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UV‑driven surface oxidation of PVC microplastics and their interaction with emerging pollutants 紫外线驱动的聚氯乙烯微塑料表面氧化及其与新兴污染物的相互作用
IF 2.3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2025-07-08 DOI: 10.1007/s00396-025-05469-6
Sadam Hussain Tumrani, Bharat Prasad Sharma, Razium Ali Soomro, Gaber A. M. Mersal, Ahmed M. Fallatah, Mohamed M. Ibrahim, Selcan Karakuş

Understanding the behavior of PVC microplastics under UV light and their interaction with antibiotics is critical for evaluating their environmental impact. Herein, a systematic investigation reveals the adsorption behavior of UV-aged PVC (UV-PVC) microplastics toward ofloxacin (OFX), focusing on compositional and morphological changes and their adsorption behavior post-aging for 30 days. The UV aging process increased the oxygen-to-carbon (O/C) ratio of PVC from 0.23 to 1.17, along with increased oxygen-containing functional groups (− OH, − C = O) that governed the interaction behavior leading to a significant improvement in adsorption capacity reaching 38.98 mg/g compared to 18 mg/g at equilibrium compared to pristine PVC (P-PVC). The enhanced interaction was particularly effective at neutral pH, where hydrogen bonding and electrostatic interactions were optimum as confirmed by DFT calculation. These findings contribute to profiling the environmental behavior of microplastics and assessing their role as a vector for emerging pharmaceutical pollutants.

Graphical Abstract

了解聚氯乙烯微塑料在紫外线下的行为及其与抗生素的相互作用对评估其环境影响至关重要。本文系统研究了UV-PVC微塑料对氧氟沙星(OFX)的吸附行为,重点研究了老化30天后PVC微塑料的组成和形态变化及其吸附行为。UV老化过程将PVC的氧碳比(O/C)从0.23提高到1.17,同时增加了控制相互作用行为的含氧官能团(- OH, - C = O),导致吸附容量显著提高,达到38.98 mg/g,而与原始PVC (P-PVC)相比,达到平衡状态时为18 mg/g。增强的相互作用在中性pH下特别有效,DFT计算证实了氢键和静电相互作用是最佳的。这些发现有助于分析微塑料的环境行为,并评估它们作为新兴药物污染物载体的作用。图形抽象
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引用次数: 0
Effective improvement of hydrophilicity and anti-fouling of PDA-modified PVDF membrane by MoS2 二硫化钼有效地改善了pda改性PVDF膜的亲水性和防污性能
IF 2.3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2025-07-05 DOI: 10.1007/s00396-025-05470-z
Chenyao Liu, Zhixiang Yan, Yanan Xing, Zhiyong Tan

A new MoS2-PDA/PVDF ultrafiltration membrane was prepared by the thermotropic phase separation/non-solvent-induced phase separation (EIPS/NIPS) method. The effects of the addition of MoS2-PDA on the hydrophilicity, microscopic morphology, and flux, flux recovery, retention, and anti-fouling properties of the composite membranes with dye wastewater and bovine serum albumin (BSA) solution were investigated. The results showed that compared with the pristine membrane, the maximum water flux of MoS2-PDA-modified membrane was 107.8 L/(m2‧h), which was 33.58% higher; the retention rates of BSA and various dyestuffs in this membrane were 92% and 95.2%, which were 10.2% and 3.6% higher, respectively; the highest flux recoveries were 88% and 84.6%, both increased by 10%. This indicates that the modified membrane provides a reference for extending the service life of ultrafiltration membranes and can achieve efficient separation and resource recovery of small molecule wastewater.

