在硫基功能化碳纳米管上组装壳层厚度可控的Au@Pt核壳纳米粒子以获得高的甲醇电催化氧化活性

本工作致力于研究核壳结构Au@Pt 纳米粒子(Au@Pt NPs)在多壁碳纳米管(MWCNTs)上的组装,试图获得高的甲醇电催化氧化活性。利用光化学晶种生长法合成了Au@Pt NPs,并通过改变Au与Pt的原子比来控制壳层(Pt层)的厚度,然后将不同壳层厚度的Au@Pt NPs组装到巯基(-SH)功能化的MWCNTs上,获得了一系列Au@Pt/MWCNTs复合物。应用透射电子显微镜(TEM)和X射线光电子能谱(XPS)研究了Au@Pt NPs和Au@Pt/MWCNTs复合物的形貌结构、表面化学组成和化学价态,并结合电化学方法研究了Au@Pt NPs的Pt壳层厚度对其组装效果的影响,以及测试了Au@Pt/MWCNTs催化剂对甲醇的电催化氧化的活性。结果表明,Au@Pt NPs通过其表面的Au或Pt与MWCNTs上的-SH形成共价键,从而实现Au@Pt NPs在MWCNTs上的组装。Pt壳层厚度对Au@Pt NPs在MWCNTs上组装的影响较大:当Pt壳层没有完全包裹Au核时,Au@Pt NPs表面暴露的Au促进了Au@Pt NPs在MWCNTs上的组装;而当Pt壳层完全包裹Au核时,Au@Pt NPs表面呈氧化态的Pt(Ⅱ)则对核壳纳米粒子的组装不利。Au、Pt原子比例为1∶1时,Au@Pt NPs能均匀地组装在MWCNTs上,且Au@Pt/MWCNTs(1∶1)催化剂对甲醇的电催化氧化具有较高的活性和稳定性。     

核壳型量子点-纳米金颗粒组装体高效检测神经性毒剂模拟剂

实验设计制备了一种由12层硫化锌包覆硒化镉的核壳型量子点(CdSe/12ZnS QDs)和纳米金颗粒(Au NPs)自组装形成的CdSe/12ZnS QDs/Au NPs复合结构, 并将其应用于神经性毒剂模拟剂氰基磷酸二乙酯(Diethyl Cyanophosphonate, DCNP)的高效检测。QDs由于与Au NPs存在荧光共振能量转移作用(Fluorescence Resonance Energy Transfer, FRET)而发生荧光猝灭, 乙酰胆碱酯酶(AChE)水解氯化硫代乙酰胆碱(ATC)生成的硫胆碱能够将量子点取代而使量子点荧光恢复。当QDs与Au NPs的摩尔浓度比为20 : 1时, QDs荧光猝灭效果最佳, AChE浓度为1.0×10 ^-3 U/L时, QDs荧光恢复效果最好。DCNP的存在会抑制AChE的活性, 减少硫胆碱的生成并降低QDs的荧光恢复效率, 通过对QDs荧光恢复效率测定能够检测DCNP。在最优条件下对DCNP的检测结果表明, 量子点的荧光恢复效率与DCNP浓度的对数在5.0×10 ^-9~5.0×10 ^-4mol/L的范围内存在良好的线性关系, 检出限达5.0×10 ^-9mol/L。     

苯乙烯-马来酸酐共聚物/氧化锌纳米粒子合成与表征

以N,N-二甲基甲酰胺为溶剂,乙酸锌为前驱物,苯乙烯-马来酸酐共聚物为大分子稳定剂,采用溶液化学法,制备了氧化锌纳米粒子。通过紫外-可见吸收光谱(UV-Vis)、荧光光谱(PL)、透射电子显微镜(TEM)等方法对合成的ZnO纳米粒子样品进行表征。结果表明,所合成样品具有量子尺寸效应,样品UV-Vis吸收光谱在350nm给出氧化锌纳米粒子的特征吸收峰,样品PL光谱显示在410nm处可产生明显的荧光发射。氧化锌纳米粒子的尺寸在50~100nm且粒径分布较窄,表明苯乙烯-马来酸酐共聚物对氧化锌纳米粒子的表面起到了良好稳定作用。     

