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Beschreibung

Presenting a wide variety of methods, this book provides a comprehensive overview of the current state -- ranging from bioanalysis to electrochemical sensing, forensics and chemistry, while also covering the toxicity aspects of nanomaterials to humans and the environment. Edited by rising stars in the field, the first section on biological analysis includes an investigation of nanoparticles and micro- and nanofluidic systems, while the second, environmental analysis, looks at the detection, monitoring, and sensing of explosives as well as pollutants, among other topics. The final part covers such advanced methods as the synthesis and characterization of gold nanorods. For analytical chemists, materials scientists, chemists working in trace analysis, and spectroscopists.

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Table of Contents

Cover

Series page

Title page

Copyright page

Preface

List of Contributors

Part 1: Biological and Chemical Analysis

1 Photoswitchable Nanoprobes for Biological Imaging Applications

1.1 Introduction

1.2 Photoswitchable Fluorescent Nanoprobes

1.3 Photoswitchable Magnetic Nanoparticles

1.4 Future Perspectives

Acknowledgments

2 Applications of Semiconductor Quantum Dots in Chemical and Biological Analysis

2.1 Introduction

2.2 History

2.3 Classifications

2.4 Characteristics

2.5 Synthesis and Surface Chemistry

2.6 Trace Analysis Using Quantum Dots

2.7 Summary

Acknowledgments

3 Nanomaterial-Based Electrochemical Biosensors and Bioassays

3.1 Introduction

3.2 Nanomaterial Labels Used in Electrochemical Biosensors and Bioassays

3.3 Nanomaterial-Based Electrochemical Devices for Point-of-Care Diagnosis

3.4 Conclusions

Acknowledgments

4 Chemical and Biological Sensing by Electron Transport in Nanomaterials

4.1 Introduction

4.2 Electron Transport through Metal Nanoparticles

4.3 Sensing Applications Based on Electron Transport in Nanoparticle Assemblies

4.4 Concluding Remarks

Acknowledgments

5 Micro- and Nanofluidic Systems for Trace Analysis of Biological Samples

5.1 Introduction

5.2 Nucleic Acid Analysis

5.3 Protein Analysis

5.4 Microfluidic Devices for Single-Cell Analysis

5.5 Conclusion

Part 2: Environmental Analysis

6 Molecularly Imprinted Polymer Submicron Particles Tailored for Extraction of Trace Estrogens in Water

6.1 Introduction

6.2 Principle of Molecular Recognition by Imprinting

6.3 Analytical Application of MIPs for Biopharmaceuticals and Toxins

6.4 Preparation of MIP Submicron Particles

6.5 Binding Properties of MIP Submicron Particles with E2

6.6 Trace Analysis of E2 in Wastewater Treatment

6.7 Current Progress

6.8 Recent Advances in MIP Technology for Continuing Development

Acknowledgments

7 Trace Detection of High Explosives with Nanomaterials

7.1 Introduction

7.2 Techniques for Trace Detection of High Explosives

7.3 Conclusions

Acknowledgments

8 Nanostructured Materials for Selective Collection of Trace-Level Metals from Aqueous Systems

8.1 Introduction

8.2 Sorbents for Trace-Metal Collection and Analysis: Relevant Figures of Merit

8.3 Thiol-Functionalized Ordered Mesoporous Silica for Heavy Metal Collection

8.4 Surface-Functionalized Magnetic Nanoparticles for Heavy Metal Capture and Detection

8.5 Nanoporous Carbon Based Sorbent Materials

8.6 Other Nanostructured Sorbent Materials

8.7 Concluding Thoughts

Acknowledgments

9 Synthesis and Analysis Applications of TiO2-Based Nanomaterials

9.1 Introduction

9.2 Synthesis of TiO2 Nanostructures

9.3 Applications of TiO2-Based Nanomaterials for Chemical Analysis

9.4 Conclusions

Acknowledgments

10 Nanomaterials in the Environment: the Good, the Bad, and the Ugly

10.1 Introduction

10.2 The Good: Nanomaterials for Environmental Sensing

10.3 The Bad: Environmental Fate of Nanomaterials

10.4 The Ugly: Detection of Nanomaterials in the Environment

10.5 Conclusions

Acknowledgments

Part 3: Advanced Methods and Materials

11 Electroanalytical Measurements at Electrodes Modified with Metal Nanoparticles

11.1 Introduction

11.2 Modification of Electrodes with Nanoparticles

11.3 Geometric Factors in Electrocatalysis by Nanoparticles

11.4 Analytical Applications of Electrodes Modified with Metal Nanoparticles

11.5 Conclusions

12 Single Molecule and Single event Nanoelectrochemical Analysis

12.1 Introduction

12.2 Basic Concepts

12.3 Single-Molecule Electrochemistry

12.4 Single-Nanoparticle Electrochemical Detection

12.5 Nanoelectrodes for Ultrasensitive Electrochemical Detection and High-Resolution Imaging

12.6 Electrochemical Detection in Nanodomains of Biological Systems

12.7 Localized Delivery and Imaging by Using Single Nanopipette-Based Conductance Techniques

