为了解决黑色页岩(BS)在作为聚合物填料应用过程中与偶联剂相互作用差、所含硫元素在加工过程中异味重等问题,本研究对黑色页岩进行煅烧加工,利用XPS、FTIR、SEM等分析了煅烧对页岩组成和形貌的影响.随后制备了煅烧BS/高密度聚乙烯(HDPE)复合材料,并测试了复合材料的热学性能、力学性能和电学性能.结果表明:煅烧去除了BS中的有机质和硫铁矿,600℃下煅烧后BS的碳原子摩尔比由35.95%下降到6.98%,而硫原子摩尔比已经不可测出,页岩保持层状结构并有片层裂碎现象,且页岩层间距略有缩小.煅烧BS/HDPE复合材料的冲击强度比天然BS/HDPE的冲击强度提升显著,这是因为煅烧后的BS与HDPE之间存在大量的界面粘接,而天然BS与HDPE之间完全分离.煅烧BS/HDPE复合材料的体积电阻率维持在4.79×1016 Ω·cm及以上,表明煅烧BS的加入对复合材料的介电性能影响较小,复合材料拥有较好的电绝缘性能.

为了研究黑色页岩作为填料应用于塑料工业的可能性,本文对桂林地区的黑色页岩进行了成分和形貌研究,发现其为纳米层状结构,主要由二氧化硅、钾长石及有机碳组成.利用不同的偶联剂与表面活性剂改性黑色页岩,制备了黑色页岩/HDPE复合材料,并对其力学性能、形貌、体积电阻率和介电常数进行了研究.结果表明:铝酸酯偶联剂与十二烷基苯磺酸钠能够改善页岩与HDPE之间的相容性,当页岩填充量为50份时,黑色页岩/HDPE复合材料的拉伸强度、冲击强度和体积电阻率有所降低,拉伸强度仍保持在23.47 MPa,冲击强度最高为6.39 kJ/m2,体积电阻率也可维持在1014 Ω·cm以上,保持了较好的力学性能和绝缘性能.

Near-infrared II (NIR-II, 1000-1700 nm) fluorescence imaging has the advantages of low light scattering and weak biological autofluorescence compared with conventional NIR (600-900 nm) fluorescence imaging and can obtain a high signal-to-noise ratio in deeper biological tissues, as well as micron-level high resolution. A great deal of effort has been directed toward the construction of conjugated polymers for effective NIR-triggered fluorescence imaging (FI) and photothermal therapy (PTT) combined therapy. However, NIR-II fluorescent materials are mainly nanoparticles prepared by coprecipitation methods, and water-soluble NIR-II materials need to be further developed. In this paper, we synthesized novel water-soluble squaric acid nanoparticles (SQ-POEGMA) with low toxicity and excellent photostability by attaching a water-soluble oligomer (POEGMA) to the small molecule squaric acid through a click chemistry reaction. The photothermal conversion efficiency of SQ-POEGMA is 33% in vitro, which can effectively inhibit the growth of cancer cells with 94% tumor inhibition rate in vivo under 808 nm laser irradiation, while no appreciable side effects were observed.

偶氮苯聚合物由于其独特的光响应性能在光分子开关、信息存储等领域具有潜在的应用,但偶氮苯顺反异构化转变及光致固液转变的影响因素仍需要更深入的研究.文中设计并合成了4种偶氮苯聚合物,对比了偶氮苯相连的柔性链对其光响应性能的影响.研究发现,引入柔性链段使偶氮苯异构化时间从20 min降到100 s,同时含柔性链段的偶氮苯聚合物具有光致固液转变的能力,而不含柔性链段的偶氮苯聚合物不能发生光致固液转变.

中国拥有丰富的黑色页岩矿物资源,制备和开发黑色页岩/聚合物复合材料对提高其利用价值及实现可持续发展有重要意义.本文首次利用热重分析对黑色页岩/HDPE复合材料的非等温热分解动力学进行了研究,运用Kissinger法和Crane法计算了黑色页岩/HDPE复合材料的热分解动力学参数.研究表明,黑色页岩对复合材料的热分解行为无明显影响,黑色页岩/HDPE复合材料热分解反应均为一阶热分解反应,热分解活化能在269.31-311.88kJ/mol之间,与纯HDPE相近.因此,黑色页岩作为填料不会增加复合材料热分解的风险,为黑色页岩的进一步开发和应用提供了基础.