Graphical Abstract

采用热致相分离/非溶剂诱导相分离(EIPS/NIPS)法制备了MoS2-PDA/PVDF超滤膜。研究了添加MoS2-PDA对染料废水和牛血清白蛋白(BSA)溶液处理复合膜的亲水性、微观形貌、通量、通量回收率、截留率和抗污染性能的影响。结果表明:mos2 - pda改性膜的最大水通量为107.8 L/(m2·h),比原始膜提高了33.58%;BSA和各种染料在该膜中的保留率分别为92%和95.2%,分别提高10.2%和3.6%;最高回收率分别为88%和84.6%,均提高10个百分点。这表明改性膜为延长超滤膜的使用寿命提供了参考,可以实现小分子废水的高效分离和资源化回收。图形抽象
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引用次数: 0
Structural and mechanical properties of hydroxyapatite, carbon fiber, and B4C in polypropylene and polymethylmethacrylate 聚丙烯和聚甲基丙烯酸甲酯中羟基磷灰石、碳纤维和B4C的结构和力学性能
IF 2.3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2025-07-04 DOI: 10.1007/s00396-025-05461-0
Mehtap Demirel

A recent study focuses on a significant deficiency in bone tissue engineering by creating polymer-based composite materials with improved thermal resistance and mechanical characteristics for use in medical contexts. Although polypropylene (PP) and poly(methyl methacrylate) (PMMA) blends are widely utilized, their mechanical strength and thermal resistance are insufficient, thereby limiting their suitability for load-bearing implants. We synthesized new composite materials by incorporating a sol–gel-produced blend of hydroxyapatite (80 wt.%), carbon fiber (10 wt.%), and boron carbide (10 wt.%) into PP/PMMA matrices in different weight proportions (25/75 and 75/25 wt.%) and varying amounts (10–30 wt.%). Thermogravimetric analysis showed a 20% increase in thermal stability, with the temperature at which degradation begins rising from 265 to 300 °C for composites containing 30 wt.% reinforcement. Results from mechanical testing showed a 15% rise in hardness (as measured by the Brinell HB30 method) and a 25% decrease in wear rate for the 75PMMA/25PP composite reinforced with 20 wt.% of the material, which was attributed to uniform distribution and strong interfacial bonding as confirmed by scanning electron microscopy–energy dispersive spectroscopy (SEM–EDS). X-Ray diffraction (XRD) and Fourier-transform infrared (FTIR) analysis revealed increased crystallinity and PO₄3⁻/B–C bonding, which correlated with enhanced performance. These results demonstrate the potential of HAp/CF/B4C-reinforced PP/PMMA composites as long-lasting biomaterials for orthopedic and dental implants, featuring enhanced thermal and mechanical properties relative to traditional blends.

Graphical Abstract

最近的一项研究通过创建具有改进的热阻和机械特性的聚合物基复合材料用于医疗环境,重点关注骨组织工程的重大缺陷。尽管聚丙烯(PP)和聚甲基丙烯酸甲酯(PMMA)共混物被广泛使用,但它们的机械强度和耐热性不足,从而限制了它们在承重植入物中的适用性。我们将羟基磷灰石(80 wt.%)、碳纤维(10 wt.%)和碳化硼(10 wt.%)以不同重量比例(25/75 wt.%和75/25 wt.%)和不同数量(10 - 30 wt.%)的溶胶-凝胶混合物加入PP/PMMA基体中,合成了新的复合材料。热重分析表明,含30% wt.%增强的复合材料的热稳定性提高了20%,开始降解的温度从265°C上升到300°C。力学测试结果表明,添加20wt .%材料增强的75PMMA/25PP复合材料的硬度提高了15%(用布氏HB30法测量),磨损率降低了25%,这是由于扫描电子显微镜-能量色散能谱(SEM-EDS)证实的均匀分布和强界面结合。x射线衍射(XRD)和傅里叶变换红外(FTIR)分析显示结晶度和PO₄3 -毒接度增加,与性能增强相关。这些结果表明HAp/CF/ b4c增强PP/PMMA复合材料作为骨科和牙科植入物的长效生物材料的潜力,相对于传统的共混物具有更高的热性能和机械性能。图形抽象
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引用次数: 0
Switchable biomolecule adsorption on 2D thermoresponsive poly(N-isopropylacrylamide)–coated gold nanowire array 二维热响应型聚n -异丙基丙烯酰胺包覆金纳米线阵列上可切换生物分子的吸附
IF 2.3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2025-07-04 DOI: 10.1007/s00396-025-05466-9
Mai Thi Tuyet Nguyen, Dung Tuan Nguyen

