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Immobilization of magnetic iron oxide nanoparticles on laponite discs - an easy way to biocompatible ferrofluids and ferrogels. 磁性氧化铁纳米颗粒在拉脱土圆盘上的固定化-一种生物相容性铁磁流体和铁凝胶的简单方法。
Pub Date : 2010-01-01 DOI: 10.1039/c0jm00061b
Vassilios Tzitzios, Georgia Basina, Aristides Bakandritsos, Costas G Hadjipanayis, Hui Mao, Dimitrios Niarchos, George C Hadjipanayis, Jiri Tucek, Radek Zboril

Magnetic nanocomposites containing iron oxide (maghemite) nanoparticles, well embedded in a synthetic clay matrix (laponite) were prepared by a new one step chemical route and characterized by TEM, XRD, magnetization measurements, Mössbauer spectroscopy, DLS, and MRI measurements. The synthetic procedure leads to non-stoichiometric γ-Fe(2)O(3) with a controllable content in the nanocomposite. Magnetic nanoparticles incorporated in the diamagnetic clay matrix exhibit a mean diameter of 13 nm, superparamagnetic behavior with a high saturation magnetization achievable at low applied magnetic fields. In-field Mössbauer spectra and ZFC/FC magnetization curves reveal a perfect ferrimagnetic ordering within nanoparticles with negligible spin frustration and interparticle interactions due to the complete coating of maghemite surfaces by the nanocrystalline laponite matrix. Magnetic iron oxide nanoparticles embedded in laponite matrix exhibit strong T(2) weighted MRI contrast. The maghemite/laponite composite particles have 200 nm hydrodynamic diameter and form very stable hydrosols and/or hydrogels depending on their concentration in water.

采用一种新的一步化学方法,将氧化铁(磁赤铁矿)纳米颗粒包埋在合成粘土基体(拉脱土)中,制备了磁性纳米复合材料,并通过TEM、XRD、磁化测量、Mössbauer光谱、DLS和MRI测量对其进行了表征。该合成过程生成了含量可控的非化学计量γ-Fe(2)O(3)纳米复合材料。磁性纳米颗粒掺入抗磁性粘土基质中,平均直径为13 nm,具有超顺磁性,在低外加磁场下具有高饱和磁化强度。现场Mössbauer光谱和ZFC/FC磁化曲线显示纳米颗粒内部具有完美的铁磁有序,可忽略自旋受挫和粒子间相互作用,这是由于纳米晶拉脱土基质完全覆盖了磁铁矿表面。磁性氧化铁纳米颗粒包埋在拉脱土基质中,表现出强烈的T(2)加权MRI对比。磁赤铁矿/拉脱石复合颗粒的水动力直径为200nm,根据其在水中的浓度不同,可形成非常稳定的水溶胶和/或水凝胶。
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引用次数: 50
Functionalization of iron oxide nanoparticles with a versatile epoxy amine linker. 氧化铁纳米颗粒与多功能环氧胺连接剂的功能化。
Pub Date : 2010-01-01 DOI: 10.1039/c0jm00808g
Michael Nickels, Jingping Xie, Jared Cobb, John C Gore, Wellington Pham

A synthetically diverse linker molecule consisting of both a terminal epoxide and a terminal amine has been synthesized and shown to have the desired reactivity. Proof of principle experimentation showed that the prepared linker molecule possessed the ability to be reactive towards dextran coated iron nanoparticles, essentially converting the surface alcohols to amines with an efficiency on average of 50 linkers per nanoparticle. Once the surface of the nanoparticles had been functionalized, the iron nanoparticles were subsequently functionalized with both folic acid and fluorescein isothiocyanate, with an average efficiency of 20 and 3 molecules per nanoparticle, respectively. The labeled nanoparticles were then incubated with both folate receptor positive and negative cell lines, which showed a preferential accumulation of the particles in the receptor positive cell line. In addition to the fluorescence based assays, accumulation of the nanoparticles was demonstrated using T2-weighted MRI imaging, which showed that the iron core of the nanoparticle was present within the desired cell line. Overall, this linker has shown the ability to functionalize the surface of nanoparticles and can theoretically be used to label a wide variety of other targeting agents or imaging agents for in vivo therapies or diagnostics.