The photoinduced solid-to-liquid transitions property of azobenzene-containing polymers (azopolymers) enables azopolymers with various promising applications. However, a general lack of knowledge regarding the influence of structure of the azobenzene derivatives on the photoinduced liquefaction hinders the design of novel azopolymers. In the present study, a series of azopolymers with side chains containing azobenzene unit bearing alkyl electron-donating groups were synthesized. The photoisomerization and photoinduced liquefaction properties of newly synthesized azopolymers were investigated. Alkyl-based electron-donating group significantly facilitate the photoisomerization process of azopolymers in solution, as the electron-donating ability of substituents increased, the time required for photoisomerization of azopolymers continually deceased. Meanwhile, the electron-donating group can drastically accelerate photoinduced solid-to-liquid transitions of azopolymers, the liquefaction rate of obtained azopolymers gradually getting quicker as the electron-donating ability of substituents increased. This study clearly demonstrates that the electron-donating group that bearing in the azobenzene group of polymer side chain play an essential role on the photoinduced solid-to-liquid transitions of azopolymers, and hence, gives an insight into how to design novel azopolymers for practical applications.

Fluorescence imaging in the second near-infrared window (NIR-II) holds promise for real-time deep tissue imaging. In this work, we design a low-band gap conjugated polymers(pTB) with donor-acceptor (D-A) structures by Stille cross-coupling reaction, which can improve the quality of fluorescence imaging and effectiveness of photothermal therapy. In order to improve the water solubility and biocompatibility of pTB, we adopted nano-deposition technology to envelop the hydrophobic polymer p113 into amphiphilic copolymer (1,2-distearoyl-phosphatidylethanolamine-methyl-polyethyleneglycol conjugate (DSPE-mPEG)) shells for NIR-II water-soluble nanoparticles (p113-PEG). The structure, properties and morphology of the polymer were analyzed by 1H-NMR, UV-Vis, dynamic light scattering (DLS) and transmission electron microscopy (1EM). The results show that the conjugated polymer nanoparticles have not only a good absorption peak at 831 nm, but also a large Stokes shift of 206 nm. In addition, the average hydrodynamic radius of pTB-PEG NPs was around 69 nm and spherical morphology was observed from TEM. And the nanoparticles also possess excellent photostability and good biocompatibility in physiological environment such as phosphate buffer saline (PBS), Dulbecco's Modified Eagle Medium (DMEM) and fetal bovine serum (FBS), indicating the potential for further in vivo application. More importantly, we used MTT assay to analyze photothermal treatment toward human breast cancer (4T1) cells in vifro, and confocal laser scanning microscopy (CLSM) tests further indicated that this material has a good photothermal therapeutic effect. To study the NIR-II fluorescence characters, we firstly detected the maximum imaging depth of pTB-PEG NPs in vifro. With the help of long-wavelength emission (>1000 nm), the imaging depth is 6 mm, far exceeding the traditional near-infrared region (NIR-I) reagents. Under 808 nm laser irradiation, the high-resolution second near-infrared window (NIR-II) fluorescence imaging of healthy mouses' blood vascular system and tumor-bearing mice was effectively achieved. In general, conjugated polymer nanoparticles (pTB-PEG) have a good biocompatibility, excellent light stability and good optical properties. It is a promising NIR-II imaging probe with a wide range of the potential for clinical imaging and live tumor imaging.