12.8 Final Remarks

Acknowledgments

13 Analytical Applications of Block Copolymer-Derived Nanoporous Membranes

13.1 Introduction

13.2 Monolithic Membranes Containing Arrays of Cylindrical Nanoscale Pores

13.3 BCP-Derived Monoliths Containing Arrays of Cylindrical Nanopores

13.4 Surface Functionalization of BCP-Derived Cylindrical Nanopores

13.5 Investigation of the Permeation of Molecules through BCP-Derived Nanoporous Monoliths and their Analytical Applications

13.6 Conclusions

Acknowledgments

14 Synthesis and Applications of Gold Nanorods

14.1 Introduction

14.2 Au Nanorod Synthesis

14.3 Signal Enhancement

14.4 Applications of Au Nanorods in Trace Analysis

14.5 Applications of Au Nanorods in Other Fields

14.6 Conclusions

Acknowledgments

Index

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The Editors

Dr. David T. Pierce

University of North Dakota

Department of Chemistry

151 Cornell Street, Stop 9024

Grand Forks, ND 58202-9024

USA

Dr. Julia Xiaojun Zhao

University of North Dakota

Department of Chemistry

151 Cornell Street, Stop 9024

Grand Forks, ND 58202-9024

USA

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No.: applied for

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.

© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

ISBN: 978-3-527-32350-0

ISBN: 978-3-527-63207-7 (epub)

ISBN: 978-3-527-64038-6 (mobi)

Preface

Trace analysis is an important topic that impacts various areas ranging from environmental monitoring to national security, food safety, clinical diagnosis, and forensic investigation. The need for sensitive and robust determinations in these areas has driven a rapid development of novel nanomaterials as well as new methodologies with which to implement them. Unfortunately, essential details of these new nanomaterials and approaches for their use have largely remained in wide-ranging journals and specialized compilations. Our goal for this book has been to provide an introduction to these new methods and materials in one source and thereby encourage the development of new, cross-disciplinary ideas among scientists from many different fields. Accordingly, this book includes a broad cross-section of nanomaterial-based methodologies and applications. Selected topics are reviewed in 14 chapters and organized in three sections.

Section I (Chapters 1–5) is dedicated to “Biological and Chemical Analysis.” The performance of biosensors and bioassays has been aided by the rapid development of nanotechnology and the application of various nanomaterials. Chapters 1 and 2 are focused on photoactive nanomaterials. Chapter 1 summarizes recent advances of photoswitchable nanoprobes that feature changes in fluorescence and magnetization. Contributions of these nanoprobes to super-resolution fluorescence imaging and acquisition of quantitative information of biological targets are reviewed. Semiconductor quantum dots (QDs) have attracted considerable attention in the fields of chemistry and biology over the past decade. Based on these recent advances, Chapter 2 reviews the fundamental properties, characteristic advantages, and synthetic methods for various semiconductor QDs. Several successful analytical applications of QDs in the field of chemistry and biology are discussed.

Chapters 3 and 4 emphasize nanomaterials-based electrochemical biosensors and bioassays. The enormous signal enhancement associated with the use of nanomaterial labels and the formation of nanomaterial–biomolecule complexes provides the basis for ultrasensitive electrochemical detection of disease-related gene or protein markers, biothreat agents, or infectious agents. Chapter 3 discusses various nanomaterials for bioanalysis, including nanoparticles, nanowires, nanotubes, and nanocarriers. The surface-dependent electron transport properties of nanomaterials are often used to develop chemical and biological sensors for trace analysis. Specifically, physical and/or chemical sorption of analytes on a nanomaterial surface may affect the rates of electron transport through a nanomaterial assembly, resulting in detectable change in its electronic conductivity. In Chapter 4, the authors review chemical and biological sensing applications based on electron transport through nanoparticle assemblies.

In addition to nanomaterials, nanodevices based on fluidics have reduced significantly the time and costs involved in chemical/biochemical experimentation. They have also permitted the study of several physical/chemical/biological systems at a fundamentally higher level. In Chapter 5, the authors describe applications of micro- and nanofluidic technology to the trace analysis of biological samples with a focus on assays involving nucleic acids, proteins/peptides, and biological cells.

