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Preparation and characterization of an improved Cu(2+)-cyclen polyurethane material that catalyzes generation of nitric oxide from S-nitrosothiols. s -亚硝基硫醇催化生成一氧化氮的Cu(2+)-环聚氨酯材料的制备与表征
Pub Date : 2012-01-01 Epub Date: 2012-08-03 DOI: 10.1039/C2JM32726K
Kun Liu, Mark E Meyerhoff

A new, stable and highly efficient Cu(2+)-cyclen-polyurethane material is described and shown to exhibit improved performance compared to prior materials for the catalytic decomposition of S-nitrosothiols to physiologically active nitric oxide.

介绍了一种稳定高效的新型Cu(2+)循环聚氨酯材料,与现有材料相比,该材料在催化s -亚硝基硫醇分解为生理活性一氧化氮方面表现出更好的性能。
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引用次数: 24
Morphology-controlled synthesis of silica nanotubes through pH- and sequence-responsive morphological change of bacterial flagellar biotemplates. 细菌鞭毛生物模板pH和序列响应的形态变化调控二氧化硅纳米管的合成。
Pub Date : 2012-01-01 Epub Date: 2012-05-21 DOI: 10.1039/C2JM31034A
Dong Li, Xuewei Qu, Salete M C Newton, Philip E Klebba, Chuanbin Mao

Bacterial flagella are naturally-occurring self-assembling protein nanofibers protruding from the bacterial surface to assist the swimming of bacteria. They are rigid and exhibit diverse morphologies depending on the ionic strength, the pH values, temperature, and subunit sequences. Here, the silica nanotubes (SNTs) with controllable morphologies were synthesized using flagella as biological templates in aqueous solution under mild conditions. The morphologies and surface features of flagella-templated SNTs can be simply tuned by adjusting the pH value or surface chemistry of flagella by peptide display. A variety of different morphologies (coiled, straight, and curly with different wavelengths) and surface features (smooth, rough, granular and pear-necklace-like) of SNTs were obtained. When pH varies from acidic to alkaline conditions, in general, SNTs varied from bundled coiled, to characteristic sinusoidal waves, helical, and straight morphology. Under genetic control, flagella displaying negatively-charged peptides exhibited thinner layer of silica condensation but rough surface. However, flagella with positively-charged peptide inserts induced the deposition of thicker silica shell with smooth surface. Incorporation of hydroxyl bearing amino acid residues such as Ser into the peptide displayed on flagella highly enhanced the biotemplated deposition of silica. This work suggests that bacterial flagella are promising biotemplates for developing an environmentally-benign and cost-efficient approach to morphology-controlled synthesis of nanotubes. Moreover, the dependency of the thickness of the silica shell on the peptides displayed on flagella helps us to further understand the mechanism of biomimetic nucleation of silica on biological templates.

细菌鞭毛是自然产生的自组装蛋白质纳米纤维,从细菌表面突出,以帮助细菌游泳。它们是刚性的,并表现出不同的形态,这取决于离子强度、pH值、温度和亚基序列。在温和条件下,以鞭毛为生物模板,在水溶液中合成了形貌可控的二氧化硅纳米管(SNTs)。通过肽显示调节pH值或鞭毛表面化学,可以简单地调整鞭毛模板snt的形态和表面特征。获得了snt的多种不同形态(不同波长的卷曲、直、卷)和表面特征(光滑、粗糙、颗粒状和梨项链状)。当pH值从酸性到碱性变化时,snt通常从束状卷曲到特征正弦波、螺旋和直线形态变化。在遗传控制下,带负电荷肽的鞭毛硅结层较薄,表面粗糙。然而,带正电荷肽插入的鞭毛诱导了表面光滑的更厚的二氧化硅壳的沉积。将含羟基氨基酸残基(如丝氨酸)结合到鞭毛上显示的肽中,可以大大增强二氧化硅的生物模板化沉积。这项工作表明,细菌鞭毛是一种有前途的生物模板,用于开发一种环境友好和经济有效的形态控制纳米管合成方法。此外,二氧化硅壳的厚度与鞭毛上显示的肽的依赖关系有助于我们进一步了解二氧化硅在生物模板上的仿生成核机制。
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引用次数: 27
A material's point of view on recent developments of polymeric biomaterials: control of mechanical and biochemical properties. 从材料的角度看聚合物生物材料的最新发展:机械和生物化学特性的控制。
Pub Date : 2011-10-14 DOI: 10.1039/C1JM11372K
Varvara Gribova, Thomas Crouzier, Catherine Picart