Application of 1064 nm activatable NIR-IIa fluorescence imaging (FI) and NIR-II photothermal therapy (PTT) results in high-resolution imaging and good deep-tissue therapy, respectively. Combining NIR-IIa FI with NIR-II PTT may allow precise diagnosis guided efficient treatment of deep-tissue tumors. However, designing a 1064 activatable theranostic nanoplatform using a single dye for both NIR-IIa FI and NIR-II PTT is a challenge. Herein, we synthesized squaraine-based semiconducting polymer nanoparticles (PSQPNs-DBCO) that were excited by a 1064 nm laser for precise NIR-IIa fluorescence imaging guided NIR-II PTT treatment. Combined with bioorthogonal labeling technology, the PSQPNs-DBCO largely accumulated in the tumor section, extremely enhancing signal-to-background ratio (SBR) of imaging and NIR-II PTT efficiency of tumor in live colorectal-bearing animals.

通过湿法涂覆和自由发泡法,制备了发泡NBR-金属复合密封板,对比了传统发泡剂(OBSH)与微球发泡剂对发泡NBR微观形貌的影响,探索了不同微球发泡剂的发泡倍率,并研究了发泡剂用量、发泡温度对密封板发泡的影响.结果 表明,聚合物发泡微球与NBR硫化体系的配合性优于传统发泡剂OBSH,利用微球发泡剂可制备厚度为1200 μm,发泡倍率高达4.40的发泡NBR-金属复合密封板;扫描电镜结果说明,复合密封板的发泡均匀,具有良好的耐油性及力学性能.

MNSiO 2 /CN40/PF nanocomposites have been fabricated in this study. Nano‐SiO 2 was initially surface‐modified with γ‐methacryloxypropyl trimethoxysilane (MPS). The resulting nano‐SiO 2 was denoted as MNSiO 2 . Core‐shell composites, MNSiO 2 /CN40, was fabricated by a solution blending method, in which MNSiO 2 served as the core and liquid acrylonitrile butadiene rubber (CN40) served as shell. Phenol formaldehyde resins (PF) were prepared by means of condensation polymerization method. MNSiO 2 /CN40/PF hybrid with a fixed weight ratio (2:98) of MNSiO 2 /CN40 composites to PF were prepared by a modified routine of preparation of pure PF. MNSiO 2 /CN40/PF nanocomposites were prepared by incorporating filler particles with MNSiO 2 /CN40/PF hybrid via melt blending, followed by compression molding method. The impact of MNSiO 2 content on the properties of the MNSiO 2 /CN40/PF nanocomposites was systematically investigated by varying the weight ratio of MNSiO 2 to CN40 in MNSiO 2 /CN40 core‐shell composites. The results revealed that MNSiO 2 /CN40 significantly enhanced the mechanical and frictional properties of the as‐prepared MNSiO 2 /CN40/PF nanocomposites. Compared to pure PF, the impact strength of MNSiO 2 /CN40/PF hybrid containing 1.0 wt% of MNSiO 2 in MNSiO 2 /CN40 composites increased by 29.2%, and the initial storage modulus was enhanced dramatically. In addition, MNSiO 2 /CN40/PF hybrid demonstrated stable friction coefficient, while the wear mechanism of pure PF was adhesive and fatigue wear. The MNSiO 2 /CN40/PF nanocomposites exhibited a combination of adhesive, abrasive, and fatigue wear. POLYM. COMPOS., 40:179–186, 2019. © 2017 Society of Plastics Engineers

A novel organic–inorganic hybrid particle (JF633-SBA-15A) was successfully prepared by solution blending method using hybrid hyperbranched polyether polyol (JF633) and surface-modified mesoporous (SBA-15). Further, JF633-SBA-15A/EP composites were fabricated by melt-blending method. The structure and morphology of JF633-SBA-15A were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetry analysis, nitrogen adsorption–desorption, and scanning electron microscopy. The mechanical and dynamic mechanical properties of JF633-SBA-15A/EP were also studied. The results demonstrated that the prepared JF633-SBA-15A hybrid particles had excellent thermal stability and unique mesoporous structural characteristics. Compared with pure EP, the maximum degradation temperature of the composites decreased and the thermal stability increased at high temperature. Notably, the JF633-SBA-15A/EP composite had better comprehensive performance. The impact strength and temperature of the glass transition (Tg) of JF633-SBA-15A/EP composites with 1.0 wt% JF633-SBA-15A increased by 32% and 23 °C, respectively. SEM images of the cross-section of the composite which reinforced with hybrid particles exhibited a rough surface and multiple dimples, indicating a ductile fracture.

