stone like zinc oxide particles onto the carbon matrix. These particles were self-assembled onto the carbon framework to produce carbon hybrid systems with unique physical, chemical, structural and functional properties. Herein, the obtained carbon hybrid systems (ZnO/C) were investigated and discussed in detail. ZnO/C hybrid systems were analyzed for surface morphology using scanning electron microscopy (SEM) that presented a 3D spherical interconnected phase and XRD analyses were used for phase crystallinity that showed new crystalline phases such as hopeite and zincite after the ZnCl2 incorporation. Surface functional groups were also analyzed by FTIR and results confirmed the presence of hydrophilic groups such as –OH, CC, and COOH on the surface of ZnO/C hybrid carbon systems. This study provided the insightful guidance for tailoring novel design of multifunctional carbon material as an adsorbent/catalyst for various applications of sustainable remediation.

Modification of polyvinyl alcohol with 2-hydroxypropionic acid and cross-linking with glutaraldehyde for the preparation of biodegradable mulch paper and its properties

Abstract The preparation of biodegradable mulch film with paper-based materials has become a significant focus in mulch film development due to the serious pollution caused by plastic mulch film. This study utilized the esterification cross-linking reaction of LA, PVA, and GA to coat the surface of paper as the substrate. FTIR, TGA, XRD, SEM, tensile testing, and oxygen, water vapor barrier performance tests were performed. The optimal conditions for film preparation were determined to be a 10 % PVA aqueous solution, 5 % GA content, and a PVA/LA/GA ratio of 1:2:1. The resulting film paper exhibited a dry strength of 6.52 kN/m, a wet strength of 0.23 kN/m, a tearing degree of 969.35 mN, a Cobb value of 12.04 g/m2, a water vapor transmission rate of 573.27 g m−2 24 h−1, and an oxygen transmission rate of 7.373 cm3 m−2 24 h−1. After a 6-week landfill degradation test, the film showed a degradation rate of 25.3 %, while still maintaining a tensile strength of 1.89 kN/m. Field application tests in greenhouses confirmed that the film paper facilitated the growth of strawberry, its mechanical and barrier properties suitable for a biodegradable paper mulch.

Preparation of novel zwitterionic polysulfone ultrafiltration membranes for the dual-enhanced antifouling and antibacterial properties by in-situ one pot crosslinking reaction

Zwitterionic polysulfone (PSf) ultrafiltration membranes were fabricated by non-solvent phase separation (NIPS) method. Herein, a casting solution at 45 °C was developed by using chloromethylated polysulfone (CMPSf), N, N-dimethylacetamide (DMAc) as a solvent, 4-amino-benzenesulfonic acid monosodium salt (ABS) as a cross-linking agent, and Na2CO3 as an acid binder. Simultaneously, the occurrence of the electrophilic substitution reaction between ABS and CMPSf caused the formation of ABS grafting CMPSf (CMPSf-g-ABS). After a specific reaction time, the casting solution was applied to cast membranes, which were subsequently submerged in coagulation bath. A zwitterionic ultrafiltration (ZUF) membrane was obtained using NIPS following the treatment of hydrochloric acid (HCl) solution (1 M mol). Because of the formation of cross-linked CMPSf-g-ABS, the results revealed that the casting solution's viscosity increased sharply from 425.4 mPa s at the initial stage (0 h) to 4810.8 mPa s (22 h). Interestingly, the morphology of the membranes with an asymmetric finger-like structure at 0 h gradually transformed to a gradient sponge-like structure after 22 h. Specifically, the ZUF membrane (M22-H) with the gel fraction of 72.1% procured after the reaction of 22 h demonstrated a low water contact angle (40.17°) and a high pure water permeance (420.4 L m−2 h−1 bar−1). The M22-H also exhibited a high flux recovery rate (FRR) (90.2%), bovine serum albumin (BSA) rejection (>95%), and Escherichia coli (E. coli) antibacterial rate (96.2%). The surface of the ZUF membrane with numerous zwitterionic groups enhances the hydration layer's energy (i region <16 nm) and creates a thick hydration layer (ii region >16 nm), causing a significant improvement in the antifouling performance. This research opens new avenues for preparing zwitterionic functional membranes.