合成了一种由末端环氧化物和末端胺组成的合成多样连接分子,并显示出所需的反应活性。原理证明实验表明,所制备的连接剂分子具有对右旋糖酐包覆的铁纳米颗粒反应的能力,基本上以平均每个纳米颗粒50个连接剂的效率将表面醇转化为胺。一旦纳米颗粒的表面被功能化,铁纳米颗粒随后被叶酸和异硫氰酸荧光素功能化,平均效率分别为每纳米颗粒20和3个分子。然后将标记的纳米颗粒与叶酸受体阳性和阴性细胞系孵育,结果表明,叶酸受体阳性细胞系中的纳米颗粒优先积累。除了基于荧光的检测外,利用t2加权MRI成像证实了纳米颗粒的积累,这表明纳米颗粒的铁核存在于所需的细胞系中。总的来说,这种连接体已经显示出纳米颗粒表面功能化的能力,理论上可以用于标记各种其他靶向剂或显像剂,用于体内治疗或诊断。
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引用次数: 19
Synthesis and characterization of highly photoresponsive fullerenyl dyads with a close chromophore antenna-C(60) contact and effective photodynamic potential. 具有密切的发色团天线- c(60)接触和有效光动力势的高光响应的富勒烯基二偶体的合成和表征。
Pub Date : 2010-01-01 DOI: 10.1039/C0JM00037J
Long Y Chiang, Prashant A Padmawar, Joy E Rogers-Haley, Grace So, Taizoon Canteenwala, Sammaiah Thota, Loon-Seng Tan, Kenneth Pritzker, Ying-Ying Huang, Sulbha K Sharma, Divya Balachandran Kurup, Michael R Hamblin, Brian Wilson, Augustine Urbas
We report the synthesis of a new class of photoresponsive C(60)-DCE-diphenylaminofluorene nanostructures and their intramolecular photoinduced energy and electron transfer phenomena. Structural modification was made by chemical conversion of the keto group in C(60)(>DPAF-C(n)) to a stronger electron-withdrawing 1,1-dicyanoethylenyl (DCE) unit leading to C(60)(>CPAF-C(n)) with an increased electronic polarization of the molecule. The modification also led to a large bathochromic shift of the major band in visible spectrum giving measureable absorption up to 600 nm and extended the photoresponsive capability of C(60)-DCE-DPAF nanostructures to longer red wavelengths than C(60)(>DPAF-C(n)). Accordingly, C(60)(>CPAF-C(n)) may allow 2γ-PDT using a light wavelength of 1000-1200 nm for enhanced tissue penetration depth. Production efficiency of singlet oxygen by closely related C(60)(>DPAF-C(2) (M)) was found to be comparable with that of tetraphenylporphyrin photosensitizer. Remarkably, the (1)O(2) quantum yield of C(60)(>CPAF-C(2) (M)) was found to be nearly 6-fold higher than that of C(60)(>DPAF-C(2) (M)), demonstrating the large light-harvesting enhancement of the CPAF-C(2) (M) moiety and leading to more efficient triplet state generation of the C(60)> cage moiety. This led to highly effective killing of HeLa cells by C(60)(>CPAF-C(2) (M)) via photodynamic therapy (200 J cm(-2) white light). We interpret the phenomena in terms of the contributions by the extended π-conjugation and stronger electron-withdrawing capability associated with the 1,1-dicyanoethylenyl group compared to that of the keto group.
本文报道了一类新型光响应型C(60)- dce -二苯基氨基芴纳米结构的合成及其分子内光致能量和电子转移现象。通过将C(60)中的酮基(>DPAF-C(n))化学转化为具有更强的吸电子性的1,1-二氰乙基(DCE),使得C(60)(>CPAF-C(n))分子的电子极化增强,从而进行结构修饰。该修饰还导致了可见光谱中主要波段的大色移,使可测量的吸收达到600 nm,并将C(60)-DCE-DPAF纳米结构的光响应能力扩展到比C(60)(>DPAF-C(n))更长的红色波长。因此,C(60)(>CPAF-C(n))可能允许使用波长为1000-1200 nm的2γ-PDT来增强组织穿透深度。密切相关的C(60)(>DPAF-C(2) (M))产生单重态氧的效率与四苯基卟啉光敏剂相当。值得注意的是,C(60)(>CPAF-C(2) (M))的(1)O(2)量子产率比C(60)(>DPAF-C(2) (M))高出近6倍,表明CPAF-C(2) (M)片段的光捕获能力大大增强,并导致C(60)> cage片段更有效地产生三重态。这导致C(60)(>CPAF-C(2) (M))通过光动力治疗(200 J cm(-2)白光)高效杀死HeLa细胞。我们从扩展π共轭的贡献和与1,1-二氰乙基相比酮基更强的吸电子能力来解释这一现象。
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引用次数: 49
Tailored Synthesis of Nitric Oxide-Releasing Polyurethanes Using O-Protected Diazeniumdiolated Chain Extenders. 使用 O 型保护重氮二醇链延伸剂定制合成释放一氧化氮的聚氨酯。
Pub Date : 2010-01-01 DOI: 10.1039/c000152j
Melissa M Reynolds, Joseph E Saavedra, Brett M Showalter, Carlos A Valdez, Anna P Shanklin, Bong K Oh, Larry K Keefer, Mark E Meyerhoff