SBS-OH模板制备CdS纳米粒子及表征

以SBS为基本原料,通过大分子化学反应制备得到羟基化SBS(SBS-OH).以N,N-二甲基甲酰胺为溶剂,SBS-OH为模板,乙酸镉及硫化钠为前驱物,在常温条件下"原位反应"制备得到CdS纳米粒子.通过UV-Vis、PL系统考察了SBS-OH浓度、前驱物浓度及配比等因素对CdS纳米粒子光学性质的影响.通过TEM对CdS纳米粒子的尺寸及形貌进行了表征.研究表明,利用SBS-OH的两亲性质,可以在极性溶剂DMF中得到具有冠状复合结构的CdS纳米粒子.随着前驱物浓度的增加,CdS纳米粒子的吸收强度增加,吸收带边红移,表现出较明显的量子尺寸效应.PL光谱表明CdS纳米粒子可以产生表面缺陷态的荧光发光特性,通过对实验结果的总结分析,探讨了复合结构CdS纳米粒子可能的形成机制.     

纳米材料在光动力治疗肿瘤领域的应用

光动力治疗(PDT),是由光敏剂(或者其纳米粒子)介导,在光的作用下,使生物分子和细胞发生形态或功能上的变化,从而诱导组织细胞损伤及坏死,被称为光敏化-氧化作用的一种非侵入治疗手段。光敏剂纳米粒子、光、单线态氧是光动力疗法的三个重要元素。目前,PDT在临床上主要应用于恶性肿瘤的治疗,具有高选择性、低毒性、微创性、靶向性好、重复治疗、治疗时间短、可与放疗和化疗协同作用等优势,在肿瘤治疗领域具有非常广泛的应用前景。根据已有文献对肿瘤的光动力治疗方法进行了综述,介绍了光敏剂(主要是纳米粒子)和光动力治疗的研究现状,展望了其未来发展方向。研究结果发现以光敏剂纳米粒子为基础的光动力治疗对肿瘤组织具有特异性吸收和滞留作用,特别对体积较小、浅表肿瘤疗效显著,对恶性肿瘤治疗也有很好的辅助作用,在肿瘤治疗领域具有广阔的应用前景。     

聚乙烯吡咯烷酮表面修饰氧化锌纳米粒子的合成与表征

以N,N-二甲基甲酰胺为溶剂,乙酸锌为前驱物,聚乙烯吡咯烷酮为表面修饰剂,采用溶液化学法,制备了氧化锌纳米粒子。通过紫外-可见吸收光谱(UV-Vis)、荧光光谱(FL)和透射电子显微镜(TEM)等方法对合成的氧化锌纳米粒子进行表征。结果表明:所合成样品具有量子尺寸效应,样品UV-Vis吸收光谱在335~350 nm给出了氧化锌纳米粒子的特征吸收峰;FL光谱显示在400,550 nm处产生荧光发射;氧化锌纳米粒子的尺寸在100 nm左右且粒径分布较窄,表明聚乙烯吡咯烷酮对氧化锌纳米粒子的表面起到良好的修饰作用。     

聚3-甲基噻吩修饰量子点硫化镉连接纳米结构TiO2复合膜电极光电化学研究

采用原位化学法在纳米结构TiO2电极上制备了量子点CdS(Q-CdS),并用电化学方法在TiO2/QCdS表面聚合3-甲基噻吩po1y(3-Methylthiophene)(PMeT).通过对PMeT修饰Q-CdS连接TiO2纳米结构膜的研究表明,PMeT和Q-CdS单独修饰纳米结构TiO2电极和PMeT修饰Q-CdS连接纳米结构TiO2电极的光电流产生的起始波长都向长波方向移动;一定条件下在可见光区光电转换效率均较纳米结构TiO2的光电转换效率有明显的提高;聚3-甲基噻吩(PMeT)与Q-CdS连接的纳米结构TiO2之间存在p-n异质结.在一定条件下p-n异质结的存在有利于光生电子/空穴的分离,提高了光电转换效率.     

