Molecularly Engineered Artificial Nanopores with Differential Selectivity and Sensitivity

目标：这项建议解决了限制纳米孔传感技术应用的一些根本和重要的障碍。具体而言，涉及纳米孔大小、表面成分和孔的稳定性，以扩大这项技术的范围，将重要的新领域包括在内，例如基因组测序，这只是许多例子中的一个。为了帮助加快这一领域的进展，我们的目标是制造和彻底评估纳米孔传感器技术的新方法。具体地说，我们建议构建人工孔，其中孔的大小和表面化学都可以在广泛的孔大小范围内精确控制。为此，一种新的热处理和脉冲等离子体化学气相沉积的组合将被用来可控和可重复地缩小孔尺寸，同时改变表面化学成分。这些分子工程纳米孔的可用性有望克服目前在这项技术的分析应用中遇到的限制。另一个重要目标涉及将这项技术扩展到几个新的、备受瞩目的应用，通过我们的方法，例如，通过两个相反的手性功能化纳米孔进行选择性差异检测，这将使手性化合物的色谱测量发生革命性的变化；类似的方案在许多其他情况下也是可能的。到目前为止，纳米孔的制造主要集中在低吞吐量的系列方法上，很少使用自下而上的技术。总的来说，关键问题仍然存在，例如纳米孔/流体界面的稳定性、纳米孔表面性质的重现性、扩展的孔稳定性以及纳米孔需要强有力的化学功能化。如本提案所述，机械稳定的纳米孔具有一系列明确定义的直径和表面化学成分，这代表着该领域的一项变革性进展。新的见解将从纳米孔中的选择性相互作用中获得，提供定量处理来评估配体的分子反应，并定义询问目标分析物的新的化学手段。这将刺激更多的研究：控制分析物通过毛孔的转移时间(这是一个非常重要的当前问题)，以及使用化学和大小不同的纳米孔阵列。这一创新还将有助于克服和取代目前劳动密集型和低产量的制造方法。拟议活动的更广泛影响？拟议中的项目将影响许多依赖于科学和工程融合的领域。例如生物启发系统的设计、环境和生命系统的传感器等。所涉及的基本原则可以整合到所有级别的教育中。研究生和本科生将参与并通过开发生物纳米界面上的交叉列出的课程模块，向他们介绍令人兴奋的分析化学、生物化学和固态制造的新维度。研究成果还将用于在我们目前举办的夏令营(为初中生/高中生)和女童夏令营(为女高中生)开发综合参与式模块，以吸引未来的成年人从事STEM职业。这些外展工作将继续进行：(1)研讨会/实验室之旅，以使UGS参与和保留在研究中；(2)通过McNair研究员计划吸引少数族裔学生；(3)在Facebook上动态地展示/曝光/讨论研究；(4)通过现场网络广播让K-12学生和教师参与进来。拟议的研究和教育努力的结果不仅将通过同行评议的文章和会议传播，而且还将通过公共媒体(广播、报纸、网络博客、公共展示)传播。UTA化学公司参加当地的州际博览会。UTA拥有Metroplex中最大的数字天文馆，K-12交通极其繁忙。我们计划在纳米孔传感器上开发一种小夹子。

Objectives: This proposal addresses a number of fundamental and important obstacles that have limited the utility of nanopore sensing technology. Specifically, nanopore size, surface composition and stability of the pores are addressed to broaden this technology to include important new areas, e.g. sequencing of genomes, as but one of many examples. To help expedite progress in this area, our objective involves fabrication and thorough evaluation of a new approach to nanopore sensor technology. Specifically, we propose construction of artificial pores in which both the size and surface chemistry of the pores are precisely controlled over a wide range of pore sizes. For this purpose, a novel combination of thermal processing, followed by pulsed plasma chemical vapor deposition, will be used to shrink pore sizes controllably and reproducibly, while simultaneously varying surface chemistry. Availability of these molecularly engineered nanopores will hopefully overcome limitations currently encountered in analytical applications of this technology. An additional important objective involves extension of this technology to several new, high profile applications to be made available via our approach, e.g., selective differential detection by two oppositely chirally functionalized nanopores which will revolutionize chromatographic measurement of chiral compounds; similar schemes will be possible in many other cases.Intellectual Merits of the Proposed Activity? To date, nanopore fabrication has focused primarily on low-throughput serial approaches, with little use of bottom-up technology. In general, key issues such as stability of nanopore/fluid interfaces, reproducibility of nanopore surface properties, extended pore stability and the need for robust chemical functionalization of the nanopores remain. The ready availability of mechanically stable nanopores, having a range of well-defined diameters and surface chemistries, as described in this proposal, represents a transformative advance in this area. New insights will be gained from selective interactions in nanopores, providing quantitative handles to evaluate the molecular responses of ligands and to define novel, chemical means of interrogating targeted analytes. This will stimulate additional studies: control of translocation times of analytes through the pores (an immensely important present problem) and the use of chemistry and size differentiated nanopore arrays. This innovation will also help overcome and replace the present labor-intensive and low-throughput fabrication methods. Broader Impacts of the Proposed Activity? The proposed project will impact many areas that depend on the confluence of sciences and engineering. Examples include design of bio-inspired systems, sensors for environment and living systems, etc. The basic principles involved can be integrated into all levels of education. Graduate and undergraduate (UG) students will be engaged and introduced to exciting new dimensions of analytical chemistry, biochemistry and solid-state fabrication through development of a cross-listed course module on the bio-nano interface. The research outcomes will be also used to develop integrative participatory modules at our presently conducted Summer Camps (for middle/high-school students) and Girlgeneering Camps (for female high school students) to attract future adults to STEM careers. These outreach endeavors will be pursued: (1) Seminars/lab-tours for involvement and retention of UGs in research; (2) Engaging minority students through the McNair Fellows program; (3) Dynamic Facebook presence for the projection/exposure/discussion of the research; (4) Engagement of K-12 students and teachers through live webcasts. The results of the proposed research and education endeavors will be disseminated not only through peer-reviewed articles and conferences, but also through public media (radio, newspaper, weblogs, public displays). UTA Chemistry participates in the local State Fair. UTA has the largest digital planetarium in the Metroplex, with extremely heavy K-12 traffic. We plan to develop a small clip on nanopore sensors.