In the present review, aerogels designate dried gels with a very high relative pore volume. These are versatile materials that are synthesized in a first step by low-temperature traditional sol-gel chemistry. However, while in the final step most wet gels are often dried by evaporation to produce so-called xerogels, aerogels are dried by other techniques, essentially supercritical drying. As a result, the dry samples keep the very unusual porous texture which they had in the wet stage. In general these dry solids have very low apparent densities, large specific surface areas, and in most cases they exhibit amorphous structures when examined by X-ray diffraction (XRD) methods. In addition, they are metastable from the point of view of their thermodynamic properties. Consequently, they often undertake a structural evolution by chemical transformation, when aged in a liquid medium and/or heat treated. As aerogels combine the properties of being highly divided solids with their metastable character, they can develop very attractive physical and chemical properties not achievable by other means of low temperature soft chemical synthesis. In other words, they form a new class of solids showing sophisticated potentialities for a range of applications. These applications as well as chemical and physical aspects of these materials were regularly detailed and discussed in a series of symposia on aerogels,1-5 the last of them being held in Albuquerque in 2000.6 Reviews were also regularly published, either on both xerogels and aerogels7 or more focused on the applications of aerogels.8-13 The particularly interesting properties of aerogels arise from the extraordinary flexibility of the solgel processing, coupled with original drying techniques. The wet chemistry is not basically different for making xerogels and aerogels. As this common basis has been extensively detailed in recent books,14 it does not need to be reviewed. Compared to traditional xerogels, the originality of aerogels comes from * To whom all correspondence should be addressed. † Institut de Recherches sur la Catalyse. ‡ Laboratoire d’Application de la Chimie à l’Environnement. 4243 Chem. Rev. 2002, 102, 4243−4265

https://is.muni.cz/el/1431/podzim2006/C7780/um/Read/2711172/aerogel_Pajonk_ChRev02_4243.pdf

Chemistry of Aerogels and Their Applications

Electrogenerated chemiluminescence (also called electrochemiluminescence and abbreviated ECL) is the process whereby species generated at electrodes undergo high-energy electron-transfer reactions to form excited states that emit light. The first detailed ECL studies were described by Hercules and Bard et al. in the mid-1960s, although reports concerning light emission during electrolysis date back to the 1920s by Harvey. After about 40 years study, ECL has now become a very powerful analytical technique and been widely used in the areas of, for example, immunoassay, food and water testing, and biowarfare agent detection. ECL has also been successfully exploited as a detector of flow injection analysis (FIA), high-performance liquid chromatography (HPLC), capillary electrophoresis, and micro total analysis (μTAS). Figure 1 illustrates a time line of various events in the development of ECL. A literature survey using SciFinder Scholar reveals that more than 2000 journal articles, book chapters, and patents on various topics of ECL have been published. The overall number of publications, as shown in Figure 2, has increased exponentially over the past 20 years, of which 40–50% were biorelated. Similar amounts of ECL papers could be also found from the Thomson ISI Web of Science as well as † Telephone (601) 266 4716; fax (601) 266 6075; e-mail wujian.miao@ usm.edu. Wujian Miao received his undergraduate diploma in chemistry from Nantong University (Nantong, China) in 1982, his M.Sc. degree in analytical chemistry from Zhongshan University (Guangzhou, China, with Jinyuan Mo) in 1991, and his Ph.D. degree in electrochemistry from Monash University (Melbourne, Australia, with Alan M. Bond) in 2000. He then served as a Research Scientist in CSIRO (Melbourne, Australia), followed by a postdoctoral fellowship at the University of Texas at Austin with Allen J. Bard in 2001. Since 2004 he has served as an assistant professor of chemistry at the University of Southern Mississippi.

Electrogenerated Chemiluminescence and Its Biorelated Applications

After having reviewed some aspects of microfluidic system preparation in the first part (1), in this second part of the review we will cover a number of standard operations (namely: sample preparation, sample injection, sample manipulation, reaction, separation, and detection) as well as some biological applications of micro total analysis systems (namely: cell culture, polymerase chain reaction, DNA separation, DNA sequencing, and clinical diagnostics). As previously, we will include papers issued from different scientific journals as well as useful abstracts from three conference proceedings: MEMS, Transducers, and μTAS. In this second part, we do not include the period covered by the history section (1975-1997) from part 1 but try to cover the relevant examples of the literature published between January 1998 and March 2002. We briefly describe articles that struck us as needing special attention, while more “standard” papers are dutifully reported in groups of interest. An article might be included in more than one section, depending on the ideas developed in it.

Micro total analysis systems. 2. Analytical standard operations and applications.