EFFECT OF DEEP EUTECTIC SOLVENT PRETREATMENT ON DEVULCANIZATION OF WASTE RUBBER POWDER

ABSTRACT The recycling of waste rubber is very important for environmental protection, but the compatibility problem restricts the recycling and application of waste rubber powder (WRP). Devulcanization of WRP has been proven to be an effective method to improve the solubilization effect. The use of environmentally friendly nontoxic solvents can not only improve the devulcanization effect but also avoid secondary pollution. Thus, in this article, an environmentally friendly deep eutectic solvent (DES) is first prepared and then applied to the devulcanization treatment of WRP. The results show that the prepared DES has a positive devulcanization effect, and the devulcanization rate can reach 50%. The devulcanization mechanism can be divided into two aspects: (1) adsorption and removal of sulfur-containing low-molecular compounds and (2) destruction of the crosslinking structure and improvement of fluidity. Observation of the microstructure showed that the rougher the surface of the desulfurized rubber powder, the more conducive to the crosslinking reaction with the matrix material to form a uniform whole. The devulcanization mechanism of DES is divided into destroying the sulfur-containing cross-linked structure and adsorbing the sulfur-containing low-molecular compounds. The surface of WRP after DES treatment is rougher and more porous, which is beneficial to the crosslinking reaction with the matrix material. Finally, the optimum process conditions for the de-crosslinking effect are determined by orthogonal test as follows: liquid-solid ratio 15∶1, temperature 120°C, time 0.5 h.

Surface-Activated Ti3C2Tx Adsorption of Acetylene Black Coupled with Polyaniline as a Signal Tag for the Detection of the ESAT-6 Antigen of Mycobacterium tuberculosis.

Early secretory antigenic target-6 (ESAT-6) is regarded as the most immunogenic protein produced by Mycobacterium tuberculosis, whose detection is of great clinical significance for tuberculosis diagnosis. However, the detection of the ESAT-6 antigen has been hampered by the expensive cost and complex experimental procedures, resulting in low sensitivity. Herein, we developed a titanium carbide (Ti3C2Tx)-based aptasensor for ESAT-6 detection utilizing a triple-signal amplification strategy. First, acetylene black (AB) was immobilized on Ti3C2Tx through a cross-linking reaction to form the Ti3C2Tx-AB-PAn nanocomposite. Meanwhile, AB served as a conductive bridge, and Ti3C2Tx can synergistically promote the electron transfer of PAn. Ti3C2Tx-AB-PAn exhibited outstanding conductivity, high electrochemical signals, and abundant sites for the loading of ESAT-6 binding aptamer II (EBA II) to form a novel signal tag. Second, N-CNTs were adsorbed on NiMn layered double hydride (NiMn LDH) nanoflowers to obtain NiMn LDH/N-CNTs, exhibiting excellent conductivity and preeminent stability to be used as electrode modification materials. Third, the biotinylated EBA (EBA I) was immobilized onto a streptavidin-coated sensing interface, forming an amplification platform for further signal enhancement. More importantly, as a result of the synergistic effect of the triple-signal amplification platform, the aptasensor exhibited a wide detection linear range from 10 fg mL-1 to 100 ng mL-1 and a detection limit of 4.07 fg mL-1 for ESAT-6. We envision that our aptasensor provides a way for the detection of ESAT-6 to assist in the diagnosis of tuberculosis.

Chronological-Programmed Black Phosphorus Hydrogel for Responsive Modulation of the Pathological Microenvironment in Myocardial Infarction.

Electroactive hydrogels have garnered extensive interest as a promising approach to myocardial tissue engineering. However, the challenges of spatiotemporal-specific modulation of individual pathological processes and achieving nontoxic bioresorption still remain. Herein, inspired by the entire postinfarct pathological processes, an injectable conductive bioresorbable black phosphorus nanosheets (BPNSs)-loaded hydrogel (BHGD) was developed via reactive oxide species (ROS)-sensitive disulfide-bridge and photomediated cross-linking reaction. Significantly, the chronologically programmed BHGD hydrogel can achieve graded modulation during the inflammatory, proliferative, and maturation phases of myocardial infarction (MI). More details, during early infarction, the BHGD hydrogel can effectively reduce ROS levels in the MI area, inhibit cellular oxidative stress damage, and promote macrophage M2 polarization, creating a favorable environment for damaged myocardium repair. Meanwhile, the ROS-responsive structure can protect BPNSs from degradation and maintain good conductivity under MI microenvironments. Therefore, the BHGD hydrogel possesses tissue-matched modulus and conductivity in the MI area, facilitating cardiomyocyte maturation and electrical signal exchange, compensating for impaired electrical signaling, and promoting vascularization in infarcted areas in the maturation phase. More importantly, all components of the hydrogel degrade into nontoxic substances without adverse effects on vital organs. Overall, the presented BPNS-loaded hydrogel offers an expandable and safe option for clinical treatment of MI.