This work presents the development of AuNW@pNIPAM, a hybrid platform combining electron beam lithography (EBL)-fabricated gold nanowire arrays (AuNWs) with thermoresponsive poly(N-isopropylacrylamide) (pNIPAM) brushes. A functionalization strategy using aryl diazonium salts, developed in our group, enables the precise confinement of the pNIPAM brushes exclusively on the AuNWs via surface initiated atom transfer radical polymerization (SI-ATRP), achieving an optimized 9 nm polymer thickness. Temperature-induced changes in the hydration state of pNIPAM were characterized using atomic force microscopy (AFM) in liquid phase verus the temperature, revealing a significant collapse of the polymer layer above the lower critical solution temperature (LCST). Concurrently, UV–vis spectroscopy demonstrated a 7-nm red shift in localized surface plasmon resonance (LSPR) due to the phase transition and a 15-nm shift upon bovine serum albumin (BSA) adsorption showcasing enhanced plasmonic sensitivity for real-time biomolecular monitoring. The reversible temperature-controlled adsorption/desorption of BSA on the AuNW@pNIPAM surface highlights the potential of this hybrid platform for applications in biosensing, drug delivery, and other bio-interfacing technologies.

Graphical abstract

这项工作介绍了AuNW@pNIPAM的发展,这是一个结合电子束光刻(EBL)制造的金纳米线阵列(aunw)和热响应性聚n -异丙基丙烯酰胺(pNIPAM)刷的混合平台。我们小组开发的一种使用芳基重氮盐的功能化策略,可以通过表面引发原子转移自由基聚合(SI-ATRP)将pNIPAM刷精确地限制在aunw上,实现优化的9纳米聚合物厚度。利用原子力显微镜(AFM)表征了pNIPAM水化状态随温度的变化,发现在较低临界溶液温度(LCST)以上,聚合物层明显坍塌。同时,紫外-可见光谱显示,由于相变,局部表面等离子体共振(LSPR)发生了7 nm的红移,牛血清白蛋白(BSA)吸附发生了15 nm的红移,表明等离子体对实时生物分子监测的敏感性增强。在AuNW@pNIPAM表面的可逆温控吸附/解吸凸显了这种混合平台在生物传感、药物传递和其他生物界面技术中的应用潜力。图形抽象
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引用次数: 0
Synthesis and characterization of polymeric films composed of polyvinyl alcohol/chitosan with superior adsorption capacity for removal of Remazol Black B 聚乙烯醇/壳聚糖聚合物膜对雷马唑黑B的吸附性能及表征
IF 2.3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2025-07-02 DOI: 10.1007/s00396-025-05464-x
Ruaa Zaidani, Zehra Gün Gök, Ayfer Koyuncu

This study used chitosan with functional groups and PVA polymer with strong film-forming-mechanical properties to obtain a new adsorbent material, and the usability of membranes bearing the combined effect of these materials in dye adsorption was investigated through experimental studies. To synthesize poly(vinyl alcohol)/chitosan (PVA/Cht) membranes, 6% (g/mL) PVA solution was mixed with a chitosan solution of 4% (g/mL) in a volumetric ratio of one to one. The PVA/Cht polymer mixture was processed into membranes via solvent casting and subsequently maintained at 150 °C for an hour to promote physical cross-linking. Fourier transform infrared spectroscopy (FTIR) was used to study the structural composition of the synthesized membranes, which verified the presence of PVA and chitosan. The membrane morphology was assessed using scanning electron microscopy (SEM), while energy dispersive spectroscopy (EDS) outcomes demonstrated the presence of carbon, oxygen, and nitrogen in the membranes. Thermogravimetric (TGA) analysis was also carried out to evaluate the membranes’ thermal stability. Following this, the membranes were also tested for their ability to adsorb Remazol Black B (RBB) dye under a range of experimental conditions. Maximum adsorption occurred with membranes at low pH (at pH 2). It was observed that adsorption time reached equilibrium in 24 h. During adsorption experiments at various incubation temperatures, the dye removing efficiency of the membranes improved with rising temperatures. When adsorption was performed with membranes at different initial dye concentrations, it was observed that there was no change in the adsorption capacity of membranes after a certain dye concentration. When adsorption experiments were conducted with varying initial adsorbent quantities, at a dye concentration of 800 mg/L, pH 2, 24-h incubation, and 0.02 g of adsorbent, the membranes reached a peak dye removing of 625.51 mg/g. Membranes have very high paint removing capacity. The usability of the obtained material as a potential adsorbent was proven; further studies will be carried out to develop the materials planned to be produced and put them into practice.