聚苯乙烯-金纳米复合材料的可控组装及表面增强拉曼散射性能

无皂乳液聚合制备单分散聚苯乙烯(PS)微球,经过阳离子化后,在其表面通过界面可控自组装方法修饰金纳米粒子(Au NPs)制备PS-Au复合物SERS基底,通过调制组装体系中Au NPs数量控制PS微球表面金纳米粒子密度。采用紫外-可见吸收光谱、扫描电子显微镜、热重分析和拉曼光谱对PS微球及PS-Au复合物的表面形貌、组成及性能进行了表征。结果显示,金纳米粒子尺寸为40 nm、体积为3 mL时,组装得到的PS-Au复合材料具有较好的分散性和稳定性,并展现出较好的表面增强拉曼散射(SERS)活性,其增强因子达到10~5。该复合物材料作为增强基底进一步被应用于农药福美双的SERS检测,其灵敏度达到0.1×10~(-6)。     

代数对芳基苄醚树枝状酞菁硅(Ⅳ)光敏产生单线态氧的影响

光敏剂产生单线态氧的能力是评价其光动力活性的因素之一。采用2,5-二甲基呋喃为吸收剂,通过高效液相色谱法研究了1-3代硝基芳基苄醚树枝配体轴向取代酞菁硅(Ⅳ)单线态氧的生成速率、生成速率常数及量子产率。结果表明,轴向取代酞菁硅(Ⅳ)单线态氧的生成速率和生成速率常数均随着树枝代数的增加而逐渐增大,低代的树枝配体轴向取代酞菁硅(Ⅳ)的单线态氧量子产率较高,这可能与不同代树枝配体对酞菁核的位点分离有关。研究将为开发轴向取代酞菁硅(Ⅳ)配合物作为新型光敏剂提供重要的理论参考。     

纳米粒子自组装无机硅/有机硅复合功能膜技术

采用自组装法对纳米粒子表面进行修饰,修饰效果表明:控制了纳米粒子的表面态,使纳米粒子稳定化;赋予纳米粒子无机硅/有机硅复合功能膜,使纳米粒子适用性广、高性能、多功能;不仅扩大了在传统产业中的应用范围,而且还可作为纳米结构的结构单元,用于自组装纳米功能器件等纳米结构材料.文中介绍了这一技术的原理、工艺、修饰效果以及特点.     

A Versatile Theranostic Nanoplatform with Aggregation-Induced Emission Properties: Fluorescence Monitoring,Cellular Organelle Targeting,and Image-Guided Photodynamic Therapy

Photosensitizers (PSs) play a key role in the photodynamic therapy (PDT) of tumors. However, commonly used PSs are prone to intrinsic fluorescence aggregation-caused quenching and photobleaching; this drawback severely limits the clinical application of PDT, necessitating new phototheranostic agents. Herein, a multifunctional theranostic nanoplatform (named TTCBTA NP) is designed and constructed to achieve fluorescence monitoring, lysosome-specific targeting, and image-guided PDT. TTCBTA with a twisted conformation and D-A structure is encapsulated in amphiphilic Pluronic F127 to form nanoparticles (NPs) in ultrapure water. The NPs exhibit biocompatibility, high stability, strong near-infrared emission, and desirable reactive oxygen species (ROSs) production capacity. The TTCBTA NPs also show high-efficiency photo-damage, negligible dark toxicity, excellent fluorescent tracing, and high accumulation in lysosome for tumor cells. Furthermore, TTCBTA NPs are used to obtain fluorescence images with good resolution of MCF-7 tumors in xenografted BALB/c nude mice. Crucially, TTCBTA NPs present a strong tumor ablation ability and image-guided PDT effect by generating abundant ROSs upon laser irradiation. These results demonstrate that the TTCBTA NP theranostic nanoplatform may enable highly efficient near-infrared fluorescence image-guided PDT.     