Cells respond to a variety of stimuli, including biochemical, topographical and mechanical signals originating from their micro-environment. Cell responses to the mechanical properties of their substrates have been increasingly studied for about 14 years. To this end, several types of materials based on synthetic and natural polymers have been developed. Presentation of biochemical ligands to the cells is also important to provide additional functionalities or more selectivity in the details of cell/material interaction. In this review article, we will emphasize the development of synthetic and natural polymeric materials with well-characterized and tunable mechanical properties. We will also highlight how biochemical signals can be presented to the cells by combining them with these biomaterials. Such developments in materials science are not only important for fundamental biophysical studies on cell/material interactions but also for the design of a new generation of advanced and highly functional biomaterials.

细胞会对各种刺激做出反应,包括来自其微环境的生化、地形和机械信号。近 14 年来,细胞对其基质机械特性的反应研究日益增多。为此,人们开发了几种基于合成和天然聚合物的材料。向细胞提供生化配体对于在细胞/材料相互作用的细节中提供额外功能或更多选择性也很重要。在这篇综述文章中,我们将着重介绍具有良好特性和可调机械性能的合成和天然聚合物材料的开发情况。我们还将重点介绍如何通过将生化信号与这些生物材料相结合,向细胞传递生化信号。材料科学的这些发展不仅对细胞/材料相互作用的基础生物物理研究很重要,而且对设计新一代先进的高功能生物材料也很重要。
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引用次数: 0
Development of reactive Pd/Fe bimetallic nanotubes for dechlorination reactions. 开发用于脱氯反应的活性钯/铁双金属纳米管。
Pub Date : 2011-07-28 Epub Date: 2011-06-11 DOI: 10.1039/c1jm11435b
Elsayed M Zahran, Dibakar Bhattacharyya, Leonidas G Bachas

We described the synthesis and characterization of a new class of bimetallic nanotubes based on Pd/Fe and demonstrated their efficacy in the dechlorination of PCB 77, a polychlorinated biphenyl. Onedimensional iron metal nanotubes of different diameters were prepared by electroless deposition within the pores of PVP-coated polycarbonate membranes using a simple technique under ambient conditions. The longitudinal nucleation of the nanotubes along the pore walls was achieved by mounting the PC membrane between two halves of a U-shape reaction tube. The composition, morphology, and structure of the Pd/Fe nanotubes were characterized by transmission electron microscopy, scanning electron microscopy, inductively coupled plasma-atomic emission spectroscopy, and X-ray powder diffraction spectroscopy. The as-prepared Pd/Fe bimetallic nanotubes were used in dechlorination of 3,3',4,4'-tetrachlorobiphenyl (PCB 77). In comparison with Pd/Fe nanoparticles, the Pd/Fe nanotubes demonstrated higher efficiency and faster dechlorination of the PCB.