Graphical Abstract

A schematic diagram of the synthesis of polymeric films composed of PVA/Cht with superior adsorption capacity for the removal of RBB dye. Created with Biorender.com.

本研究以带官能团的壳聚糖和具有强成膜力学性能的聚乙烯醇聚合物为材料,制备了一种新型的吸附材料,并通过实验研究考察了承载这两种材料联合作用的膜在染料吸附中的可用性。为合成聚乙烯醇/壳聚糖(PVA/Cht)膜,将6% (g/mL)的PVA溶液与4% (g/mL)的壳聚糖溶液以1:1的体积比混合。通过溶剂铸造将PVA/Cht聚合物混合物加工成膜,随后在150℃下保持1小时以促进物理交联。利用傅里叶变换红外光谱(FTIR)研究了合成膜的结构组成,证实了聚乙烯醇和壳聚糖的存在。使用扫描电子显微镜(SEM)评估膜形态,而能量色散光谱(EDS)结果显示膜中存在碳,氧和氮。热重分析(TGA)对膜的热稳定性进行了评价。在此之后,在一系列实验条件下,还测试了膜吸附Remazol Black B (RBB)染料的能力。在低pH (pH 2)时,膜的吸附量最大。观察到吸附时间在24 h左右达到平衡。在不同培养温度下的吸附实验中,膜的脱染效率随着温度的升高而提高。当膜在不同初始染料浓度下进行吸附时,观察到在一定的染料浓度后膜的吸附能力没有变化。在不同初始吸附剂用量下进行吸附实验,在染料浓度为800 mg/L、pH为2、孵育24 h、吸附剂用量为0.02 g的条件下,膜的去除率达到625.51 mg/g。膜具有非常高的除漆能力。证明了所得材料作为潜在吸附剂的可用性;将进行进一步的研究,以开发计划生产的材料并将其付诸实践。具有优异吸附能力的PVA/Cht聚合物膜的合成原理图。创建与Biorender.com。
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引用次数: 0
pH-responsive in situ gelation via phenylboronate-glucamine ester-crosslinking in modified hyaluronan at physiological pH 在生理pH下,通过苯基硼酸-氨基葡萄糖酯-交联改性透明质酸进行pH响应的原位凝胶化
IF 2.3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2025-07-02 DOI: 10.1007/s00396-025-05463-y
Ryotaro Miki, Tsutomu Yamaki, Masaki Uchida, Hideshi Natsume

In situ gelling materials that rapidly form gels upon contact with body fluids are highly attractive for clinical applications. Boronate ester-crosslinked materials can create flexible, pH-responsive hydrogels. In this study, we focused on glucamine as the cis-diol-containing moiety in phenylboronic acid (BA) derivatives. We developed a modified hyaluronan acidic system composed of BA derivative-modified hyaluronan and glucamine-modified hyaluronan. 3-Amino-4-fluorophenylboronic acid and D-glucamine were modified onto sodium hyaluronate through condensation reaction, and mixed modified hyaluronan systems were prepared. We investigated the effect of pH on the rheological properties of the modified hyaluronan system and examined the binding constants (K) between BA derivatives and glucamine. The mixed modified hyaluronan system (pH 3.9) which combined the higher degree of substitution gelled quickly upon injection into a buffer solution at pH 7.4. The system exhibits significant pH dependence, with gelling properties increasing markedly as the pH rises from 4.4 to 7.4. For glucamine, the K values increased as the pD rose from 5.8 to 8.3. We concluded that successful pH-responsive in situ gelation requires a high degree of polymer substitution and strong K values between the BA derivative and the cis-diol moiety. Glucamine was identified as an effective cis-diol-containing moiety for BA derivatives.