A simple method to prepare anion exchange membrane by PVA/EVOH/MIDA for acid recovery by diffusion dialysis.

Given the substantial environmental pollution from industrial expansion, environmental protection has become particularly important. Nowadays, anion exchange membranes (AEMs) are widely used in wastewater treatment. With the use of polyvinyl alcohol (PVA), ethylene-vinyl alcohol (EVOH) copolymer, and methyl iminodiacetic acid (MIDA), a series of cross-linked AEMs were successfully prepared using the solvent casting technique, and the network structure was formed in the membranes due to the cross-linking reaction between PVA/EVOH and MIDA. Fourier transform infrared spectrometer, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy were used to analyze the prepared membranes. At the same time, its comprehensive properties which include water uptake, linear expansion rate, ion exchange capacity, thermal stability, chemical stability, and mechanical stability were thoroughly researched. In addition, diffusion dialysis performance in practical applications was also studied in detail. The acid dialysis coefficient (UH+) ranged from 10.2 to 35.6 × 10-3 m/h. Separation factor (S) value ranged from 25 to 38, which were all larger than that of the commercial membrane DF-120 (UH+: 8.5 × 10-3 m/h, S: 18.5). The prepared membranes had potential application value in acid recovery.

Starch Glutaraldehyde Cross-Linked Hydrogel for Drug Release Properties.

In this study, we synthesized and characterized a novel starch glutaraldehyde cross-linked hydrogel for drug release. The hydrogel exhibited excellent properties such as absorption capacity and drug release. By optimizing the cross-linking reaction using varying concentrations of glutaraldehyde and reaction time, we obtained a hydrogel with a three-dimensional network structure, superior swelling properties, and mechanical strength. The results revealed doxycycline sustained and controlled drug release over a prolonged period, which could be adjusted by altering the cross-linking density of the hydrogel. Overall, the starch glutaraldehyde cross-linked hydrogel shows great promise as a drug delivery system with controlled release properties, applicable in pharmaceuticals and tissue engineering.

Electric-Tree Resistant Performance and Thermal Charge-Carrier Dissipation Mechanism of Voltage Stabilizer-Modified EPDM

In order to improve electric-tree resistant performance and dielectric breakdown strength of ethylene-propylene-diene misch-polymere (EPDM) material used for cable accessory reinforce insulation, the two specific aromatic ketone compounds—vinylphenylacetone (VPE) and 4-propylene oxyxy-2-hydroxydibenzenone (AOHBP) are employed as two paradigms of voltage stabilizer for chemical-graft modifications. Electric-tree resistances and insulation performances of modified EPDM materials and their charge trapping mechanism of thermoelectron inhibitions are studied by the accelerated electric-tree aging experiments, alternating current (AC) dielectric breakdown tests, surface potential trap-level analyses and first-principles calculations. Both the two species of voltage stabilizers are effective for promoting electric-tree inception voltage and dielectric breakdown strength, leading to a high extension of electric-tree morphology and smaller dimension of electric-trees growth, in which AOHBP is more significant. The two species of voltage stabilizers have been successfully grafted onto EPDM molecular-chains in thermal-chemistry crosslinking reactions of EPDM, introducing multiple shallow levels of charge traps, which reduces the energy released by trapping charge carriers and thus alleviates electric-tree aging of EPDM. The AOHBP and VPE represent a high electron affinity and a small electronic energy gap, which is competent of assimilating the kinetic energies of hot charge carriers whilst restricting Auger electronic excitation. Especially, the benzene group in voltage stabilizer renders shallow level charge traps with a larger carrier capture cross-section than deep traps and simultaneously possesses the high atomic vibration frequencies similar as electronic-transition energies, which results in effective dissipation on the kinetic energies of hot charge carriers. This mechanism dominates to increase electric-tree resistance and insulation strength of EPDM. The present study proves the important role of voltage stabilizers in improving insulation performance of EPDM material, and reveals the refrigeration mechanism on hot charge carriers for restricting electric-tree growth, which provides a significant strategy of chemical modifications for developing high-insulation cable accessory materials.