The suitability of electrowetting-on-dielectric (EWD) microfluidics for true lab-on-a-chip applications is discussed. The wide diversity in biomedical applications can be parsed into manageable components and assembled into architecture that requires the advantages of being programmable, reconfigurable, and reusable. This capability opens the possibility of handling all of the protocols that a given laboratory application or a class of applications would require. And, it provides a path toward realizing the true lab-on-a-chip. However, this capability can only be realized with a complete set of elemental fluidic components that support all of the required fluidic operations. Architectural choices are described along with the realization of various biomedical fluidic functions implemented in on-chip electrowetting operations. The current status of this EWD toolkit is discussed. However, the question remains: which applications can be performed on a digital microfluidic platform? And, are there other advantages offered by electrowetting technology, such as the programming of different fluidic functions on a common platform (reconfigurability)? To understand the opportunities and limitations of EWD microfluidics, this paper looks at the development of lab-on-chip applications in a hierarchical approach. Diverse applications in biotechnology, for example, will serve as the basis for the requirements for electrowetting devices. These applications drive a set of biomedical fluidic functions required to perform an application, such as cell lysing, molecular separation, or analysis. In turn, each fluidic function encompasses a set of elemental operations, such as transport, mixing, or dispensing. These elemental operations are performed on an elemental set of components, such as electrode arrays, separation columns, or reservoirs. Examples of the incorporation of these principles in complex biomedical applications are described.

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Digital microfluidics: is a true lab-on-a-chip possible?

Integrated microfluidic devices

A silica-based solid-phase extraction system suitable for incorporation into a microchip platform (micro-total analytical system; micro-TAS) would find utility in a variety of genetic analysis protocols, including DNA sequencing. The extraction procedure utilized is based on adsorption of the DNA onto bare silica. The procedure involves three steps: (i) DNA adsorption in the presence of a chaotropic salt, (ii) removal of contaminants with an alcohol/water solution, and (iii) elution of the adsorbed DNA in a small volume of buffer suitable for polymerase chain reaction (PCR) amplification. Multiple approaches for incorporation of this protocol into a microchip were examined with regard to extraction efficiency, reproducibility, stability, and the potential to provide PCR-amplifiable DNA. These included packing microchannels with silica beads only, generating a continuous silica network via sol-gel chemistry, and combinations of these. The optimal approach was found to involve immobilizing silica beads packed into the channel using a sol-gel network. This method allowed for successful extraction and elution of nanogram quantities of DNA in less than 25 min, with the DNA obtained in the elution buffer fraction. Evaluation of the eluted DNA indicated that it was of suitable quality for subsequent amplification by PCR.

Toward a microchip-based solid-phase extraction method for isolation of nucleic acids

A novel, high hydrolysis ratio sol-gel route for the biocompatible production of macroporous silica gels is presented. This route exploits the two step nature of the gelation reaction to remove undesired alcohol by-products from an acidic aqueous sol prior to gelation. These alcohol-free sols will gel when the pH is raised to the physiologic range in a two-step, acid/base catalyzed process. Furthermore, monolithic macroporous samples can be produced in a controlled manner by introducing water-soluble organic polymers into the sol.

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Cells in sol-gels I : A cytocompatible route for the production of macroporous silica gels

The longitudinal acoustic velocity in silica aerogel is presented as a function of the interstitial gas type and pressure. This was measured using air-coupled ultrasonic transducers configured for differential pulse transit time measurements. The results are interpreted in terms of the thermal relaxation of the acoustic pulse. The microscale temperature oscillations of the gas and solid phases of the aerogel due to the acoustic pulse are not identical if the rate of heat transfer between the two phases is slow compared to the period of the acoustic oscillation. The energy transferred from the gas to the solid phase is lost to the acoustic propagation and, thus, reduces the amplitude and velocity of the acoustic wave. The gas type and pressure may provide independent variables for probing these effects in aerogel.

/pdf/microscale-thermal-relaxation-during-acoustic-propagation-in-2efumutyq1.pdf

Microscale thermal relaxation during acoustic propagation in aerogel and other porous media

An approach for building DNA hybridization arrays has been developed, in which silica aquogel arrays are produced using micropiezoelectric printheads. When supercritically dried, the pads in these gel arrays have a footprint size of 0.4 ± 0.1 mm in diameter in which the porous silica has a density of 0.045 g cm −3 , pore diameters ranging between a few nanometers and 0.5 μm, and internal surface areas >800 m 2 g −1 (5 × 10 −4 m 2 per pad). This enormous internal surface area, combined with reasonable accessibility to internal binding sites, makes aquogel pads ideally suited for hybridization arrays. Silanized probe DNA was immobilized within the gel pads during gelation, and hybridization was carried out with fluorescently labeled target DNA. The array sites containing probe DNA and the control sites without probes are readily distinguishable using laser-assisted fluorescent scanning.

The design and testing of a silica sol–gel-based hybridization array

A sol and a method for forming a sol that can be used to immobilize biological materials and/or form robust macroporous gels. As needed, sols that are compatible with biological materials can be produced. Also as needed, robust macroporous gels can be formed by introducing dispersants to suitable sols.

John F.T. Conroy

Papers

Toward a microchip-based solid-phase extraction method for isolation of nucleic acids

Cells in sol-gels I : A cytocompatible route for the production of macroporous silica gels

Microscale thermal relaxation during acoustic propagation in aerogel and other porous media

The design and testing of a silica sol–gel-based hybridization array

Sol-gel biomaterial immobilization