Graphical Abstract

在与体液接触后迅速形成凝胶的原位凝胶材料在临床应用中具有很高的吸引力。硼酸酯交联材料可以制成柔性的、ph值敏感的水凝胶。在本研究中,我们重点研究了苯硼酸(BA)衍生物中含有顺式二醇的氨基葡萄糖。研制了由BA衍生物-改性透明质酸和氨基葡萄糖-改性透明质酸组成的改性透明质酸体系。通过缩合反应将3-氨基-4-氟苯硼酸和d -氨基葡萄糖胺改性为透明质酸钠,制备了混合改性透明质酸体系。研究了pH对改性透明质酸体系流变学性质的影响,并测定了BA衍生物与氨基葡萄糖的结合常数(K)。混合修饰透明质酸体系(pH 3.9)结合了较高取代度,在pH 7.4的缓冲溶液中注射后迅速凝胶化。该体系表现出明显的pH依赖性,当pH值从4.4上升到7.4时,胶凝性能显著提高。葡萄糖胺的K值随pD从5.8升高到8.3而升高。我们得出结论,成功的ph响应原位凝胶化需要高度的聚合物取代和BA衍生物和顺式二醇部分之间的强K值。葡萄糖胺被确定为BA衍生物中有效的顺式二醇。图形抽象
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引用次数: 0
The anti-freezing, water-resistant, adhesive, and solvent-free polyionic gels for wireless and underwater strain sensing 抗冻,防水,粘接,无溶剂多离子凝胶用于无线和水下应变传感
IF 2.3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2025-07-01 DOI: 10.1007/s00396-025-05465-w
Haiyan Du, Yifan Zhao, Nan Zhang, Jun Shen

The anti-freezing and water-resistant gels strain sensors have great potential applications in flexible wearable devices, underwater communication, and deep-sea exploration. However, the poor adhesion, high swelling, low stretchability, or decreased conductivity of most gels in water hinders the stable signal transmission of the strain sensors. In this work, multifunctional polyionic gels with anti-freezing, water resistance, high adhesion, and wireless strain sensing ability were prepared by the one-step ultraviolet (UV) initiated copolymerization of butyl acrylate (BA), acrylic acid (AA), and 1-allyl-3-octylimidazole tetrafluoroborate ([AOIM][BF4]). The high-density ionic groups in the macromolecular chains of poly(1-allyl-3-octylimidazole tetrafluoroborate) (P[AOIM][BF4]) endowed the gels with excellent conductivity, which made the gel strain sensors suitable for monitoring the human joint movements, speech recognition, and other strain sensing. Because polybutyl acrylate (PBA) and P[AOIM][BF4] are hydrophobic polymers, water molecules are hardly dispersed into the gel matrix, and the gels could maintain good flexibility and conductivity underwater or at low temperature. The gel sensors were connected with the wireless signal transmission module, which monitored finger tapping underwater, speech recognition, and human joint movement at − 20 ℃. The anti-freezing and water-resistant properties depended on the P[AOIM][BF4] content in the gels. The anti-freezing, water resistance, and high adhesion provide the polyionic gels with new application prospects in telemedicine health, underwater communications, etc. Using UV irradiation to copolymerize ionic liquid monomers with traditional monomers for preparing the polyionic gels is efficient, environmentally friendly, and free of solvents. The strategy to fabricate the multifunctional gels could be expanded to other functional soft matters.

Graphical Abstract

The multifunctional polyionic gels could be used for underwater communication, speech recognition, and wireless motion monitoring at − 20 ℃.