Heavy-atomic construction of photosensitizer nanoparticles for enhanced photodynamic therapy of cancer

A new type of heavy-atom-affected Pluronic (F-127) nanoparticle (FIC NP) for photodynamic therapy (PDT) is reported. FIC NPs are formulated with biocompatible constituents, and contain densely integrated iodinated aromatic molecules that form a structurally rigid core matrix and stably encapsulate photosensitizers in a monomeric form. Tiny nanoparticles (≈10 nm) are prepared by aqueous dispersion of photosensitizer-embedded aromatic nanodomains, which self-assemble by phase separation from the Pluronic melt mixture. By using spectroscopic studies and cellular experiments, the following is demonstrated: 1) enhanced singlet-oxygen generation by means of the intraparticle heavy-atom effect on the embedded photosensitizer, 2) facilitated cell uptake due to the small nanoscopic size as well as the Pluronic surface characteristics, and thereby 3) actual enhancement of PDT efficacy for a human breast-cancer cell line (MDA-MB-231), which validates a photophysically motivated nanoformulation approach toward an advanced photosensitizing nanomedicine.     

First Demonstration of Gold Nanorods‐Mediated Photodynamic Therapeutic Destruction of Tumors via Near Infra‐Red Light Activation

Previously, a large volume of papers reports that gold nanorods (Au NRs) are able to effectively kill cancer cells upon high laser doses (usually 808 nm, 1–48 W/cm²) irradiation, leading to hyperthermia‐induced destruction of cancer cells, i.e, photothermal therapy (PTT) effects. Combination of Au NRs‐mediated PTT and organic photosensitizers‐mediated photodynamic therapy (PDT) were also reported to achieve synergistic PTT and PDT effects on killing cancer cells. Herein, we demonstrate for the first time that Au NRs alone can sensitize formation of singlet oxygen (¹O₂) and exert dramatic PDT effects on complete destrcution of tumors in mice under very low LED/laser doses of single photon NIR (915 nm, <130 mW/cm²) light excitation. By changing the NIR light excitation wavelengths, Au NRs‐mediated phototherapeutic effects can be switched from PDT to PTT or combination of both. Both PDT and PTT effects were confirmed by measurements of reactive oxygen species (ROS) and heat shock protein (HSP 70), singlet oxygen sensor green (SOSG) sensing, and sodium azide quenching in cellular experiments. In vivo mice experiments further show that the PDT effect via irradiation of Au NRs by 915 nm can destruct the B16F0 melanoma tumor in mice far more effectively than doxorubicin (a clinically used anti‐cancer drug) as well as the PTT effect (via irradiation of Au NRs by 780 nm light). In addition, we show that Au NRs can emit single photon‐induced fluorescence to illustrate their in vivo locations/distribution.     

Array of ZnO nanoparticle-sensitized ZnO nanorods for UV photodetection

Vertically aligned ZnO nanorod (NR) arrays have been successfully synthesized on ITO-glass substrate by hydrothermal growth. Chemical bath deposition method was used to deposit ZnO nanoparticles (NPs) onto the ZnO NRs. These structures were applied in fabricating ZnO NPs sensitized ultraviolet (UV) photodetectors (PDs). Incorporation of ZnO NPs onto ZnO NRs results in distinct improvement of optical properties of ZnO NRs, i.e., significant enhancement of emission as well as effective suppression of defects emission in ZnO. Furthermore, there is a noticeable blue-shift in absorption spectra compared with that of ZnO NRs structure. I–V characteristics show that the sensitized structure improved photocurrent almost twice that of unsensitized ZnO NRs. Consequently, these findings may open new opportunities for the integration of different ZnO nanostructures for application in UV region particularly fabrication of UV PDs.     