In situ studies of the aggregation behavior of traditional surfactants at the liquid interface using spectroscopic methods are often significantly affected by the large volume of fluorescent groups, such as pyrene. Fluorescent-Gemini surfactants provide an ideal solution since the fluorescent block can be designed as a spacer or a tail. In this work, we report the synthesis of a new fluorescent-Gemini surfactant with a rigid spacer (referred to as 8-TBT-8). The aggregation behavior and application in cell-membrane imaging were investigated. The unique aggregation behavior in an organic solvent and aqueous solution was studied using spectroscopy. UV-vis and photoluminescence spectra of 8-TBT-8 revealed that this new fluorescent surfactant forms H aggregates in organic solution to give blue emission, whereas it forms J aggregates in aqueous solution to give green fluorescence under UV light. In addition, the fluorescence intensity of 8-TBT-8 increases abruptly at concentrations higher than the critical micellization concentration. Good photostability and a unique structure make the synthesized Gemini surfactant very suitable for membrane imaging.

Phototherapy has great promise for precise cancer diagnosis and effective therapy, but the development of one multifunctional nanoplatform for synergistic photodynamic therapy (PDT) and photothermal therapy (PTT) at a single excitation wavelength remains a challenge. In this work, a perylene diimide zwitterionic polymer PDS-PDI was synthesized via atom transfer radical polymerization (ATRP). This polymer was designed for photoacoustic imaging (PAI) guided synergistic PDT and PTT with single 660 nm near-infrared (NIR) light irradiation. The prepared PDS-PDI polymer presents high photothermal conversion efficiency (η ≈ 40%) and efficient singlet oxygen quantum yield (ΦΔ ≈ 16.7%) under 660 nm laser irradiation. Polymer PDS-PDI also acts as a contrast agent for PAI, offering real-time monitoring in tumor sites. Additionally, in vitro and in vivo assays indicate that polymer PDS-PDI has good biocompatibility and effective tumor destruction ability under 660 nm laser irradiation. In brief, polymer PDS-PDI prepared in this study could be applied as a dual-mode phototherapeutic agent under single laser irradiation.

Water-soluble zwitterionic diketopyrrolopyrrole (DPP-SPMA) for fluorescence/photoacoustic imaging guided photodynamic/photothermal therapy with favorable renal excretion and ultralow cytotoxicity.

Superhydrophobic and oleophilic sponges have been demonstrated as promising candidates for oil/water separation. However, there are still challenges in large-scale fabrication of superhydrophobic sponges with low cost and feasible method for industrial applications. Herein, we report a superhydrophobic and oleophilic melamine sponge functionalized by a uniform polydimethylsiloxane (PDMS) film that can be easily coated onto the sponge skeleton through UV-assisted thiol-ene click reactions. The PDMS films are characterized by a hierarchically striped microstructure with an average distance less than 2 μm. Because of the striped microstructure and the hydrophobic property of silicone, a high contact angle of 156.2° was achieved. Importantly, the interconnected open-cell structure of the melamine sponge was preserved by adapting the thickness of the PDMS film. The PDMS-coated melamine sponge exhibited a desirable absorption capacity of 103-179 times its own weight with oils and organic solvents. The excellent mechanical properties of melamine and the flexibility of PDMS enable the PDMS-coated melamine sponges to be squeezed repeatedly without collapsing. This study offers a robust and effective approach in large-scale preparation of a superhydrophobic sponge for large-scale oil spill containment and environmental remediation by the inexpensive commercial polymethylvinylsilicone and facile dip-coating/UV-curing method.

通过Suzuki偶联反应和傅克酰基化反应制得了一系列新型的以共轭荧光分子噻吩-苯-噻吩为连接链的双子表面活性剂,利用季铵化反应在共轭链的两侧修饰亲水单元,合成了新型的具有不同疏水链长的季铵盐型双子表面活性剂(m-TBT-m),其结构和性能经UV-Vis,FL和1 H NMR表征.结果表明:8-TBT-8、10-TBT-10、12-TBT-12、14-TBT-14及16-TBT-16的临界胶束浓度(CMC)分别为1×10-6mol·L-1、4×10-6mol·L-1、1×10-5 mol·L-1、2×10-5 mol·L-1和4×10-5 mol·L-1.