防冻防水凝胶应变传感器在柔性可穿戴设备、水下通信、深海探测等方面具有很大的应用潜力。然而,大多数凝胶在水中的粘附性差、膨胀性高、拉伸性低或电导率降低,阻碍了应变传感器稳定的信号传输。本研究采用紫外引发一步共聚丙烯酸丁酯(BA)、丙烯酸(AA)和1-烯丙基-3-辛基咪唑四氟硼酸盐([AOIM][BF4])制备了具有抗冻、耐水、高粘附和无线应变传感能力的多功能多离子凝胶。聚(1-烯丙基-3-辛基咪唑四氟硼酸盐)(P[AOIM][BF4])大分子链上的高密度离子基团赋予凝胶优异的导电性,使凝胶应变传感器适用于监测人体关节运动、语音识别等应变传感。由于聚丙烯酸丁酯(PBA)和P[AOIM][BF4]是疏水聚合物,水分子很难分散到凝胶基质中,凝胶在水下或低温下都能保持良好的柔韧性和导电性。凝胶传感器与无线信号传输模块连接,监测水下手指敲击、语音识别、−20℃下人体关节运动。凝胶的防冻防水性能与P[AOIM][BF4]含量有关。其防冻、耐水、高粘附性等特点,在远程医疗卫生、水下通信等领域具有新的应用前景。利用紫外线照射将离子液体单体与传统单体共聚制备多离子凝胶,具有高效、环保、无溶剂等优点。该方法可推广到其他功能性软物质的制备中。该多功能多离子凝胶可用于- 20℃下的水下通信、语音识别和无线运动监测。
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引用次数: 0
Optimization of nanoemulsion preparation process using response surface methodology and its application in the synthesis of nano polypyrrole electrode materials 响应面法优化纳米乳制备工艺及其在纳米聚吡咯电极材料合成中的应用
IF 2.3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2025-06-27 DOI: 10.1007/s00396-025-05462-z
Zhiwei Liu, Zerui Hao, Fangnan Liang, Shuo Zhang

Oil-in-water nanoemulsions as “nanoreactors” demonstrate application potential in constructing conductive polymer-based nanofunctional materials. This study introduces response surface methodology (RSM) to optimize the preparation process of the blank nanoemulsion, which is further used to synthesize polypyrrole (PPy) electrode materials. The blank nanoemulsions were prepared via a phase inversion emulsification method using a cyclohexane/Span 80-Tween 80/water system. A three-factor, three-level Box-Behnken design (BBD) was employed to reveal the dominant effect on the average droplet size of the nanoemulsion. Under conditions of an oil-to-emulsifier mass ratio of 2:1, an oil-to-water mass ratio of 1:10, and an emulsification temperature of 60 °C, a blank nanoemulsion with an average particle size of 130.3 ± 10 nm and an emulsification index of 99% was prepared. Utilizing this blank nanoemulsion as a confined reaction medium, nano-PPy electrode materials were synthesized via nanoemulsion polymerization. It was found that when the pyrrole (Py) monomer addition is less than 20 wt% of the dispersed phase, the Py has little impact on the properties of the original nanoemulsion system. The prepared spherical nano-PPy exhibits a specific surface area of 79.2 m2 g−1 and a particle size of ~ 100.0 nm, with a relatively narrow particle size distribution. Electrochemical test results indicate that the nano-PPy exhibits a specific capacitance of 153.4 F g−1 at a current density of 0.5 A g−1. After 2000 charge–discharge cycles, the capacitance retention rate is 63.6%, higher than other traditional in situ polymerization methods. This study provides new insights into the synthesis of conductive polymer electrode materials.