Variation of Young's modulus suggested the main active sites for four different aging plastics at an early age time

Precisely determining which bonds are more sensitive when plastic aging occurs is critical to better understand the mechanisms of toxic release and microplastics formation. However, the relationship between chemical bonds with the active aging sites changes and the aging behavior of plastics at an early age is still unclear. Herein, the mechanical behavior of four polymers with different substituents was characterized by the high-resolution AFM. Young's modulus (YM) changes suggested that the cleavage of C-Cl bonds in PVC, C-H bonds in PE and PP, and C-F bonds in PTFE are the main active aging sites for plastic aging. The aging degree of the plastics followed the order of PVC > PP > PE > PTFE. Two aging periods exhibited different YM change behavior, the free radical and cross-linking resulted in a minor increase in YM during the initiation period. Numerous free radicals formed and cross-linking reaction happened, causing a significant increase in YM during the propagation period. Raman spectroscopy verified the formation of microplastics. This research develops promising strategies to quantitatively evaluate the aging degrees using AFM and establish the relationship between chemical bonds and mechanical behavior, which would provide new method to predict plastic pollution in actual environments.

Preparation of a superior soy protein adhesive with high solid content by enzymatic hydrolysis combined with cross-linking modification

The production of traditional wood adhesives relies on petrochemical resources and puts enormous pressure on the ecosystem. Therefore, it is important to use bio-based soy protein adhesives to replace traditional adhesives. However, soy protein adhesives have the problems of low solid content, high viscosity and poor water resistance. In this study, we combined enzymatic hydrolysis with cross-linking modification to reduce the molecular mass of soy protein and increase the solid content of adhesive, constructed a uniform and tight covalent bond cross-linking network in the adhesive. Through this modification strategy, we prepared a soy protein adhesive with high solid content, suitable viscosity and excellent bonding strength. The results showed that compared with 0-SPI adhesive, the viscosity of 4-SPI-18/PA/TA adhesive decreased by 61.6%, reached 21899 mPa·s. Meanwhile, the residual rate of the adhesive increased by 18% (59%), the moisture absorption rate reduced by 7.8% to reach 3.8%. The dry/wet shear strength of modified adhesive increased by 56.1% (1.28 MPa) and 44.3% (0.88 MPa), respectively, and the tensile strain at break increased by 58.1% (14.84%). This is because enzymolysis improved its coating performance, and formed mechanical interlocking with wood. In addition, the amount of SPI increased, and more protein molecules participated in the cross-linking reaction, forming a more uniform and compact cross-linking network structure in the adhesive, effectively improving the bonding strength and toughness. This study provides a novel approach for the preparation of cleaning and tenacious adhesives, aiming to explore a green development model.

The influence of UV radiation on the properties of GFRP laminates in underwater conditions

Degradation of polymer composites is a significant problem in many engineering aspects. Due to the interaction of various degradation factors during the exploitation of composites, a synergistic effect of destruction is observed. The article describes the phenomena occurring in glass fiber reinforced polyester laminates under the influence of ultraviolet radiation (UV) in an aquatic environment. The laminates were exposed to UV-A, UV-B and UV-C radiation for 1000 h in free-air and underwater conditions. During the test, the materials were immersed at stable depth of 1 mm and 10 mm, respectively. The three-point bending tests performed on the samples after being exposed to UV showed an increase in the flexural strength of the composites. Simultaneously, degradation of the outer surface layer was observed. The degradation removed the thin resin film from the surface which resulted in a direct exposure of the reinforcing fibers to the environment. The transformations taking place in the deeper layers of the composite increased the mechanical strength due to the additional cross-linking reactions excited by the energy arising from the radiation. Moreover, the formation of polymer structures from free styrene remaining after the technological process and the occurrence of free radical reactions as a result of the cage effect was also observed.

A Soy Protein-Based Film Based on Chemical Treatment and Microcrystalline Cellulose Reinforcement Obtained from Corn Husk Byproducts.