Nitric oxide (NO) has been shown to exhibit significant anti-platelet activity and its release from polymer matrices has been already utilized to increase the biocompatibility of various blood-contacting devices. Herein, details of a new synthetic approach for preparing NO-releasing diazeniumdiolated polyurethanes (PU) are described. The method's utility is demonstrated by the incorporation of methoxymethyl- or sugar-protected pre-formed diazeniumdiolate moieties directly into chain extender diols which are then incorporated into the polyurethane backbone. This approach provides the ability to control the number of diazeniumdiolate groups incorporated into the polymer backbone, and hence the surface flux of NO that can ultimately be liberated from polymeric films prepared from the new PU materials. The method provides a means of covalently attaching diazeniumdiolate groups to polyurethanes in a form that resists dissociation of NO during processing but can be activated for spontaneous NO release via hydrolysis of the carbohydrate or methoxymethyl moieties under basic and acidic conditions, respectively.

一氧化氮(NO)已被证明具有显著的抗血小板活性,从聚合物基质中释放一氧化氮已被用于提高各种血液接触设备的生物相容性。本文详细介绍了制备释放一氧化氮的重氮二醇化聚氨酯(PU)的新合成方法。该方法的实用性体现在将甲氧基甲基或糖保护的预成形重氮二醇分子直接加入扩链二元醇中,然后再将其加入聚氨酯骨架中。这种方法可以控制加入聚合物骨架中的重氮二酸酯基团的数量,从而控制最终从新型聚氨酯材料制备的聚合物薄膜中释放出来的 NO 的表面通量。该方法提供了一种将二硫代二氮杂环戊烷基团共价连接到聚氨酯上的方法,这种共价连接的形式可在加工过程中阻止 NO 的解离,但可在碱性和酸性条件下分别通过碳水化合物或甲氧基甲基的水解激活 NO 的自发释放。
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引用次数: 0
Synthesis and Characterization of Tunable Rainbow Colored Colloidal Silver Nanoparticles Using Single-Nanoparticle Plasmonic Microscopy and Spectroscopy. 利用单纳米粒子等离子体显微镜和光谱学合成和表征可调谐彩虹色胶体银纳米粒子。
Pub Date : 2010-01-01 Epub Date: 2010-09-30 DOI: 10.1039/C0JM01990A
Tao Huang, Xiao-Hong Nancy Xu