Graphical abstract

水包油纳米乳液作为“纳米反应器”在构建导电聚合物基纳米功能材料方面显示出巨大的应用潜力。本研究引入响应面法(RSM)优化空白纳米乳的制备工艺,并将其用于合成聚吡咯(PPy)电极材料。采用环己烷/Span 80- tween 80/水体系,采用反相乳化法制备空白纳米乳。采用三因素三水平Box-Behnken设计(BBD)揭示了对纳米乳平均液滴尺寸的主导影响。在油与乳化剂质量比为2:1,油与水质量比为1:10,乳化温度为60℃的条件下,制得平均粒径为130.3±10 nm,乳化指数为99%的空白纳米乳。以空白纳米乳液为反应介质,采用纳米乳液聚合法制备了纳米聚吡啶电极材料。研究发现,当吡咯(Py)单体的加入量小于分散相的20% wt%时,Py对原纳米乳体系的性能影响不大。制备的球形纳米ppy比表面积为79.2 m2 g−1,粒径为~ 100.0 nm,粒径分布较窄。电化学测试结果表明,在0.5 a g−1电流密度下,纳米ppy的比电容为153.4 F g−1。经过2000次充放电循环,电容保持率为63.6%,高于其他传统的原位聚合方法。本研究为导电聚合物电极材料的合成提供了新的思路。图形抽象
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引用次数: 0
Hydrodynamic and equilibrium properties of sodium chitin/chitosan carboxymethyl ether macromolecules in dilute aqueous solution of different ionic strength 几丁质钠/壳聚糖羧甲基醚大分子在不同离子强度的稀水溶液中的水动力学和平衡性质
IF 2.3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2025-06-26 DOI: 10.1007/s00396-025-05453-0
Olga Dommes, Olga Okatova, Anna Gosteva, Georges M. Pavlov

The behavior of Na-carboxymethyl ether of chitin/chitosan (weak polyampholyte)—poly-N-acetyl-D-glucose-2-amine derivative—was studied in dilute solutions using a set of hydrodynamic methods (sedimentation velocity, translational diffusion, viscous flow of dilute solutions) in a wide range of ionic strengths from approximately 10−6 to 4.5 M NaCl. The molar masses and scaling relationships (Kuhn–Mark–Houwink–Sakurada equations) were determined in 0.2 M NaCl, where polyelectrolyte effects are virtually suppressed. The Kuhn segment length (persistent length) of chitin/chitosan Na-carboxymethyl ether chains in 0.2 M NaCl was estimated using the Multi-HYDFIT suite (A. Ortega et. al., 2011 Methods 54, 115–123. https://doi.org/10.1016/j.ymeth.2010.12.004), which is a method for computer processing of an array of experimental data obtained in a series of independent experiments. As a result, the following estimates were obtained: Kuhn segment length A = 24 ± 4 nm, hydrodynamic chain diameter d = 1.7 ± 0.7 nm. For the first time, using a method proposed earlier (G. M. Pavlov et al., 2006 Rus. J. Appl. Chem., 79(9), 1407–1412. https://doi.org/10.1134/s1070427206090035), intrinsic viscosity of Na-carboxymethyl ether of chitin/chitosan in salt-free solutions, where most strong polyelectrolyte effects were demonstrated, was estimated. Viscometric data were interpreted using the persistent cylinder theory (Yamakawa-Fujii), which led to an estimate of the equilibrium rigidity A ≥ 500 nm. This estimate is discussed within the framework of modern theories of polyelectrolyte linear chains.

Graphical Abstract

采用一套流体动力学方法(沉降速度、平移扩散、稀溶液粘性流动)研究了壳聚糖/壳聚糖(弱聚两性电解质)-聚n -乙酰- d -葡萄糖-2-胺衍生物- na -羧甲基醚在约10−6 ~ 4.5 M NaCl离子强度范围内的稀溶液行为。在0.2 M NaCl溶液中,测定了聚电解质效应几乎被抑制的摩尔质量和标度关系(Kuhn-Mark-Houwink-Sakurada方程)。利用Multi-HYDFIT套件(A. Ortega et. al. 2011 Methods 54, 115-123)估算了几丁质/壳聚糖na -羧甲基醚链在0.2 M NaCl中的库恩段长度(持续长度)。https://doi.org/10.1016/j.ymeth.2010.12.004),这是一种计算机处理一系列独立实验中获得的一系列实验数据的方法。得到库恩段长度a = 24±4 nm,水动力链直径d = 1.7±0.7 nm。第一次使用早先提出的方法(G. M. Pavlov et al., 2006 Rus。j:。化学。, 79(9), 1407-1412。https://doi.org/10.1134/s1070427206090035),几丁质/壳聚糖的na -羧甲基醚在无盐溶液中的特性粘度,其中最强的聚电解质效应被证明,估计。使用持续圆柱体理论(Yamakawa-Fujii)解释粘度数据,得出平衡刚度A≥500 nm的估计。这个估计是在聚电解质线性链的现代理论框架内讨论的。图形抽象
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引用次数: 0
First-principles study of the photoelectric properties of alkaline earth metal (Be/Mg/Ca/Sr/Ba)-doped monolayers of WSe2 碱土金属(Be/Mg/Ca/Sr/Ba)掺杂WSe2单层光电性质的第一性原理研究
IF 2.3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2025-06-26 DOI: 10.1007/s00396-025-05460-1
Jiali Liu, Zhenhua Wang, Guang-Yu Zhang, Guowen Yuan, Mohan Gao, Jinchao Ma, Hang Zheng, Zhenjia Zhou, Yuanyuan Fu, Suifeng Huo, Yuxi Yao