我们描述了一种基于钯/铁的新型双金属纳米管的合成和特性,并证明了它们在多氯联苯 PCB 77 的脱氯过程中的功效。在环境条件下,采用一种简单的技术,在涂有 PVP 的聚碳酸酯膜的孔隙中进行无电解沉积,制备出了不同直径的一维铁金属纳米管。通过将 PC 膜安装在 U 型反应管的两半之间,实现了纳米管沿孔壁的纵向成核。透射电子显微镜、扫描电子显微镜、电感耦合等离子体原子发射光谱和 X 射线粉末衍射光谱对 Pd/Fe 纳米管的组成、形态和结构进行了表征。制备的钯/铁双金属纳米管被用于 3,3',4,4'-四氯联苯(PCB 77)的脱氯。与 Pd/Fe 纳米粒子相比,Pd/Fe 纳米管对 PCB 的脱氯效率更高、速度更快。
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引用次数: 0
Evolution of Zinc Oxide Nanostructures through Kinetics Control. 动力学控制下氧化锌纳米结构的演化。
Pub Date : 2011-05-14 DOI: 10.1039/C1JM10918A
Jian Shi, Hao Hong, Yong Ding, Yunan Yang, Weibo Cai, Xudong Wang

In-depth understanding of the kinetics of the vapor deposition process is substantial for advancing this capable bottom-up nanostructure synthesis approach into a versatile large-scale nanomanufacturing technology. In this paper, we report a systematic study of the vapor deposition kinetics of ZnO nanomaterials under controlled atmosphere and properly refined deposition conditions. The experiments clearly evidenced the self-catalyzed growth of ZnO NWs via the formation of ZnO nanoflowers. This result illustrated how ZnO morphologies were associated with the discrepancy between oxidation rate and condensation rate of Zn. The capability of switching the NW morphologies and possibly mechanisms was demonstrated by kinetically controlling the deposition system. The high Zn composition during the deposition resulted in strongly luminescent NWs, which can be used for optical imaging applications. This research discovered a fundamental kinetics that governs the mechanisms and morphology selection of nanostructures in a non-catalyst growth system.

深入了解气相沉积过程的动力学对于将这种自下而上的纳米结构合成方法推进到通用的大规模纳米制造技术是至关重要的。在本文中,我们报道了在可控气氛和适当细化的沉积条件下ZnO纳米材料气相沉积动力学的系统研究。实验通过ZnO纳米花的形成清楚地证明了ZnO纳米ws的自催化生长。这一结果说明了ZnO的形貌与Zn的氧化速率和缩合速率的差异之间的关系。通过对沉积系统进行动力学控制,证明了其改变NW形貌的能力和可能的机制。在沉积过程中,高锌成分导致了强发光的NWs,可用于光学成像应用。本研究发现了在非催化剂生长系统中控制纳米结构的机制和形态选择的基本动力学。
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引用次数: 32
Bio-imaging, detection and analysis by using nanostructures as SERS substrates. 利用纳米结构作为SERS基底的生物成像、检测和分析。
Pub Date : 2011-04-14 DOI: 10.1039/C0JM03301D
Wei Xie, Penghe Qiu, Chuanbin Mao

Surface-enhanced Raman scattering (SERS) is a phenomenon that occurs on nanoscale-roughed metallic surface. The magnitude of the Raman scattering signal can be greatly enhanced when the scatterer is placed in the very close vicinity of the surface, which enables this phenomenon to be a highly sensitive analytical technique. SERS inherits the general strongpoint of conventional Raman spectroscopy and overcomes the inherently small cross section problem of a Raman scattering. It is a sensitive and nondestructive spectroscopic method for biological samples, and can be exploited either for the delivery of molecular structural information or for the detection of trace levels of analytes. Therefore, SERS has long been regarded as a powerful tool in biomedical research. Metallic nanostructure plays a key role in all the biomedical applications of SERS because the enhanced Raman signal can only be obtained on the surface of a finely divided substrate. This review focuses on progress made in the use of SERS as an analytical technique in bio-imaging, analysis and detection. Recent progress in the fabrication of SERS active nanostructures is also highlighted.

