Showing papers in "Chemical Reviews in 2013"

Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis

Abstract: A fundamental aim in the field of catalysis is the development of new modes of small molecule activation. One approach toward the catalytic activation of organic molecules that has received much attention recently is visible light photoredox catalysis. In a general sense, this approach relies on the ability of metal complexes and organic dyes to engage in single-electron-transfer (SET) processes with organic substrates upon photoexcitation with visible light. Many of the most commonly employed visible light photocatalysts are polypyridyl complexes of ruthenium and iridium, and are typified by the complex tris(2,2′-bipyridine) ruthenium(II), or Ru(bpy)32+ (Figure 1). These complexes absorb light in the visible region of the electromagnetic spectrum to give stable, long-lived photoexcited states.1,2 The lifetime of the excited species is sufficiently long (1100 ns for Ru(bpy)32+) that it may engage in bimolecular electron-transfer reactions in competition with deactivation pathways.3 Although these species are poor single-electron oxidants and reductants in the ground state, excitation of an electron affords excited states that are very potent single-electron-transfer reagents. Importantly, the conversion of these bench stable, benign catalysts to redox-active species upon irradiation with simple household lightbulbs represents a remarkably chemoselective trigger to induce unique and valuable catalytic processes. Open in a separate window Figure 1 Ruthenium polypyridyl complexes: versatile visible light photocatalysts.

Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources

Abstract: Renewable Resources Robert-Jan van Putten,†,‡ Jan C. van der Waal,† Ed de Jong,*,† Carolus B. Rasrendra,‡,⊥ Hero J. Heeres,*,‡ and Johannes G. de Vries* †Avantium Chemicals, Zekeringstraat 29, 1014 BV Amsterdam, the Netherlands ‡Department of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands DSM Innovative Synthesis BV, P.O. Box 18, 6160 MD Geleen, the Netherlands Department of Chemical Engineering, Institut Teknologi Bandung, Ganesha 10, Bandung 40132, Indonesia

Luminescent chemodosimeters for bioimaging.

Abstract: Yuming Yang,†,§ Qiang Zhao,‡,§ Wei Feng,† and Fuyou Li*,† †Department of Chemistry and State Key Laboratory of Molecular Engineering of Polymers and Institutes of Biomedical Sciences, Fudan University, Shanghai 200433, P. R. China ‡Key Laboratory for Organic Electronics and Information Displays (KLOEID) and Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications, Nanjing 210046, P. R. China.

Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2 Fixation

Abstract: Two major energy-related problems confront the world in the next 50 years. First, increased worldwide competition for gradually depleting fossil fuel reserves (derived from past photosynthesis) will lead to higher costs, both monetarily and politically. Second, atmospheric CO_2 levels are at their highest recorded level since records began. Further increases are predicted to produce large and uncontrollable impacts on the world climate. These projected impacts extend beyond climate to ocean acidification, because the ocean is a major sink for atmospheric CO2.1 Providing a future energy supply that is secure and CO_2-neutral will require switching to nonfossil energy sources such as wind, solar, nuclear, and geothermal energy and developing methods for transforming the energy produced by these new sources into forms that can be stored, transported, and used upon demand.