We introduce a novel strategy to enhance the fluorescence brightness of organic-molecule-based nanoparticles in the second near-infrared window (NIR-II, 1000-1700 nm) by fabricating J-aggregate nanoparticles SQP-NPs(J). Our prepared J-aggregate nanoparticles SQP-NPs(J) show an emission maximum near 1100 nm, and the emission intensity is 4.8-fold higher than that of H-aggregate SQP-NPs(H). In addition, SQP-NPs(J) can be used for NIR-II imaging guided photothermal therapy on MCF-7 tumor-bearing mice due to the fact that SQP-NPs(J) have highly effective photothermal properties, which are significant for precise tumor diagnostics and treatments.

Near-infrared (NIR) absorbing nanoagents with functions of photoacoustic imaging (PAI) and photothermal therapy (PTT) have received great attention for cancer therapy. However, endowing them with multifunctions, especially targeting ability, for enhancing in vivo PAI/PTT generally suffers from the problems of synthetic complexity and low surface density of function groups. We herein report high density glycopolymers coated perylenediimide nanoparticles (PLAC-PDI NPs), self-assembled by poly(lactose)-modified perylenediimide (PLAC-PDI), as tumor-targeted PAI/PTT nanoagents. Atom transfer radical polymerization and click reaction were used in sequence to prepare PLAC-PDI, which can accurately control the content of poly(lactose) (PLAC) in PLAC-PDI and endow PLAC-PDI NPs with high density PLAC surface. The high density PLAC surface provided NPs with long-time colloidal stability, outstanding stability in serum and light, and specific targeting ability to cancer cells and tumors. Meanwhile, PLAC-PDI NPs also presented high photothermal conversion efficiency of 42% by virtue of strong π-π interactions among perylenediimide molecules. In living mice, PAI experiments revealed that PLAC-PDI NPs exhibited effective targeting ability and enhanced PTT efficacy to HepG2 tumor compared with control groups, lactose blocking, and ASGP-R negative tumor groups. Overall, our work provids new insights for designing glycopolymers-based therapeutic nanoagents for efficient tumor imaging and antitumor therapy.

A glycopolymer modified water-soluble conjugated polymer brush was developed for Hep G2 tumor targeted photodynamic therapy.

Combination of photodynamic therapy (PDT) with small interfering RNA (siRNA) therapy has become a major strategy in cancer treatment for enhancing anticancer efficacy. However, developing nanoplatform that can promote siRNA release and collaborate with efficient PDT under NIR light irradiation is still a big challenge. Photo‐induced charge‐variable conjugated polyelectrolyte brushes encapsulating upconversion nanoparticles (UCNP@CCPEB) as an efficient nanoplatform are reported. Cationic conjugated polyelectrolyte brush (CCPEB) is synthesized through quaternary ammoniation of N‐functionalized polyfluorene brush by photodegradable 2‐nitrobenzyl‐2‐bromoacetate. CCPEB with abundant positive charges and intrinsic photosensitizer (PS) performance is good for integrating siRNA carrier and PS into one molecule. The obtained CCPEB next encapsulates upconversion nanoparticle for realizing its NIR light excitation. Agarose gel electrophoresis experiments show that UCNP@CCPEB present good stability and excellent siRNA‐loading capacity (1 mol UCNP@CCPEB to at least 32.5 mol siRNA). Under 980 nm light irradiation, UCNP@CCPEB exhibit efficient single oxygen production for PDT. Concurrently, the photoresponsive cationic side‐chain of CCPEB turns into zwitterionic chain and thus accelerates its siRNA release to 80%. In vitro and in vivo experiments show that the successful A549 tumor suppression is achieved by UCNP@CCPEB/siPlk1 complex under 980 irradiation. It is envisioned that UCNP@CCPEB can serve as an efficient platform for combining various phototherapies together.