Developing an environmentally friendly soy protein-based film that offers excellent performance has garnered considerable interest while also posing a significant challenge. Herein, we propose the strategy of covalent and noncovalent cross-linking to improve the mechanical properties of the films. First, chemical denaturation was carried out under the combined action of sodium sulfite, sodium dodecyl sulfate, sodium hydroxide, and urea to reshape the structure of the protein to improve the solubility of protein and release active groups. Then, microcrystalline cellulose (MCC) derived from low-cost agro-industrial byproducts (corn husk) was employed to balance the covalent cross-linking reaction between proteins and the noncovalent reaction between MCC and protein. The results indicate that the structure and properties of the soy protein-based films were modified and improved through chemical treatment in conjunction with biomass enhancement. It is concluded that the addition of 1% MCC improves the tensile strength, elastic modulus, water solubility, and water vapor permeability of "MCC-1%" by 64.7, 75.9, 22.7, and 12.9%, respectively. Additionally, the resulting film of "MCC-1%" exhibits better resistance to thermal degradation and improved thermo-stability. However, the elongation at break decreased by increasing the addition of MCC. Thus, this work may provide a simple and affordable approach to preparing a high-performing soy protein-based film.

Highly transparent and flame‐retardant polyvinyl alcohol membranes crosslinked with 2‐methyl‐2,5‐dioxo‐1,2‐oxaphospholane

AbstractIn the present paper, crosslinked polyvinyl alcohol (PVA) membranes with high transparency and excellent flame retardancy were obtained by blending 2‐methyl‐2,5‐dioxo‐1,2‐oxaphospholane (OP) with a PVA water solution at the molecular scale. Fourier transform infrared spectrometry and differential scanning calorimetry were used to investigate the crosslinking reaction. The surface morphology and micromechanical assessments of the membrane were examined using nanoindentation. The limited oxygen index (LOI) and vertical flame microscale combustion calorimetry, thermogravimetric analysis, scanning electron microscopy (SEM), energy‐dispersive spectroscopy (EDS), and x‐ray photoelectron spectroscopy (XPS) were employed to evaluate the flame retardancy and reveal the corresponding mechanisms. It was found that OP reacted with PVA below 120°C. The crosslinked membranes have a rougher surface and higher hydrophilicity and lower hardness and modulus than pure PVA does. The crosslinked membranes exhibit enhanced flame retardancy and high transparency. The membrane passes the UL 94 V 0 rating with an LOI of 27.6% and achieves a transmittance of 90.2% when the OP content is 20 wt.%. The SEM, EDS, and XPS results demonstrate that the interaction between OP and PVA effectively promotes the formation of a continuous and stable char in the condensed phase.

Luminescent hollow spherical nanoparticles with enhanced imaging contrast through hydrogen bonding connected micelles

Herein, we propose an innovative method for synthesizing luminescent hollow spherical nanoparticles. Our method involves the construction of hydrogen bonding connected micelles (HBCMs) utilizing inter-polymer complexes of poly(styrene-alt-hydroxyphenylmaleimide)/poly(4-vinylpyridine) (poly(S-alt-HPMI)/P4VP), which could undergo self-assembly, resulting in the formation of core/shell nanostructures in the selective solvent. The aim was to incorporate two types of fluorescent compounds, namely tris(4–bromophenyl)amine (TPA–Br3) and 1,1,2,2–tetrakis(4–bromophenyl)ethene (TPE–Br4), as the cross-linkers to enhance the shell structures of HBCMs and using dimethylformamide (DMF) was employed to remove the core structures, aiming to pursue the formation of luminescent hollow spheres. Transmission electron microscopy (TEM) images confirmed the formation of self-assembled spherical structures formed by poly(S-alt-HPMI)/P4VP inter-polymer complexes. The morphological features, hydrogen bonding interactions, particle sizes, cross-linking reactions, core removal, and thermal properties were thoroughly investigated by TEM, atomic force microscope (AFM), dynamic light scattering (DLS) instrument, Fourier transform infrared (FTIR) spectroscopy, 1H nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) analyses. Moreover, the optical properties were also explored by fluorescence microscope and photoluminescence (PL). This evidence indicates that the HBCMs could be directly cross-linked with TPA–Br3 or TPE–Br4 and subsequently transformed into hollow spheres by the addition of DMF. Fluorescent particles featuring hollow spheres could be prepared successfully without traditional dye staining or labeling. This advancement holds promising potential for applications in nano-carriers with improved imaging contrast.