Precise Two‐Photon Photodynamic Therapy using an Efficient Photosensitizer with Aggregation‐Induced Emission Characteristics

Two‐photon photodynamic therapy (PDT) is able to offer precise 3D manipulation of treatment volumes, providing a target level that is unattainable with current therapeutic techniques. The advancement of this technique is greatly hampered by the availability of photosensitizers with large two‐photon absorption (TPA) cross section, high reactive‐oxygen‐species (ROS) generation efficiency, and bright two‐photon fluorescence. Here, an effective photosensitizer with aggregation‐induced emission (AIE) characteristics is synthesized, characterized, and encapsulated into an amphiphilic block copolymer to form organic dots for two‐photon PDT applications. The AIE dots possess large TPA cross section, high ROS generation efficiency, and excellent photostability and biocompatibility, which overcomes the limitations of many conventional two‐photon photosensitizers. Outstanding therapeutic performance of the AIE dots in two‐photon PDT is demonstrated using in vitro cancer cell ablation and in vivo brain‐blood‐vessel closure as examples. This shows therapy precision up to 5 µm under two‐photon excitation.     

HClO-Activated Fluorescence and Photosensitization from an AIE Nanoprobe for Image-Guided Bacterial Ablation in Phagocytes

Bacteria hiding in host phagocytes are difficult to kill, which can cause phagocyte disorders resulting in local and systemic tissue damage. Effective accumulation of activatable photosensitizers (PSs) in phagocytes to realize selective imaging and on-demand photodynamic ablation of bacteria is of great scientific and practical interests for precise bacteria diagnosis and treatment. Herein, HClO-activatable theranostic nanoprobes, DTF-FFP NPs, for image-guided bacterial ablation in phagocytes are introduced. DTF-FFP NPs are prepared by nanoprecipitation of an HClO-responsive near-infrared molecule FFP and an efficient PS DTF with aggregation-induced emission characteristic using an amphiphilic polymer Pluronic F127 as the encapsulation matrix. As an energy acceptor, FFP can quench both fluorescence and production of reactive oxygen species (ROS) of DTF, thus eliminating the phototoxicity of DTF-FFP NPs in normal cells and tissues. Once delivered to the infection sites, DTF-FFP NPs light up with red fluorescence and efficiently generate ROS owing to the degradation of FFP by the stimulated release of HClO in phagocytes. The selective activation of fluorescence and photosensitization is successfully confirmed by both in vitro and in vivo results, demonstrating the effectiveness and theranostic potential of DTF-FFP NPs in precise bacterial therapy.     

Spatiotemporally Synchronous Oxygen Self-Supply and Reactive Oxygen Species Production on Z-Scheme Heterostructures for Hypoxic Tumor Therapy

Photodynamic therapy (PDT) efficacy has been severely limited by oxygen (O₂) deficiency in tumors and the electron–hole separation inefficiency in photosensitizers, especially the long-range diffusion of O₂ toward photosensitizers during the PDT process. Herein, novel bismuth sulfide (Bi₂S₃)@bismuth (Bi) Z-scheme heterostructured nanorods (NRs) are designed to realize the spatiotemporally synchronous O₂ self-supply and production of reactive oxygen species for hypoxic tumor therapy. Both narrow-bandgap Bi₂S₃ and Bi components can be excited by a near-infrared laser to generate abundant electrons and holes. The Z-scheme heterostructure endows Bi₂S₃@Bi NRs with an efficient electron–hole separation ability and potent redox potentials, where the hole on the valence band of Bi₂S₃ can react with water to supply O₂ for the electron on the conduction band of Bi to produce reactive oxygen species. The Bi₂S₃@Bi NRs overcome the major obstacles of conventional photosensitizers during the PDT process and exhibit a promising phototherapeutic effect, supplying a new strategy for hypoxic tumor elimination.     