Noble metal nanoparticles (NPs) possess size- and shape- dependent optical properties, suggesting the possibility of tuning desired optical properties of ensemble NPs at single NP resolution and underscoring the importance of probing the sizes and shapes of single NPs in situ and in real-time. In this study, we synthesized twelve colloids of Ag NPs. Each colloid contains various sizes and shapes of single NPs, showing rainbow colors with peak-wavelength of absorption spectra from 393 to 738 nm. We correlated the sizes and shapes of single NPs determined by high-resolution transmission electron microscopy (HRTEM) with scattering localized surface plasmon resonance (LSPR) spectra of single NPs characterized by dark-field optical microcopy and spectroscopy (DFOMS). Single spherical (2-39 nm in diameter), rod (2-47 nm in length with aspect ratios of 1.3-1.6), and triangular (4-84 nm in length with thickness of 2-27 nm) NPs show LSPR spectra (λ(max)) at 476±5 or 533±12, 611±23, and 711±40 nm, respectively. Notably, we observed new cookie-shaped NPs, which exhibit LSPR spectra (λ(max)) at 725±10 nm with a shoulder peak at 604±5 nm. Linear correlations of sizes of any given shape of single NPs with their LSPR spectra (λ(max)) enable the creation of nano optical rulers (calibration curves) for identification of the sizes and shapes of single NPs in solution in real time using DFOMS, offering the feasibility of using single NPs as multicolored optical probes for study of dynamics events of interest in solutions and living organisms at nm scale in real time.

贵金属纳米颗粒(NPs)具有尺寸和形状相关的光学性质,这表明在单个NP分辨率下调整系综NPs所需光学性质的可能性,并强调了原位和实时探测单个NPs尺寸和形状的重要性。在这项研究中,我们合成了12种银NPs胶体。每个胶体包含不同大小和形状的单个NPs,呈现彩虹色,吸收光谱峰波长在393 ~ 738 nm之间。我们将高分辨率透射电子显微镜(HRTEM)测定的单个纳米粒子的大小和形状与暗场光学显微复制和光谱(doms)表征的单个纳米粒子的散射局部表面等离子体共振(LSPR)光谱相关联。单球形NPs(直径2 ~ 39 nm)、棒状NPs(长度2 ~ 47 nm,宽高比为1.3 ~ 1.6)和三角形NPs(长度4 ~ 84 nm,厚度2 ~ 27 nm)的LSPR光谱(λ(max))分别为476±5或533±12、611±23和711±40 nm。值得注意的是,我们观察到新的饼干状NPs,其LSPR光谱(λ(max))在725±10 nm处,肩峰在604±5 nm处。任意形状的单个纳米粒子的大小与其LSPR光谱(λ(max))之间的线性相关性,使得使用DFOMS可以创建纳米光学尺子(校准曲线)来实时识别溶液中单个纳米粒子的大小和形状,从而提供了使用单个纳米粒子作为多色光学探针来实时研究溶液和生物体中感兴趣的动力学事件的可行性。
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引用次数: 228
Photocatalytic Properties of Porous Silicon Nanowires. 多孔硅纳米线的光催化性能。
Pub Date : 2010-01-01 DOI: 10.1039/c0jm00493f
Yongquan Qu, Xing Zhong, Yujing Li, Lei Liao, Yu Huang, Xiangfeng Duan

Porous silicon nanowires are synthesized through metal assisted wet-chemical etch of highly-doped silicon wafer. The resulted porous silicon nanowires exhibit a large surface area of 337 m(2)·g(-1) and a wide spectrum absorption across the entire ultraviolet, visible and near infrared regime. We further demonstrate that platinum nanoparticles can be loaded onto the surface of the porous silicon nanowires with controlled density. These combined advancements make the porous silicon nanowires an interesting material for photocatalytic applications. We show that the porous silicon nanowires and platinum nanoparticle loaded porous silicon nanowires can be used as effective photocatalysts for photocatalytic degradation of organic dyes and toxic pollutants under visible irradiation, and thus are of significant interest for organic waste treatment and environmental remediation.

采用高掺杂硅片的金属辅助湿化学蚀刻法合成多孔硅纳米线。所得多孔硅纳米线具有337 m(2)·g(-1)的大表面积,在整个紫外、可见光和近红外波段具有广泛的光谱吸收。我们进一步证明了铂纳米粒子可以在密度可控的情况下加载到多孔硅纳米线的表面。这些综合的进步使多孔硅纳米线成为光催化应用的有趣材料。研究结果表明,多孔硅纳米线和负载铂纳米粒子的多孔硅纳米线可作为可见光光催化降解有机染料和有毒污染物的有效光催化剂,在有机废物处理和环境修复中具有重要意义。
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引用次数: 116
Fabrication and functional characterization of goldnanoconjugates for potential application in ovarian cancer. 金纳米共轭物的制备和功能表征,有望应用于卵巢癌的治疗。
Pub Date : 2010-01-01 DOI: 10.1039/b913224d
Chitta Ranjan Patra, Resham Bhattacharya, Priyabrata Mukherjee