Aerobic Copper-Catalyzed Organic Reactions

Abstract: The chemistry of copper is extremely rich because it can easily access Cu0, CuI, CuII, and CuIII oxidation states allowing it to act through one-electron or two-electron processes. As a result, both radical pathways and powerful two-electron bond forming pathways via organmetallic intermediates, similar to those of palladium, can occur. In addition, the different oxidation states of copper associate well with a large number of different functional groups via Lewis acid interactions or π-coordination. In total, these feature confer a remarkably broad range of activities allowing copper to catalyze the oxidation and oxidative union of many substrates. Oxygen is a highly atom economical, environmentally benign, and abundant oxidant, which makes it ideal in many ways.1 The high activation energies in the reactions of oxygen require that catalysts be employed.2 In combination with molecular oxygen, the chemistry of copper catalysis increases exponentially since oxygen can act as either a sink for electrons (oxidase activity) and/or as a source of oxygen atoms that are incorporated into the product (oxygenase activity). The oxidation of copper with oxygen is a facile process allowing catalytic turnover in net oxidative processes and ready access to the higher CuIII oxidation state, which enables a range of powerful transformations including two-electron reductive elimination to CuI. Molecular oxygen is also not hampered by toxic byproducts, being either reduced to water, occasionally via H2O2 (oxidase activity) or incorporated into the target structure with high atom economy (oxygenase activity). Such oxidations using oxygen or air (21% oxygen) have been employed safely in numerous commodity chemical continuous and batch processes.3 However, batch reactors employing volatile hydrocarbon solvents require that oxygen concentrations be kept low in the head space (typically <5–11%) to avoid flammable mixtures, which can limit the oxygen concentration in the reaction mixture.4,5,6 A number of alternate approaches have been developed allowing oxidation chemistry to be used safely across a broader array of conditions. For example, use of carbon dioxide instead of nitrogen as a diluent leads to reduced flammability.5 Alternately, water can be added to moderate the flammability allowing even pure oxygen to be employed.6 New reactor designs also allow pure oxygen to be used instead of diluted oxygen by maintaining gas bubbles in the solvent, which greatly improves reaction rates and prevents the build up of higher concentrations of oxygen in the head space.4a,7 Supercritical carbon dioxide has been found to be advantageous as a solvent due its chemical inertness towards oxidizing agents and its complete miscibility with oxygen or air over a wide range of temperatures.8 An number of flow technologies9 including flow reactors,10 capillary flow reactors,11 microchannel/microstructure structure reactors,12 and membrane reactors13 limit the amount of or afford separation of hydrocarbon/oxygen vapor phase thereby reducing the potential for explosions. Enzymatic oxidizing systems based upon copper that exploit the many advantages and unique aspects of copper as a catalyst and oxygen as an oxidant as described in the preceding paragraphs are well known. They represent a powerful set of catalysts able to direct beautiful redox chemistry in a highly site-selective and stereoselective manner on simple as well as highly functionalized molecules. This ability has inspired organic chemists to discover small molecule catalysts that can emulate such processes. In addition, copper has been recognized as a powerful catalyst in several industrial processes (e.g. phenol polymerization, Glaser-Hay alkyne coupling) stimulating the study of the fundamental reaction steps and the organometallic copper intermediates. These studies have inspiried the development of nonenzymatic copper catalysts. For these reasons, the study of copper catalysis using molecular oxygen has undergone explosive growth, from 30 citations per year in the 1980s to over 300 citations per year in the 2000s. A number of elegant reviews on the subject of catalytic copper oxidation chemistry have appeared. Most recently, reviews provide selected coverage of copper catalysts14 or a discussion of their use in the aerobic functionalization of C–H bonds.15 Other recent reviews cover copper and other metal catalysts with a range of oxidants, including oxygen, but several reaction types are not covered.16 Several other works provide a valuable overview of earlier efforts in the field.17 This review comprehensively covers copper catalyzed oxidation chemistry using oxygen as the oxidant up through 2011. Stoichiometric reactions with copper are discussed, as necessary, to put the development of the catalytic processes in context. Mixed metal systems utilizing copper, such as palladium catalyzed Wacker processes, are not included here. Decomposition reactions involving copper/oxygen and model systems of copper enzymes are not discussed exhaustively. To facilitate analysis of the reactions under discussion, the current mechanistic hypothesis is provided for each reaction. As our understanding of the basic chemical steps involving copper improve, it is expected that many of these mechanisms will evolve accordingly.

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

Abstract: The review covers the knowledge on photoremovable protecting groups and includes all relevant chromophores studied in the time period of 2000–2012; the most relevant earlier works are also discussed.