Enhancing Photodynamic Therapy through Resonance Energy Transfer Constructed Near‐Infrared Photosensitized Nanoparticles

Photodynamic therapy (PDT) is an important cancer treatment modality due to its minimally invasive nature. However, the efficiency of existing PDT drug molecules in the deep‐tissue‐penetrable near‐infrared (NIR) region has been the major hurdle that has hindered further development and clinical usage of PDT. Thus, herein a strategy is presented to utilize a resonance energy transfer (RET) mechanism to construct a novel dyad photosensitizer which is able to dramatically boost NIR photon utility and enhance singlet oxygen generation. In this work, the energy donor moiety (distyryl‐BODIPY) is connected to a photosensitizer (i.e., diiodo‐distyryl‐BODIPY) to form a dyad molecule ( RET‐BDP ). The resulting RET‐BDP shows significantly enhanced absorption and singlet oxygen efficiency relative to that of the acceptor moiety of the photosensitizer alone in the NIR range. After being encapsulated with biodegradable copolymer pluronic F‐127‐folic acid (F‐127‐FA), RET‐BDP molecules can form uniform and small organic nanoparticles that are water soluble and tumor targetable. Used in conjunction with an exceptionally low‐power NIR LED light irradiation (10 mW cm^?2), these nanoparticles show superior tumor‐targeted therapeutic PDT effects against cancer cells both in vitro and in vivo relative to unmodified photosensitizers. This study offers a new method to expand the options for designing NIR‐absorbing photosensitizers for future clinical cancer treatments.     

A Highly Efficient and Photostable Photosensitizer with Near‐Infrared Aggregation‐Induced Emission for Image‐Guided Photodynamic Anticancer Therapy

Photodynamic therapy (PDT), which relies on photosensitizers (PS) and light to generate reactive oxygen species to kill cancer cells or bacteria, has attracted much attention in recent years. PSs with both bright emission and efficient singlet oxygen generation have also been used for image‐guided PDT. However, simultaneously achieving effective ¹O₂ generation, long wavelength absorption, and stable near‐infrared (NIR) emission with low dark toxicity in a single PS remains challenging. In addition, it is well known that when traditional PSs are made into nanoparticles, they encounter quenched fluorescence and reduced ¹O₂ production. In this contribution, these challenging issues have been successfully addressed through designing the first photostable photosensitizer with aggregation‐induced NIR emission and very effective ¹O₂ generation in aggregate state. The yielded nanoparticles show very effective ¹O₂ generation, bright NIR fluorescence centered at 820 nm, excellent photostability, good biocompatibility, and negligible dark in vivo toxicity. Both in vitro and in vivo experiments prove that the nanoparticles are excellent candidates for image‐guided photodynamic anticancer therapy.     

Polypeptide-based artificial erythrocytes conjugated with near infrared photosensitizers for imaging-guided photodynamic therapy

Photodynamic therapy (PDT) combining with near infrared (NIR) imaging is attractive. However, the intrinsic hypoxia in tumor and consumption of oxygen during treatment will decrease PDT. Here an artificial red cell was prepared using polypeptides conjugated hemoglobin as an oxygen carrier. A NIR photosensitizer-brominated 4,4-difluoro-4-bora-3a,a-diaza-s-indacene (BODIPY-Br₂) possessing both high fluorescence emission and singlet oxygen generation efficiency was synthesized and also conjugated to polypeptides to achieve NIR imaging-guided PDT. In vitro studies performed on HepG2 cancer cells verified the oxygen carrier, cancer tracing and curing abilities of the as-prepared polymeric nanoparticles. Even under hypoxia condition, it also obviously increases the cell killing rate when exposed light at a low energy (25 mW/cm², 10 min). Meanwhile, the fluorescence of BODIPY in NPs would light up cells for real-time imaging. These results show the potential of the biocompatible and biodegradable P-Hb-B NPs for enhancement of simultaneous tracing and treating of cancer.