Based on first principles, the electronic structure and optical properties of monolayer WSe2 doped with alkaline earth metal (Be/Mg/Ca/Sr/Ba) are investigated. The results show that all doping systems exhibit excellent formation potential and structural stability. Compared with monolayer WSe2, alkaline earth metal doping induces lattice distortion and generates impurity levels. Meanwhile, the relative effective mass of electrons and holes in all doping systems is more deviated from one. Therefore, the recombination of photogenerated electron–hole pairs is effectively inhibited after doping. In addition, doping monolayer WSe2 with alkaline earth metals increases its static dielectric constant and enhances its polarizability. Notably, the Mg-WSe2 system exhibits the highest static dielectric constant, indicating the strongest polarization capacity. The absorption spectra of the doped system show a redshift in the low-energy region, which expands the response range to sunlight after the introduction of impurities. From band alignment analysis, we can conclude that other doping systems, except the Ba-WSe2 system, show superior visible light absorption and effectively inhibit photogenerated electron–hole pair recombination, indicating their potential as photocatalysts for water decomposition.

Graphical Abstract

Monolayer WSe2 within the two-dimensional transition metal dichalcogenides (TMDCs) material family exhibits broad potential in optoelectronic devices and photocatalysis owing to their direct bandgap characteristics. In this work, upon doping alkaline earth metal into a monolayer WSe2, denoted as X-WSe2 (X = Be, Mg, Ca, Sr, Ba), intriguing alterations are observed in the electronic and optoelectronic properties. Furthermore, apart from the Ba-WSe2 system, other doped systems exhibit suitable energy band edge positions, making them promising candidates for high-performance photocatalysts.

基于第一性原理,研究了碱土金属(Be/Mg/Ca/Sr/Ba)掺杂单层WSe2的电子结构和光学性质。结果表明,所有掺杂体系均表现出良好的形成势和结构稳定性。与单层WSe2相比,碱土金属掺杂引起晶格畸变,产生杂质水平。同时,所有掺杂体系中电子和空穴的相对有效质量都有较大的偏离。因此,掺杂后有效地抑制了光生电子-空穴对的复合。此外,碱土金属掺杂单层WSe2提高了其静态介电常数,增强了其极化率。值得注意的是,Mg-WSe2体系的静态介电常数最高,表明其极化能力最强。掺杂体系的吸收光谱在低能区出现红移,杂质的引入扩大了对太阳光的响应范围。从带对分析中,我们可以得出结论,除了Ba-WSe2体系外,其他掺杂体系表现出更好的可见光吸收,并有效抑制光生电子-空穴对复合,表明它们具有作为水分解光催化剂的潜力。二维过渡金属二硫族化合物(TMDCs)材料家族中的单层WSe2由于其直接带隙特性在光电子器件和光催化方面具有广阔的潜力。在这项工作中,将碱土金属掺杂到单层WSe2中,标记为X-WSe2 (X = Be, Mg, Ca, Sr, Ba),观察到电子和光电子性质的有趣变化。此外,除了Ba-WSe2体系外,其他掺杂体系都表现出合适的能带边缘位置,使它们成为高性能光催化剂的有希望的候选者。
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Colloid and Polymer Science
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