In this paper we report the surface modification and functional characterization of a gold nanoparticle-based drug delivery system for potential therapeutic application in ovarian cancer. It is currently recognized that nanotechnology may play a pivotal role in drug delivery by increasing efficacy and reducing toxicity of anti-cancer drugs. Here, we report the fabrication of a gold nanoparticles (AuNP) based drug delivery system consisting of folic acid (FA), mercapto-polyethylene glycol (PEG-SH) with a molecular weight of 2000 (designated as PSH2-2K or PSH) and cis-platin (CP) [Au-PSH-CP-FA] for potential therapeutic application in ovarian cancer. Fabrication is done in a three steps incubation process at room temperature (RT). The gold nanoconjugates are characterized with several physico-chemical techniques such as UV-Vis (UV-Visible spectroscopy), TEM (Transmission electron microscopy), ICP (Inductively coupled plasma) and radioactivity measurement with a scintillation counter. Attachment and release profiles of FA from the gold nanoconjugates are performed using (3)H-labelled FA ((3)H-FA). The expressions of folate receptor (FR) for ovarian cancer cell lines (OV-167, OVCAR-5), human umbilical vein endothelial cells (HUVEC) and ovarian surface epithelial (OSE) cells are determined by FACS analysis. Quantitation of platinum content in the nanoconjugates and its release profile is determined by platinum (Pt) analysis using ICP-MS. Biological functional characterization using in vitro proliferation assay demonstrates that Au-PSH-CP-FA not only retains the cytotoxic effect of CP, but it protects the normal cells from the cytotoxic insult, while enhancing the cytotoxic effect on the tumor cells. In future, this strategy may be utilized as a strategy for the treatment of ovarian cancers and may overcome the core side effect issues in anticancer therapy.

在本文中,我们报告了一种基于金纳米粒子的给药系统的表面改性和功能表征,该系统有望应用于卵巢癌的治疗。目前,人们已经认识到纳米技术可以提高抗癌药物的疗效并降低其毒性,从而在给药过程中发挥关键作用。在此,我们报告了一种基于金纳米粒子(AuNP)的给药系统,该系统由叶酸(FA)、分子量为 2000 的巯基聚乙二醇(PEG-SH)(命名为 PSH2-2K 或 PSH)和顺式铂(CP)[Au-PSH-CP-FA]组成,有望应用于卵巢癌的治疗。制备过程分为三个步骤,在室温(RT)下孵育。金纳米共轭物采用多种物理化学技术进行表征,如 UV-Vis(紫外可见光谱)、TEM(透射电子显微镜)、ICP(电感耦合等离子体)和闪烁计数器的放射性测量。使用 (3)H 标记的叶酸((3)H-FA)分析了金纳米共轭物中叶酸的附着和释放情况。卵巢癌细胞系(OV-167、OVCAR-5)、人脐静脉内皮细胞(HUVEC)和卵巢表面上皮细胞(OSE)的叶酸受体(FR)的表达量通过 FACS 分析进行测定。通过使用 ICP-MS 进行铂(Pt)分析,确定纳米共轭物中铂含量的定量及其释放情况。利用体外增殖试验进行的生物功能特性分析表明,Au-PSH-CP-FA 不仅保留了 CP 的细胞毒性作用,而且还能保护正常细胞免受细胞毒性损伤,同时增强对肿瘤细胞的细胞毒性作用。未来,这种策略可作为治疗卵巢癌的一种策略,并可克服抗癌治疗中的核心副作用问题。
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引用次数: 0
A photochemically initiated chemistry for coupling underivatized carbohydrates to gold nanoparticles. 将未充分活化的碳水化合物与金纳米颗粒耦合的光化学引发化学反应。
Pub Date : 2009-12-21 DOI: 10.1039/B917900C
Xin Wang, Olof Ramström, Mingdi Yan