Section II (Chapters 6–10) is dedicated to “Environmental Analysis.” Nano­materials have shown great potential for improving the detection and extraction of trace contaminants in the environment, but they may themselves pose an environmental hazard if released. Chapter 6 focuses on the analysis of water contaminated with endocrine-disrupting chemicals by the use of molecularly imprinted polymers (MIPs). This chapter gives an overview of significant achievements to improve the performance of MIPs in solid-phase extraction using particles during the last two years. Chapter 7 reviews current research on trace detection and quantification of nitrated and peroxide-based high explosives with various techniques involving nanomaterials. In particular, sensors based on electrochemistry, fluorescence, microcantilevers, and metal oxide semiconductive nanoparticles are discussed.

Hazardous metals are another important class of environmental pollutants. The authors of Chapter 8 survey the use of nanostructured materials for the selective collection of trace-level metals from aqueous systems. It has been shown that, when correctly constructed, these nanomaterials are superior sorbents and can be used to enhance trace level analysis. In addition to newly developed nanomaterials, some traditional nanomaterials, such as TiO2, have demonstrated new applications for trace detection, particularly in environmental analysis. Several TiO2-based nanostructures important in analysis applications are introduced in Chapter 9, including colloidal and mesoporous TiO2 nanoparticles, TiO2 nanotubes, TiO2-based hybrids, and TiO2 nanofilms. Also described are sample pretreatment and analyte preconcentration methods based on the strong adsorption of organic and inorganic species onto TiO2 nanomaterials.

In Chapter 10 the authors bring an interesting perspective to the use of engineered nanoparticles (ENPs). Not only are recent advances in the use of ENPs for environmental sensing described, but the environmental fate and toxicity of ENPs are also discussed.

Section III (Chapters 11–14) is dedicated to “Advanced Methods and Materials.” Here the development of new nanomaterials and new methods for trace analysis are discussed. In Chapter 11, a wide variety of analytical methods employing electrodes modified with nanoparticles are summarized. Chapter 12 focuses on the analysis of single molecules or single events using nanoelectrodes and combined optical and electrochemical methods.

Chapters 13 and 14 focus on the development and application of several new nanomaterials. Membranes derived from block copolymers (BCPs) and containing arrays of cylindrical nanoscale pores are described in Chapter 13. Recent achievements indicate that BCP-derived nanoporous monoliths are promising materials to develop highly efficient separation membranes for biomolecules and detection devices with high selectivity and sensitivity. Chapter 14 introduces gold nanorods (AuNRs) and a broad range of applications that transcend the now-familiar gold nanoparticle. The methods of synthesis and unique physicochemical characteristics of AuNRs are described in detail and their most recent uses in trace analysis are discussed.

We hope that you find this book useful during your research and that it proves helpful in developing new avenues for trace analysis. We certainly look forward to receiving your feedback. Finally, and most especially, we wish to thank each of the contributors to this book. Without their dedication and expertise, this work would never have been possible.