表面增强拉曼散射(SERS)是发生在纳米级粗糙金属表面的一种现象。当散射体放置在非常接近表面的位置时,拉曼散射信号的幅度可以大大增强,这使得这种现象成为一种高灵敏度的分析技术。SERS继承了传统拉曼光谱的一般优点,克服了拉曼散射固有的小截面问题。这是一种灵敏且无损的生物样品光谱方法,既可用于传递分子结构信息,也可用于检测痕量分析物。因此,SERS一直被认为是生物医学研究的有力工具。金属纳米结构在SERS的所有生物医学应用中起着关键作用,因为增强的拉曼信号只能在精细划分的衬底表面获得。本文综述了SERS作为一种分析技术在生物成像、分析和检测中的应用进展。本文还重点介绍了SERS活性纳米结构制备的最新进展。
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引用次数: 112
Photolithography of Dithiocarbamate-Anchored Monolayers and Polymers on Gold. 二硫代氨基甲酸酯锚定单分子层和聚合物在金上的光刻技术。
Pub Date : 2011-03-28 DOI: 10.1039/c0jm04153j
Alexei P Leonov, Alexander Wei

Dithiocarbamate (DTC)-anchored monolayers and polymers were investigated as positive resists for UV photolithography on planar and roughened Au surfaces. DTCs were formed in situ by the condensation of CS(2) with monovalent or polyvalent amines such as linear polyethyleneimine (PEI) under mildly basic aqueous conditions, just prior to surface passivation. The robust adsorption of the polyvalent PEI-DTC to Au surfaces supported high levels of resistance to photoablation, providing opportunities to generate thin films with gradient functionality. Treatment of photopatterned substrates with alkanethiols produced binary coatings, enabling a direct visual comparison of DTC- and thiol-passivated surfaces against chemically induced corrosion using confocal microscopy.

研究了二硫代氨基甲酸酯(DTC)锚定的单层和聚合物作为平面和粗糙金表面UV光刻的正性抗蚀剂。在表面钝化之前,CS(2)与一价或多价胺(如线性聚乙烯亚胺(PEI))在温和的碱性水条件下原位缩合形成dtc。多价PEI-DTC对Au表面的强大吸附支持了高水平的光烧蚀抗性,为生成具有梯度功能的薄膜提供了机会。用烷硫醇处理光图型衬底产生二元涂层,可以使用共聚焦显微镜直接直观地比较DTC和硫醇钝化表面对化学诱导腐蚀的影响。
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引用次数: 14
Controllable synthesis of NaYF(4) : Yb,Er upconversion nanophosphors and their application to in vivo imaging of Caenorhabditis elegans. NaYF(4) : Yb,Er 上转换纳米磷的可控合成及其在草履虫体内成像中的应用。
Pub Date : 2011-02-28 DOI: 10.1039/c0jm02854a
Jing Chen, Changrun Guo, Meng Wang, Lei Huang, Liping Wang, Congcong Mi, Jing Li, Xuexun Fang, Chuanbin Mao, Shukun Xu

β-NaYF(4) : Yb,Er upconversion nanoparticles (UCNPs) can emit bright green fluorescence under near-infrared (NIR) light excitation which is safe to the body and can penetrate deeply into tissues. The application of UCNPs in biolabeling and imaging has received great attention recently. In this work, β-NaYF(4) : Yb,Er UCNPs with an average size of 35 nm, uniformly spherical shape, and surface modified with amino groups were synthesized by a one-step green solvothermal approach through the use of room-temperature ionic liquids as the reactant, co-solvent and template. The as-prepared UCNPs were introduced into Caenorhabditis elegans (C. elegans) to achieve successful in vivo imaging. We found that longer incubation time, higher UCNP concentration and smaller UCNP size can make the in vivo fluorescence of C. elegans much brighter and more continuous along their body. The worms have no apparent selectivity on ingestion of the UCNPs capped with different capping ligands while having similar size and shape. The next generation of worms did not show fluorescence under excitation. In addition, low toxicity of the nanoparticles was demonstrated by investigating the survival rates of the worms in the presence of the UCNPs. Our work demonstrates the potential application of the UCNPs in studying the biological behavior of organisms, and lays the foundation for further development of the UCNPs in the detection and diagnosis of diseases.