A Triple Shape Memory Material of Trans‐Polyisoprene/Polycaprolactone with Customizable Response Temperature Controlled by Crosslinking Density

AbstractBody‐temperature responsive shape memory polymers (SMPs) attract a lot of attention with the application in biomedicine. Multiple SMPs regulate the response temperature through the proportion of their stationary and reversible phases by changing the molecular weight of the polymer or the components of the composite. Herein, a crosslinking reaction of trans‐polyisoprene (TPI) and polycaprolactone (PCL) initiated by benzoyl peroxide gave a SMP of TPI/PCL, whose shape memory property is realized by stage‐division crystallization zone. Under the fixed ratio of TPI:PCL, the crystallization performance of TPI/PCL is controlled by the crosslinking density. The response temperatures of the components in TPI/PCL are selected for the stage‐division crystallization zone, making excellent shape memory performance at corresponding response temperatures. For the further achievement in controllable response temperature within a certain range, the relationship model between crosslinking density and response temperature is established, obtaining the customizable response temperature ranging 37–55 °C. The presented facile regulation method for response temperature will provide a new idea for the SMPs development.

Self-signal electrochemical identification of circulating tumor DNA employing poly-xanthurenic acid assembled on black phosphorus nanosheets

A self-signal electrochemical identification interface was prepared for the determination of circulating tumor DNA (ctDNA) in peripheral blood based on poly-xanthurenic acid (PXTA) assembled on black phosphorus nanosheets (BPNSs) acquired through simple ultrasonication method. The BPNSs with large surface area could be integrated with the xanthurenic acid (XTA) monomers by right of physisorption, and hence improved the electropolymerization efficiency and was beneficial to the enlargement of the signal response of PXTA. The assembled PXTA/BPNSs composite with attractive electrochemical activity was adopted as a platform for the recognition of DNA immobilization and hybridization. The probe ssDNA was covalently fixed onto the PXTA/BPNSs composite with plentiful carboxyl groups through the terminate free amines of DNA probes by use of the 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and N-hydrosulfosuccinimide cross-linking reaction, accompanied with the decline of the self-signal response. When the hybridization between the probe ssDNA and the target DNA was accomplished, the self-signal response of the composite interface reproduced by virtue of the shaping of helix construction. The determination limit of the assembled DNA identification interface was 2.1 × 10−19 mol/L, and the complementary target DNA concentrations varied from 1.0 × 10−18 mol/L to 1.0 × 10−12 mol/L. The DNA identification platform displayed magnificent sensitivity, specificity and stability, and was efficaciously implemented to the mensuration of ctDNA derived from colorectal cancer.

Reprocessable and self-healable boronic-ester based poly(styrene-b-isoprene-b-styrene) vitrimeric elastomer with improved thermo-mechanical property and adhesive performance

It is fascinating to develop vitrimeric elastomers with excellent processability and improved physical properties through incorporating reversible covalent bonds into traditional thermoplastic elastomers. In this work, a poly(styrene-b-isoprene-b-styrene) (SIS) thermoplastic elastomer was selected as the base elastomer and converted into vitrimer through peroxide-induced crosslinking reaction with di-vinyl-terminated boronic ester crosslinker. Kissinger model predicts that the activation energy of vitrimer crosslinking process is slightly higher than that of chemical crosslinking process. The peroxide content was adjusted to tune the composition of permanent chemical crosslinks and dynamic chemical crosslinks. In this way, SIS vitrimer elastomer with tailored multiple network structure was successfully prepared. The stress relaxation behavior of all SIS-BE samples shows Arrhenius-type temperature-dependency and the bond-exchange activation energy (Ea) of SIS-D0.5-B5 sample was estimated as 44.14 kJ/mol. SIS vitrimer elastomer shows improved creep-resistance, comparative mechanical strength and elastic recovery in relative to crosslinked SIS elastomer while maintaining good reprocessbility and self-healing efficiency. Additionally, SIS vitrimeric elastomer shows an increased lap-shear strength from 0.53 MPa to 1.02 MPa with the increase of DCP content. Therefore, we have demonstrated the potential for industrial-scale production of SIS vitrimer elastomer and its applications as reprocessable and healable adhesives.