The sensitive optoelectronic properties of metal nanoparticles make nanoparticle-based materials a powerful tool to study fundamental biorecognition processes. Here we present a new and versatile method for coupling underivatized carbohydrates to gold nanoparticles (Au NPs) via the photochemically induced reaction of perfluorophenylazide (PFPA). A one-pot procedure was developed where Au NPs were synthesized and functionalized with PFPA by a ligand-exchange reaction. Carbohydrates were subsequently immobilized on the NPs by a fast light activation. The coupling reaction was efficient, resulting in high coupling yield as well as high ligand surface coverage. A colorimetric system based on the carbohydrate-modified Au NPs was used for the sensitive detection of carbohydrate-protein interactions. Binding and cross-reactivity studies were carried out between carbohydrate-functionalized Au NPs and lectins. Results showed that the surface-bound carbohydrates not only retained their binding affinities towards the corresponding lectin, but also exhibited affinity ranking consistent with that of the free ligands in solution.

金属纳米粒子灵敏的光电特性使基于纳米粒子的材料成为研究基本生物识别过程的有力工具。在这里,我们介绍了一种通过全氟苯基叠氮化物(PFPA)的光化学诱导反应将未充分活化的碳水化合物与金纳米粒子(Au NPs)耦合的多功能新方法。我们开发了一种一锅程序,通过配体交换反应合成 Au NPs 并用 PFPA 进行功能化。随后通过快速光激活将碳水化合物固定在 NPs 上。耦合反应非常高效,不仅耦合产率高,而且配体表面覆盖率也很高。基于碳水化合物修饰的 Au NPs 的比色系统可用于灵敏检测碳水化合物与蛋白质之间的相互作用。在碳水化合物功能化 Au NPs 和凝集素之间进行了结合和交叉反应研究。结果表明,表面结合的碳水化合物不仅保持了与相应凝集素的结合亲和力,而且其亲和力等级与溶液中游离配体的亲和力等级一致。
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引用次数: 0
Nanoparticle technology: Addressing the fundamental roadblocks to protein biomarker discovery. 纳米粒子技术:解决蛋白质生物标记物发现的基本障碍。
Pub Date : 2009-08-07 DOI: 10.1039/b822264a
Alessandra Luchini, Caterina Longo, Virginia Espina, Emanuel F Petricoin, Lance A Liotta

The incorporation of affinity baits into N-isopropylacrylamide-hydrogel-based nanoparticles offers a novel technology that addresses the major analytical challenges of disease biomarker discovery. In solution in complex biologic fluids (e.g. blood or urine), core-shell bait-containing nanoparticles can perform three functions in one step: (a) sieve molecules according to size, (b) sequestrate and concentrate target analytes, and (c) protect analytes from degradation.

在基于 N-isopropylacrylamide-hydrogel 的纳米颗粒中加入亲和性诱饵提供了一种新型技术,可解决疾病生物标记物发现过程中的主要分析难题。在复杂生物液体(如血液或尿液)的溶液中,含有核壳诱饵的纳米颗粒可一步实现三种功能:(a)根据分子大小筛分分子,(b)螯合和浓缩目标分析物,以及(c)保护分析物不被降解。
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引用次数: 0
Biomedical applications of chemically-modified silk fibroin. 化学改性丝素蛋白的生物医学应用。
Pub Date : 2009-06-23 DOI: 10.1039/b905802h
Amanda R Murphy, David L Kaplan

Silk proteins belong to a class of unique, high molecular weight, block copolymer-like proteins that have found widespread use in biomaterials and regenerative medicine. The useful features of these proteins, including self-assembly, robust mechanical properties, biocompatibility and biodegradability can be enhanced through a variety of chemical modifications. These modifications provide chemical handles for the attachment of growth factors, cell binding domains and other polymers to silk, expanding the range of cell and tissue engineering applications attainable. This review focuses on the chemical reactions that have been used to modify the amino acids in silk proteins, and describes their utility in biomedical applications.

丝蛋白属于一类独特的、高分子量的嵌段共聚物样蛋白,在生物材料和再生医学中有着广泛的应用。这些蛋白质的有用特性,包括自组装、强大的机械性能、生物相容性和生物降解性,可以通过各种化学修饰来增强。这些修饰为生长因子、细胞结合域和其他聚合物在丝上的附着提供了化学处理,扩大了细胞和组织工程应用的范围。本文综述了近年来用于修饰丝蛋白氨基酸的化学反应及其在生物医学上的应用。
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引用次数: 383
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