β-NaYF(4):Yb,Er 上转换纳米粒子(UCNPs)在近红外(NIR)光激发下可发出明亮的绿色荧光,对人体安全,可深入组织。近年来,UCNPs 在生物标记和成像中的应用受到了广泛关注。本研究以室温离子液体为反应物、助溶剂和模板,采用一步绿色溶热法合成了平均尺寸为 35 nm、球形均匀、表面经氨基修饰的β-NaYF(4) : Yb,Er UCNPs。将制备好的 UCNPs 导入秀丽隐杆线虫(C. elegans)体内,成功实现了体内成像。我们发现,较长的孵育时间、较高的 UCNP 浓度和较小的 UCNP 尺寸可使秀丽隐杆线虫体内的荧光更亮、更连续。蠕虫在摄取不同封端配体而大小和形状相似的 UCNP 时没有明显的选择性。下一代蠕虫在激发下不显示荧光。此外,通过研究蠕虫在 UCNPs 存在下的存活率,证明了纳米颗粒的低毒性。我们的工作证明了 UCNPs 在研究生物行为方面的潜在应用,并为进一步开发 UCNPs 在疾病检测和诊断方面的应用奠定了基础。
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引用次数: 0
Fabrication of Covalently Crosslinked and Amine-Reactive Microcapsules by Reactive Layer-by-Layer Assembly of Azlactone-Containing Polymer Multilayers on Sacrificial Microparticle Templates. 通过在人工微粒模板上反应性逐层组装含氮内酯的聚合物多层来制造共价交联胺活性微胶囊
Pub Date : 2011-02-14 DOI: 10.1039/C0JM02633F
Eric M Saurer, Ryan M Flessner, Maren E Buck, David M Lynn

We report on the fabrication of covalently crosslinked and amine-reactive hollow microcapsules using 'reactive' layer-by-layer assembly to deposit thin polymer films on sacrificial microparticle templates. Our approach is based on the alternating deposition of layers of a synthetic polyamine and a polymer containing reactive azlactone functionality. Multilayered films composed of branched poly(ethylene imine) (BPEI) and poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) were fabricated layer-by-layer on the surfaces of calcium carbonate and glass microparticle templates. After fabrication, these films contained residual azlactone functionality that was accessible for reaction with amine-containing molecules. Dissolution of the calcium carbonate or glass cores using aqueous ethylenediamine tetraacetic acid (EDTA) or hydrofluoric acid (HF), respectively, led to the formation of hollow polymer microcapsules. These microcapsules were robust enough to encapsulate and retain a model macromolecule (FITC-dextran) and were stable for at least 22 hours in high ionic strength environments, in low and high pH solutions, and in several common organic solvents. Significant differences in the behaviors of capsules fabricated on CaCO(3) and glass cores were observed and characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Whereas capsules fabricated on CaCO(3) templates collapsed upon drying, capsules fabricated on glass templates remained rigid and spherical. Characterization using EDS suggested that this latter behavior results, at least in part, from the presence of insoluble metal fluoride salts that are trapped or precipitate within the walls of capsules after etching of the glass cores using HF. Our results demonstrate that the assembly of BPEI/PVDMA films on sacrificial templates can be used to fabricate reactive microcapsules of potential use in a wide range of fields, including catalysis, drug and gene delivery, imaging, and biomedical research.

我们报告了利用 "反应 "逐层组装技术在牺牲微粒模板上沉积聚合物薄膜,制造共价交联胺反应空心微胶囊的情况。我们的方法基于合成多胺和含有反应性氮内酯官能团的聚合物的交替沉积层。我们在碳酸钙和玻璃微粒模板表面逐层制作了由支化聚(乙烯亚胺)(BPEI)和聚(2-乙烯基-4,4-二甲基氮内酯)(PVDMA)组成的多层薄膜。制作完成后,这些薄膜含有可与含胺分子反应的残余氮内酯官能团。分别使用乙二胺四乙酸(EDTA)或氢氟酸(HF)水溶液溶解碳酸钙或玻璃芯,可形成空心聚合物微胶囊。这些微胶囊足以封装和保留模型大分子(FITC-葡聚糖),并且在高离子强度环境、低pH值和高pH值溶液以及几种常见有机溶剂中至少能稳定存在22小时。使用扫描电子显微镜(SEM)和能量色散 X 射线光谱(EDS)观察和表征了在 CaCO(3) 和玻璃芯上制造的胶囊在行为上的显著差异。在 CaCO(3) 模板上制作的胶囊在干燥时会塌陷,而在玻璃模板上制作的胶囊则保持坚硬和球形。利用 EDS 进行的表征表明,后一种行为至少部分是由于存在不溶性金属氟化物盐造成的,这些盐在使用 HF 蚀刻玻璃核心后被截留或沉淀在胶囊壁内。我们的研究结果表明,在牺牲模板上组装 BPEI/PVDMA 薄膜可用于制造活性微胶囊,在催化、药物和基因递送、成像和生物医学研究等广泛领域具有潜在用途。
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引用次数: 0
Tuning PEG-DA hydrogel properties via solvent-induced phase separation (SIPS)(). 通过溶剂诱导相分离(SIPS)调整PEG-DA水凝胶性质()。
Pub Date : 2011-01-01 Epub Date: 2011-10-21 DOI: 10.1039/C1JM13943F
Brennan Margaret Bailey, Vivian Hui, Ruochong Fei, Melissa Ann Grunlan

Poly(ethylene glycol) diacrylate (PEG-DA) hydrogels are widely utilized to probe cell-material interactions and ultimately for a material-guided approach to tissue regeneration. In this study, PEG-DA hydrogels were fabricated via solvent-induced phase separation (SIPS) to obtain hydrogels with a broader range of tunable physical properties including morphology (e.g. porosity), swelling and modulus (G'). In contrast to conventional PEG-DA hydrogels prepared from an aqueous precursor solution, the reported SIPS protocol utilized a dichloromethane (DCM) precursor solution which was sequentially photopolymerized, dried and hydrated. Physical properties were further tailored by varying the PEG-DA wt% concentration (5 wt%-25 wt%) and M(n) (3.4k and 6k g mol (-1)). SIPS produced PEG-DA hydrogels with a macroporous morphology as well as increased G' values versus the corresponding conventional PEG-DA hydrogels. Notably, since the total swelling was not significantly changed versus the corresponding conventional PEG-DA hydrogels, pairs or series of hydrogels represent scaffolds in which morphology and hydration or G' and hydration are uncoupled. In addition, PEG-DA hydrogels prepared via SIPS exhibited enhanced degradation rates.

聚乙二醇二丙烯酸酯(PEG-DA)水凝胶被广泛用于探测细胞-物质相互作用,并最终用于材料引导的组织再生方法。在本研究中,通过溶剂诱导相分离(SIPS)制备PEG-DA水凝胶,获得具有更广泛可调物理性质的水凝胶,包括形态(例如孔隙度),膨胀和模量(G')。与传统的由水前驱体溶液制备的PEG-DA水凝胶不同,SIPS方案使用了二氯甲烷(DCM)前驱体溶液,该前驱体溶液依次进行光聚合、干燥和水化。通过改变PEG-DA wt%浓度(5 wt%-25 wt%)和M(n) (3.4k和6k g mol(-1)),进一步调整其物理性质。SIPS生产的PEG-DA水凝胶具有大孔形态,与相应的常规PEG-DA水凝胶相比,G′值增加。值得注意的是,由于总的肿胀与相应的常规PEG-DA水凝胶相比没有明显变化,因此成对或系列的水凝胶代表了形态和水化或G′和水化不耦合的支架。此外,通过SIPS制备的PEG-DA水凝胶的降解率也有所提高。
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引用次数: 19
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Journal of Materials Chemistry
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