Protein Analysis by Shotgun/Bottom-up Proteomics

Abstract: According to Genome Sequencing Project statistics (http://www.ncbi.nlm.nih.gov/genomes/static/gpstat.html), as of Feb 16, 2012, complete gene sequences have become available for 2816 viruses, 1117 prokaryotes, and 36 eukaryotes.1–2 The availability of full genome sequences has greatly facilitated biological research in many fields, and has greatly contributed to the growth of proteomics. Proteins are important because they are the direct bio-functional molecules in the living organisms. The term “proteomics” was coined from merging “protein” and “genomics” in the 1990s.3–4 As a post-genomic discipline, proteomics encompasses efforts to identify and quantify all the proteins of a proteome, including expression, cellular localization, interactions, post-translational modifications (PTMs), and turnover as a function of time, space and cell type, thus making the full investigation of a proteome more challenging than sequencing a genome. There are possibly 100,000 protein forms encoded by the approximate 20,235 genes of the human genome,5 and determining the explicit function of each form will be a challenge. The progress of proteomics has been driven by the development of new technologies for peptide/protein separation, mass spectrometry analysis, isotope labeling for quantification, and bioinformatics data analysis. Mass spectrometry has emerged as a core tool for large-scale protein analysis. In the past decade, there has been a rapid advance in the resolution, mass accuracy, sensitivity and scan rate of mass spectrometers used to analyze proteins. In addition, hybrid mass analyzers have been introduced recently (e.g. Linear Ion Trap-Orbitrap series6–7) which have significantly improved proteomic analysis. “Bottom-up” protein analysis refers to the characterization of proteins by analysis of peptides released from the protein through proteolysis. When bottom-up is performed on a mixture of proteins it is called shotgun proteomics,8–10 a name coined by the Yates lab because of its analogy to shotgun genomic sequencing.11 Shotgun proteomics provides an indirect measurement of proteins through peptides derived from proteolytic digestion of intact proteins. In a typical shotgun proteomics experiment, the peptide mixture is fractionated and subjected to LC-MS/MS analysis. Peptide identification is achieved by comparing the tandem mass spectra derived from peptide fragmentation with theoretical tandem mass spectra generated from in silico digestion of a protein database. Protein inference is accomplished by assigning peptide sequences to proteins. Because peptides can be either uniquely assigned to a single protein or shared by more than one protein, the identified proteins may be further scored and grouped based on their peptides. In contrast, another strategy, termed ‘top-down’ proteomics, is used to characterize intact proteins (Figure 1). The top-down approach has some potential advantages for PTM and protein isoform determination and has achieved notable success. Intact proteins have been measured up to 200 kDa,12 and a large scale study has identified more than 1,000 proteins by multi-dimensional separations from complex samples.13 However, the top-down method has significant limitations compared with shotgun proteomics due to difficulties with protein fractionation, protein ionization and fragmentation in the gas phase. By relying on the analysis of peptides, which are more easily fractionated, ionized and fragmented, shotgun proteomics can be more universally adopted for protein analysis. In fact, a hybrid of bottom-up and top-down methodologies and instrumentation has been introduced as middle-down proteomics.14 Essentially, middle-down proteomics analyzes larger peptide fragments than bottom-up proteomics, minimizing peptide redundancy between proteins. Additionally the large peptide fragments yield similar advantages as top-down proteomics, such as gaining further insight into post-translational modifications, without the analytical challenges of analyzing intact proteins. Shotgun proteomics has become a workhorse for the analysis of proteins and their modifications and will be increasingly combined with top-down methods in the future. Figure 1 Proteomic strategies: bottom-up vs. top-down vs. middle-down. The bottom-up approach analyzes proteolytic peptides. The top-down method measures the intact proteins. The middle-down strategy analyzes larger peptides resulted from limited digestion or ... In the past decade shotgun proteomics has been widely used by biologists for many different research experiments, advancing biological discoveries. Some applications include, but are not limited to, proteome profiling, protein quantification, protein modification, and protein-protein interaction. There have been several reviews nicely summarizing mass spectrometry history,15 protein quantification with mass spectrometry,16 its biological applications,5,17–26 and many recent advances in methodology.27–32 In this review, we try to provide a full and updated survey of shotgun proteomics, including the fundamental techniques and applications that laid the foundation along with those developed and greatly improved in the past several years.

Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology.

Abstract: Chemistries that Facilitate Nanotechnology Kim E. Sapsford,† W. Russ Algar, Lorenzo Berti, Kelly Boeneman Gemmill,‡ Brendan J. Casey,† Eunkeu Oh, Michael H. Stewart, and Igor L. Medintz*,‡ †Division of Biology, Department of Chemistry and Materials Science, Office of Science and Engineering Laboratories, U.S. Food and Drug Administration, Silver Spring, Maryland 20993, United States ‡Center for Bio/Molecular Science and Engineering Code 6900 and Division of Optical Sciences Code 5611, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States College of Science, George Mason University, 4400 University Drive, Fairfax, Virginia 22030, United States Department of Biochemistry and Molecular Medicine, University of California, