The controlled synthesis of anisotropic polymer particles with precisely tunable morphologies remains a significant challenge in polymer science. Here, we report a straightforward and scalable strategy for the synthesis of Janus-like polymer particles via oxygen-tolerant photo-mediated reversible addition-fragmentation chain transfer (RAFT) Pickering emulsion polymerization. This method eliminates the need for prior deoxygenation, inert gas protection, or additives, offering a green and operationally simple approach to functional polymer particles. Key particle properties-including wettability, size, rigidity, and flexibility-can be precisely tuned by modulating the monomer-to-crosslinker ratio, introducing a third monomer, and varying the size of the calcium carbonate nanoparticle Pickering stabilizer. Notably, using 50-nm calcium carbonate nanoparticles enables the systematic evolution of particle morphology from spherical to fragmented, compositionally anisotropic Januslike architectures. The resulting Janus-like polymer particles exhibit superior performance as solid emulsifiers for oil-in-water cinnamaldehyde (CA) emulsions, achieving exceptional stability and a sustained release profile (85% over 20 days, following the Weibull model). These emulsions demonstrate enhanced and sustained antibacterial activity against both E. coli and S. aureus, outperforming free CA. In a practical food preservation application, the Pickering emulsion reduces banana weight loss from 12.24% (blank control) to 8.97% and significantly delays peel browning over seven days. This work establishes a novel and green synthetic methodology for the controlled preparation of functional Janus-like polymer particles, with promising implications for polymer-based delivery systems in pharmaceutical and agricultural applications.
Polyimide (PI) composite films incorporating silica hollow nanoparticles (SHN) were successfully fabricated, exhibiting a distinct asymmetric structure. The surface morphology, composition, optical properties, and mechanical performance of the films were systematically investigated. Scanning electron microscopy and atomic force microscopy confirmed the preferential segregation of SHN toward the top surface, attributed to their low density and high surface activity. This led to a rougher top surface with a higher SHN concentration, while the bottom surface remained relatively smooth with a dominant PI phase. Optical measurements revealed a significant reduction in reflectance, particularly on the rough top surface, while maintaining high transmittance. Mechanical analysis, including tensile testing and nanoindentation, demonstrated that SHN incorporation enhanced the elastic modulus and hardness of the films, with the bottom surface exhibiting superior mechanical properties due to the compact stacking of PI and SHN. These findings provide valuable insights into the structural design of antireflective PI composite films and underscore the critical role of hollow nanoparticle surface activity in determining film morphology and functionality.
The development of flexible materials and intelligent technology has made the realization of electronic skin (e-skin) possible. It is a challenge to design biomimetic electronic skin with high sensitivity and self-healing ability. For this reason, a liquid metal-graphene aerogel/multi-wall carbon nanotubes-polyurethane (LM-GA/MWCNTs-PU) composite flexible pressure sensor was developed to mimic human skin. Among its components, the graphene aerogel carrying liquid metal mimics subcutaneous tissue, multi-wall carbon nanotubes enhance the conductivity and toughness of the matrix, and polyurethane is added to improve the self-healing ability of the composite. As a piezoresistive sensor, it exhibits high sensitivity (8.37kPa-1), excellent fatigue resistance (with stability maintained over at least 10,000 uninterrupted cycles), and a rapid response time (254/220ms), which facilitates the real-time tracking of human motion and signal transmission. The resulting LM-GA/MWCNTs-PU composite has potential applications in the fields of intelligent flexible wearables and physiological signal transmission devices.
This research aims to optimize the thermal stability of polyimide (PI) films and evaluate their insulating properties in flexible electronic devices. The thermal stability of PI films was optimized by chemical modification, physical doping, and other methods, and their insulating properties were systematically evaluated using key indicators such as breakdown field strength and dielectric constant. The research results show that through chemical modification methods such as molecular structure design and copolymer modification, as well as physical doping methods such as inorganic particle doping and application of nanocomposites, the thermal stability of PI films has been significantly improved. In addition, during the evaluation of insulating properties, it was found that the optimized PI films exhibit more stable breakdown field strength and dielectric constant under different environmental conditions, providing theoretical and practical support for the widespread application of PI films in the field of flexible electronic devices.
Aromatic polyimide is widely used in microelectronics as dielectric packaging layers. There is a high demand to reduce its dielectric constant to meet the fast development of communication technology. Here we report a simple and eco-friendly approach to preparing polyimide films with a lowered dielectric constant by adding silica hollow nanospheres with an average size of 100 nm in an aqueous solution of poly(amic acid) salt, and subsequent film casting and thermal imidization. The silica hollow nanospheres present a uniform distribution in polyimide matrix after surface modification with 3-aminopropyltriethoxysilane. The dielectric constant of the resulting composite films decreases linearly with particle loading till 15 wt% and reaches the lowest value of 2.5. The surface hardness and elastic modulus of the films improve by adding hollow nanospheres, while maintaining high optical transparency, high flexibility and a low coefficient of thermal expansion.
Hierarchical polyimides (PIs) not only show outstanding thermal stability and high mechanical strength but also have great advantages in terms of microstructure and surface area, which makes them highly valuable in various fields such as aerospace, microelectronics, adsorption, catalysis, and energy storage. However, great challenges still remain in the synthesis of hierarchical PIs with well-defined microstructure. Herein, polyamide acid salts (PAAS) with tunable ionization degree are synthesized first via the polymerization of dianhydride and diamine monomers in deionized water with 1,2-dimethylimidazole (DMIZ). Then cationic cetyltrimethylammonium chloride (CTAC) is added to the PAAS aqueous solution to induce the formation of polyelectrolyte-surfactant complexes based on electrostatic interaction. After a typical hydrothermal reaction (HTR) procedure, hierarchical PIs with different microstructures such as urchin-like PI microparticles, flower-like PI microparticles, and lamellar PI petals can be fabricated simply by changing the additive amount of DMIZ and CTAC. The nanostructure self-assemblies of PAAS are dominated by the charges on macromolecular chains and the formation of hierarchical structures of polymers is ascribed to a geometrical selection process during crystal growth. This work provides valuable insights into the self-assembly behaviors of polyelectrolyte systems for synthesizing well-defined hierarchical polymers.
Two-dimensional transition metal carbides/nitrides (MXenes) hold significant promise across diverse domains such as energy, catalysis, environmental science, and life sciences due to their distinct physical and chemical properties. This review focuses on the utilization of Ti-based MXenes specifically for photocatalytic applications. It critically evaluates the structural properties, fabrication strategies, and theoretical simulations of Ti-based MXenes tailored for photocatalysis. Firstly, the structural, electronic and optical properties of Ti-based MXenes are highlighted. Secondly, this review compares the merits and demerits of different fabrication techniques, offering a broad overview of fabrication methods for Ti-based MXenes. Afterwards, strategies aimed at enhancing photocatalytic performance, including interface engineering, defect introduction, heteroatom doping, and morphology control, are summarized. Then this review encapsulates the first-principles calculations and in-situ characterizations related to the fabrication process and photocatalytic mechanism of Ti-based MXenes. Furthermore, it extensively explores the emerging applications of Ti-based MXenes in energy, environmental remediation, and biomedicine. Forward-looking perspectives and insights are finally provided to stimulate innovative ideas and research methodologies for the design, synthesis, and integration of Ti-based MXenes into photocatalytic systems.
One-pot aqueous-phase synthesis of polyimides (PIs) offers great economic and environmental benefits and improves the hydrolytic stability of the precursor (polyamic acid) obviously. However, this method is only suitable for the polymerization of very limited dianhydride and diamine monomers up to now. In this study, the most commonly used dianhydrides and diamines for the preparation of commercially available PI products were selected for one-pot aqueous-phase synthesis of various polyamic acid salts (PAAS). The effects of the structure of monomers, the reaction temperature and the adding process of the organic base on the polymerization reaction were explored by rotational rheology, nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy. The polymerization products obtained via the aqueous-phase route show high molecular weight when the reaction conditions have been optimized. Various PI films prepared by the thermal imidization of corresponding PAAS demonstrate good optical transparency, excellent thermal stability, and outstanding mechanical and electrical properties. This work proposes the reaction mechanism of PAAS via one-pot aqueousphase route and utilizes this novel polymerization strategy to synthesize high-molecular-weight PIs from typical aromatic dianhydride and diamine monomers.
Water-in-water (w/w) emulsions have been recognized for their broad applications in foods, cosmetics, and biomedical engineering. In this work, silica Janus nanosheets (JNs) with polyacrylic acid (PAA) chains grafted on one surface via crushing functional silica foams, and used silica JNs as Pickering stabilizer to produce stable water-in-water (w/w) emulsions from the aqueous two-phase system (ATPS) containing methacrylic acid (MAA) and NaCl are prepared. The interfacial area of w/w emulsions increases linearly with the concentration of silica JNs, and the interfacial coverage of nanosheets is calculated to be about 98%. After polymerizing w/w emulsions prepared from MAA/NaCl ATPS, it is found that silica JNs are entrapped at the interface of w/w emulsions with the smooth PAA-grafted surface located toward MAA-rich phase due to their specific interaction. These results show that functional silica JNs can be used as a promising amphiphilic Pickering stabilizer to produce well-defined w/w emulsions for numerous application fields.
Near-infrared fluorescent cholangiography (NIRFC) with indocyanine green (ICG) as the developer yields clear visualization of the extrahepatic bile ducts and is effective in identifying key structures. Here, we analyzed and compared the surgical outcomes of fluorescent and conventional laparoscopy in cholecystectomy of various difficulties and then assessed the value of NIRFC. This retrospective study collected clinical data from partial patients who underwent laparoscopic cholecystectomy (LC) at the Department of Hepatobiliary and Pancreatic Surgery, Zhongnan Hospital of Wuhan University between 2020 and 2021. The study subjects were classified into ICG-assisted and white-light laparoscopy. Two cohorts with homogeneous baseline status were selected based on 1:1 ratio propensity score matching (PSM). Multivariate logistic regression analysis was performed to predict independent risk factors for LC difficulty. Thereafter, the matched cases were classified into difficult and easy subgroups by combining difficulty score and gallbladder disease type, and then the surgical outcomes of the two groups were compared. This study included a total of 624 patients. The patients were classified into the ICG group (n = 218) and the non-ICG group (n = 218) after a 1:1 ratio PSM. Our data showed significant differences between the groups in operative time (P = 0.020), blood loss (P = 0.016), length of stay (P = 0.036), and adverse reaction (P = 0.023). Stratified analysis demonstrated that ICG did not significantly improve the surgical outcomes in simple cases (n = 208). On the other hand, in difficult cases (n = 228), NIRFC shortened operative time (P = 0.003) and length of stay (P = 0.015), reduced blood loss (P = 0.028) and drain placement rate (P = 0.015), and had fewer adverse reactions (P = 0.023). The data showed that five cases were converted to laparotomy while two cases had minor bile leaks in the non-ICG group. There was no bile duct injury (BDI) in all the cases. Furthermore, high BMI, history of urgent admission and abdominal surgery, palpable gallbladder, thickened wall, and pericholecystic collection were risk factors for surgical difficulty. ICG-assisted NIRFC provides real-time biliary visualization. In complicated conditions such as acute severe inflammation, dense adhesions, and biliary variants, the navigating ability of fluorescence can enhance the operation progress, reduce the possibility of conversion or serious complications, and improve the efficiency and safety of difficult LC.
BackgroundIndocyanine green (ICG) fluorescence imaging technology is increasingly widely used in laparoscopic hepatectomy. However, whether it can provide long-term survival benefits to patients with liver malignancies remains unclear. This study investigated the clinical effect of laparoscopic hepatectomy for hepatocellular carcinoma (HCC) using ICG imaging technology.MethodsWe retrospectively analyzed HCC patients who underwent laparoscopic hepatectomy at Zhongnan Hospital of Wuhan University from January 2016 to December 2020. Propensity score matching (PSM) was used to match patients undergoing ICG fluorescence navigation laparoscopic hepatectomy (ICG-FNLH) with those undergoing conventional laparoscopic hepatectomy (CLH) in a 1:1 ratio to minimize the influence of confounding factors. We compared perioperative status and long-term prognosis between the two groups and performed multivariate analysis to identify risk factors associated with overall survival and recurrence-free survival.ResultsThe original cohort consisted of 141 patients, with 50 patients in each group (100 patients in total) after PSM. The anatomical liver resection rate, R0 resection rate, and resection margin distance in the ICG-FNLH group were higher than those in the CLH group. The intraoperative blood loss was lower than that in the CLH group. The recurrence-free survival and overall survival of the ICG-FNLH group were better than those of the CLH group. ICG-FNLH improved the recurrence-free survival of HCC patients (hazard ratio [HR] = 2.165, 95% confidence interval [CI]: 1.136-4.127, P = 0.024).ConclusionsCompared with CLH, ICG-FNLH can improve the recurrence-free survival rate of patients with hepatocellular carcinoma and may help to improve the long-term prognosis of patients.
Sulfur mustard (HD), a highly toxic vesicant used as a Chemical Warfare Agent (CWA), can remain for a few weeks once leaked into the environment. This work investigated the mass uptake of sulfur mustard vapor on thin water and ice films as well as air-water/ice interfacial and bulk partitioning of sulfur mustard under several typical environmental conditions by using a flow tube reactor. The partition constant of sulfur mustard in the sea water was close to that of pure water, and greater than that in the river water. The effects of water properties (including salinity, humic -like substance contents, and surface tension) on the air-water partitioning of HD were investigated. The adsorption enthalpies and entropies of HD uptake in thin water film were obtained from the temperature dependence was 20.76±1.08 kJ/mol and 71.58±3.91 J/mol. The quasi-liquid layer on the ice surface appeared to play a crucial role in the adsorption process as the ice thickness decreased. The data collected in this study are essential in developing effective strategies for managing and mitigating the risks associated with the leakage of chemical warfare agents containing sulfur mustard.
Silica Janus nanoparticles have great potential to improve the compatibility of immiscible polymer blends due to their synergetic amphiphilicity and Pickering effect. However, a great challenge of the scalable production of Janus nanoparticles still remains because of the complex preparation procedure and strict synthesis conditions. Herein, high internal phase emulsion templates stabilized by hyperbranched vinyl-substituted polyethox-ysiloxane alone are used as microreactors to realize the well-defined functionalization of porous materials in the oil phase and aqueous phase independently. Janus nanoshards (JNs) are then obtained via crushing the formed silica aerogels, followed by grafting polyolefin elastomer (POE) chains on the opposite surface with polystyrene (PS) chains. The morphology of the silica JNs is observed by field-emission scanning electron microscopy and transmission electron microscopy. The prepared silica JNs can anchor at the interface of PS/POE blends to manipulate the phase morphology and improve the adhesion of two phases. Synchronous strengthening and toughening of the polymer blends are achieved by using functional silica JNs as compatibilizers. This work proposes a new strategy for the large-scale production of silica JNs suitable for compatibilizing immiscible polymer blends.
Hypothesis: Constructing a segregated network in electrically conductive polymer composites (ECPCs) is an effective method to lower the electrical percolation threshold. The segregated network structure can be formed naturally via polymerizing Pickering high internal phase emulsions (HIPEs) because solid particles are assembled at water-oil interfaces. However, most Pickering stabilizers show poor electrical conductivity. In this work, we propose a facile method to prepare lightweight ECPCs with well-controlled segregated structure via Ti3C2Tx-stabilized HIPE templating. Experiments: Hydrophilic Ti(3)C(2)T(x)flakes are delicately hydrophobized with a double-chain cation surfactant. The morphology of Ti(3)C(2)T(x )flakes is investigated by transmission electron microscopy (TEM) and atom force microscopy (AFM). The surface properties of modified Ti(3)C(2)T(x )are characterized by zeta potential and water contact angle tests. The stability of Ti3C2Tx-stabilized emulsions, and the structure of prepared ECPCs are systematically investigated. Findings: Surface modified Ti(3)C(2)T(x )flakes are used to stabilize water-in-oil (w/o) HIPEs for the first time. After the polymerization of continuous oil phase, ECPCs are successfully prepared with closed-cell porous structure. The pore size and size distribution of porous composites can be tailored by varying the content of Ti(3)C(2)T(x )flakes. The Ti(3)C(2)T(x )flakes are mainly immobilized at the water-oil interface and eventually form the segregated network in composites. Combining the unique segregated network and the outstanding metallic conductivity of Ti3C2Tx, the prepared porous polymer composites exhibit good conductivity even with ultralow Ti(3)C(2)T(x )content of 0.016 vol%. (C) 2022 Elsevier Inc. All rights reserved.
Laparoscopic right posterior hepatectomy is considered difficult on the basis of the surgery difficulty scoring system. In this study, we evaluated the safety and effectiveness of the technical application of indocyanine green (ICG) fluorescence imaging-guided laparoscopic right posterior hepatectomy. Twenty-six patients who underwent ICG fluorescence imaging-guided laparoscopic right posterior hepatectomy at Hepatobiliary and Pancreatic Surgery Department of Zhongnan Hospital, Wuhan University, from June 2018 to December 2019, were included. The influence of patient position, trocar placement, hepatic inflow occlusion, central venous pressure (CVP), and the ICG fluorescence imaging-guided method were analyzed. In 17 patients, the left lateral position was maintained when the main tumor was in the S7, and in the remaining nine patients, the supine position was maintained with the right side of the body raised when the main tumor was in the S6. Ten patients who underwent preoperative injection of ICG were successfully developed for nonanatomical hepatectomy. Sixteen patients received intraoperative ICG injection for anatomical hepatectomy (2 cases had positive imaging findings, 14 cases had negative imaging findings, and 2 cases had failed imaging findings). All patients underwent the Pringle maneuver during the procedure. Four patients were preset with subhepatic vena cava blocking and one patient with suprahepatic inferior vena cava blocking. CVP was controlled at 3.00 ± 0.63 (mean ± SD) cmH2O. The operative time was 216.14 ± 52.05 min, and the bleeding volume was 128.57 ± 75.55 ml. Four patients had Clavien–Dindo level I complications, and one had level III complications. Postoperative hospitalization duration was 6.19 ± 1.40 days. There were 14 patients with hepatocellular carcinoma, 9 with metastatic liver malignancies, 2 with hepatic hemangioma, 1 with focal nodular hyperplasia of the liver, and 10 with hepatitis B liver cirrhosis. ICG fluorescence imaging guidance could be helpful for the safe implementation of laparoscopic right posterior hepatectomy.
Commercial fillers are widely used in the industrial manufacturing of silicone-based sealants such as CaCO3 filled polydimethylsiloxane (PDMS). The surface property of calcium carbonate, which is readily influenced by the adsorbed water and chemical modifiers, results in different rheological performances of the composites. However, it is difficult to characterize the surface due to the multiple contributions from the morphology, functional groups, and pore structure. In this work, the surface property was differentiated by the surface energies using inverse gas chromatography (IGC). The dispersive interaction was determined by n -alkanes (C-7-C-10), and the specific components were evaluated by cyclohexane, benzene, trichloroethylene, and tetrachloroethylene. The calcium carbonates showed the different dispersive interaction and the varied specific component on the modified surface. It was suggested that the dispersive interaction between calcium carbonate fillers and PDMS impacted the viscosity of the formed composite.
目的 探索肝脏术后严重肝缺血或淤血对病人生存预后的影响,探讨病情恢复过程中面临的问题和规律,以及临床治疗的关键措施.方法 回顾8例肝脏术后发生严重缺血、淤血性并发症病人,归纳该类并发症的临床病程及治疗要点;通过倾向性评分匹配方法匹配常规手术对照组,分析研究组(8例)和对照组(30例)术后肝功能、术后住院时间和住院费用的差异.结果 与对照组比较,研究组术后肝功能明显下降,术后住院时间和住院费用均明显增高,差异具有统计学意义(P<0.05).经关键性引流、补充血浆制品和白蛋白等治疗,8例病人全部存活,无死亡病例,随访至今未发现严重后遗症.结论 肝缺血、淤血性并发症病人因其一系列病理生理变化导致术后肝功能下降,术后住院时间和住院费用升高,但病人基本可获得较好预后.术前和术中应积极预防该类并发症发生,治疗过程中需注意动态监测病人病情并对病情变化做出及时干预,关键性引流、补充血浆制品和白蛋白可能是治疗中的重要环节.
Stretchable hydrogels have undergone a rapid development in recent years particularly for wearable strain sensors. However, most of hydrogel-based sensors exhibit poor mechanical properties. Here, we report a highly stretchable porous composite hydrogel that has a tensile strain of 400% and a compressive strain of 80%. The porous hydrogel is composed of polyvinyl alcohol (PVA) and copolymer of N-(3-sulfopropyl)-N-methacroyloxyethyl-N,N-dimethylammonium betaine (SBMA) and acrylamide (AM) prepared via graphene oxide (GO)-stabilized Pickering aqueous foam templates. The pore morphology of the composite hydrogels was observed by field emission scanning electron microscope (FE-SEM). The tensile and compressive curves of porous hydrogels with different GO concentrations were characterized. GO can act as Pickering stabilizer to produce aqueous foams and also construct the physical cross-linking network in porous hydrogels to improve their mechanical strength. In addition, when GO is reduced by L-ascorbic acid, it provides effective electric pathways in porous hydrogels with the conductive percolation of less than 0.40 wt%. The composite hydrogels thus exhibit excellent strain sensitivity and can be used to detect various human motions. The facile preparation process of the porous composite hydrogels with outstanding performance properties facilitates the development of flexible wearable strain sensing materials.
HYPOTHESIS:Janus nanosheets, which have two surfaces of different functionalities, exhibit unique interfacial properties. In this work, we propose a facile and scalable technique for preparation of silica-based Janus nanosheets, which is based on formation of high internal phase water-in-oil emulsions stabilized solely by alkyl-substituted polyethoxysiloxanes due to their hydrolysis-induced interfacial activity. EXPERIMENTS:Janus nanosheets are then obtained by crushing the silica foams converted from such emulsions. The morphology of Janus nanosheets is investigated by field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The chemical structure of functional silica materials is characterized by Fourier transform infrared spectroscopy (FT-IR). The asymmetric structure of silica nanosheets is observed by confocal laser scanning microscopy. FINDINGS:The resulting nanosheets have a rough hydrophobic surface and a smooth hydrophilic one, and are capable of stabilizing Pickering oil-in-water emulsions. Remarkably, pH-responsiveness of emulsions can be attained using the nanosheets whose hydrophilic surface is substituted with amino groups. Fast oil-water separation is achieved by the Janus nanosheets, which has been demonstrated by the nanosheets with a polystyrene-coated hydrophobic surface. This work paves a new avenue for large-scale production of functional silica-based Janus nanosheets suitable for numerous promising applications.
Functional porous materials show extensive applications in the environment, biology, aerospace, and so on. In this work, the generation of silica foams and functionalization of pore surface were simultaneously realized through an interfacial sol-gel reaction within high internal phase emulsion (HIPE) microreactors, where a hyperbranched polyethoxysiloxane (PEOS) was used as the sole stabilizer for the HIPEs. With various functional substances containing amino, epoxy, and carboxyl groups initially dissolved in the aqueous phase of HIPEs, these functional groups could be grafted onto the pore surface in the process of forming silica foams. Amino-functionalized silica foam showed fast adsorption of sunset yellow, and the adsorption capacity could reach as high as 1213.13 mg/g. Sodium polyacrylate-modified silica foam exhibited good adsorption capacity of cationic dyes and metal ions, e.g., 280.11 mg/g to methylene and 226.24 mg/g to Cu(II). Epoxy-functionalized silica foam particles were confirmed with a pronounced activity at the oil/water interface due to their Janus-like surface, which could be used as Pickering stabilizer. This HIPE-based synthesis strategy for silica foams shows promising future in adsorption, emulsion stabilization, and compatibilization.