David T. Pierce

Julia Xiaojun Zhao

Grand Forks, USA, January 2010

List of Contributors

R. Shane Addleman

Pacific Northwest National Laboratory

P.O. Box 999

Richland, WA 99352

USA

Meenu Baloda

North Dakota State University

Department of Chemistry and Molecular Biology

Fargo, ND 58102

USA

John T. Bays

University of Oregon

P.O. Box 999

Eugene, OR 97403

USA

Timothy G. Carter

University of Oregon

Department of Chemistry and Materials Science Institute

Eugene, OR 97403-1253

USA

Jai-Pil Choi

California State University – Fresno

Department of Chemistry

2555 East San Ramon Avenue M/S SB70

Fresno, CA 93740-8034

USA

Rhett J. Clark

University of Alberta

Department of Chemistry

11227 Saskatchewan Dr.

Edmonton, Alberta

Canada T6G 2G2

James A. Cox

Miami University

Department of Chemistry and Biochemistry

501 East High Street

Oxford, OH 45056

USA

Zack De Maleki

Carleton University

Department of Chemistry

1125 Colonel By Drive

Ottawa, Ontario

Canada K1S 5B6

Debashis Dutta

University of Wyoming

Department of Chemistry

1000 East University Avenue

Laramie, WY 82071

USA

Anastasiya Dzhun,

Carleton University

Department of Chemistry

1125 Colonel By Drive

Ottawa, Ontario

Canada K1S 5B6

Nenny Fahruddin

University of North Dakota

Department of Chemistry

151 Cornell Street

Grand Forks, ND 58202-9024

USA

Sean A. Fontenot

University of Oregon

Department of Chemistry and Materials Science Institute

Eugene, OR 97403-1253

USA

Glen E. Fryxell

Pacific Northwest National Laboratory

P.O. Box 999

Richland, WA 99352

USA

Cunwang Ge

Nantong University

School of Chemistry and Chemical Engineering

Nantong

226007

China

Anant Gurung

North Dakota State University

Department of Chemistry and Molecular Biology

Fargo, ND 58102

USA

Yuqing He

Guangzhou Institute of Dermatology

Department of Dermatology

Guangzhou

510095

China

Takashi Ito

Kansas State University

Department of Chemistry

111 Willard Hall

Manhattan, KS 66506-0401

USA

Yuhui Jin

University of North Dakota

Department of Chemistry

151 Cornell Street

Grand Forks, ND 58202-9024

USA

Xiaohui Jing

Nantong University

School of Chemistry and Chemical Engineering

Nantong

226007

China

Carrie L. John

University of North Dakota

Department of Chemistry

151 Cornell Street

Grand Forks, ND 58202-9024

USA

Darren W. Johnson

University of Oregon

Department of Chemistry and Materials Science Institute

Eugene, OR 97403-1253

USA

Edward Lai

Carleton University

Department of Chemistry

1125 Colonel By Drive

Ottawa, Ontario

Canada K1S 5B6

Aize Li

University of North Dakota

Department of Chemistry

151 Cornell Street

Grand Forks, ND 58202-9024

USA

Alexander D.Q. Li

Washington State University

Department of Chemistry

Pullman, WA 99164

USA

Yuehe Lin

Pacific Northwest National Laboratory

Richland, WA 99351

USA

Guodong Liu

North Dakota State University

Department of Chemistry and Molecular Biology

Fargo, ND 58102

USA

Qiang Ma

Jilin University

Department of Analytical Chemistry

College of Chemistry

Changchun

130012

China

Xun Mao

North Dakota State University

Department of Chemistry and Molecular Biology

Fargo, ND 58102

USA

Wujian Miao

The University of Southern Mississippi

Department of Chemistry and Biochemistry

118 College Drive

Hattiesburg, MS 39406

USA

Shanlin Pan

The University of Alabama

Department of Chemistry

Tuscaloosa, AL 35487-0336

USA

Suman Parajuli

The University of Southern Mississippi

Department of Chemistry and Biochemistry

118 College Drive

Hattiesburg, MS 39406

USA

D.M. Neluni T. Perera

Kansas State University

Department of Chemistry

111 Willard Hall

Manhattan, KS 66506-0401

USA

David T. Pierce

University of North Dakota

Department of Chemistry

151 Cornell Street

Grand Forks, ND 58202-9024

USA

Jian Shi

Nantong University

School of Chemistry and Chemical Engineering

Nantong 226007

China

Shaina L. Strating

University of North Dakota

Department of Chemistry

151 Cornell Street

Grand Forks, ND 58202-9024

USA

Xingguang Su

Jilin University

Department of Analytical Chemistry

College of Chemistry

Changchun, 130012

China

Benjamen C. Sun

University of North Dakota

Department of Chemistry

151 Cornell Street

Grand Forks, ND 58202-9024

USA

Zhiyuan Tian

Washington State University

Department of Chemistry

Pullman, WA 99164

USA

Jonathan G.C. Veinot

University of Alberta

Department of Chemistry

11227 Saskatchewan Dr.

Edmonton, Alberta

Canada T6G 2G2

Gangli Wang

Georgia State University

Department of Chemistry

Atlanta, GA 30302-4098

USA

Cynthia L. Warner

Pacific Northwest National Laboratory

P.O. Box 999

Richland, WA 99352

USA

Marvin G. Warner

Pacific Northwest National Laboratory

P.O. Box 999

Richland, WA 99352

USA

Charles S. Wong

University of Winnipeg

Richardson College for the Environment, Environmental Studies Program and Department of Chemistry

515 Portage Ave.

Winnipeg Manitoba

Canada R3B 2E9

Wuwei Wu,

Washington State University

Department of Chemistry

Pullman, WA 99164

USA

Shuping Xu

Jilin University

State Key Laboratory of Supramolecular Structure and Materials

Changchun 130012

China

Wassana Yantasee

Pacific Northwest National Laboratory

P.O. Box 999

Richland, WA 99352

USA

Julia X. Zhao

University of North Dakota

Department of Chemistry

151 Cornell Street

Grand Forks, ND 58202-9024

USA

Julia Xiaojun Zhao

University of North Dakota

Department of Chemistry

151 Cornell Street

Grand Forks, ND 58202-9024

USA

Shouzhong Zou

Miami University

Department of Chemistry and Biochemistry

501 East High Street

Oxford, OH 45056

USA

Part 1: Biological and Chemical Analysis

1

Photoswitchable Nanoprobes for Biological Imaging Applications

Zhiyuan Tian, Wuwei Wu, and Alexander D.Q. Li

1.1 Introduction

Fluorescence imaging is widely used to study biological processes because it provides abundant information non-invasively regarding various biological mechanisms. The diffraction limit, however, restricts the best resolution of conventional fluorescence imaging techniques to a level two of orders of magnitude coarser than nano-sized molecules, leaving many intracellular organelles and molecular structures unresolvable. For example, fluorescent probes under conventional fluorescence microscope cannot be localized to accuracy better than 250 nm because of the diffraction limit barrier. Most biological targets such as RNA, DNA, and proteins form nanometer scale structures in cells, thus higher resolution beyond the diffraction limit of ca. 250 nm is essential to detect and monitor biological mechanisms at the single-molecule level.

Far-field fluorescence microscopy techniques with increased spatial resolution have the potential to convert microscopy into nanoscopy and thus enable near-molecular scale spatial resolution [1, 2]. Specifically, several super-resolution far-field fluorescence imaging techniques with 20 to 30 nm lateral and 50 to 60 nm axial imaging resolutions have been developed to circumvent the diffraction limit. These techniques include stimulated emission depletion (STED) microscopy [3–6] and reversible saturable optically linear fluorescent transitions (RESOLFT) mic­roscopy [7–9], stochastic optical reconstruction (STORM) microscopy [10–12], photo­activated localization(PALM) microscopy [13–17], photoactuated uni­molecular logical switching attained reconstruction (PULSAR) microscopy [18] , and other methods using similar principles [19]. Each of these techniques share a common underlying principle: images with high-resolution are obtained based on the switching of the fluorescent probes between two distinctively different fluorescent states, either fluorescent “ON” and “OFF” states or two fluorescent states with distinct color. In other words, the fluorescent probes employed must be actively modulated (usually via photoswitching or photoactivation) in time to ensure that only an optically resolvable subset of fluorophores is activated at any time in a diffraction-limited region, thereby allowing their localization with high accuracy. From this viewpoint, the development of fluorescence microscopy with ultrahigh spatial resolution depends, to a great extent, on the construction of photoswitchable fluorescent probes.

In addition to the contribution to super-resolution imaging, a dual-color photo­switchable fluorescent probe can highlight the biological target from its background despite the presence of autofluorescence in the target matrix [20, 21]. Besides photoswitching, high emission intensity of the fluorescent probe is also highly desirable. For example, both PULSAR and STORM rely on the detection of a single fluorescent probe and the location of fluorescent probe with high accuracy. The total number of photons that one fluorophore site can emit before photobleaching is an important photophysical parameter and ultimately determines the spatial resolution of the obtained fluorescence image. With single-molecule fluorophores as labeling reagents, rapid photobleaching and limited emission intensity per labeled site greatly hinder further improvement in imaging resolution. With fluorescent nanoparticles as labeling reagents, the overall fluorescence signal output from individual nanoparticle is proportional to the product of fluorescence efficiency and loading density of the encapsulated dyes. Because a large number of fluorophores is encapsulated inside a single nanoparticle, nanoparticles produce strong emission when properly excited [22, 23]. Newly developed photoswitchable fluorescent nanoparticles are expected to overcome limits of single-molecule fluorophores and therefore contribute to the further development of fluorescence imaging.

Several types of photoswitchable nanoprobes, including inorganic semicon­ductor nanoparticles, metal/metal oxide nanoparticles, polymeric nanoparticles, vesicle-like probes, and cloned photoactivatable proteins have been developed to date for various applications. Among them, nanoprobes with photoswitchable fluorescence [24–41] and magnetization [42–49] have drawn considerable attention for their important applications in biological fluorescence imaging and magnetic resonance imaging. Hence, in this chapter we outline the major classes of photoswitchable nanoprobes developed recently with an emphasis on fluorescent and magnetic nanoparticles and their roles in biological imaging. Although other photoswitchable features are also interesting, such as photoswitchable conductance [50–53] and surface wettability [54], we limit our scope to photoswitchable nanoprobes for biological applications.

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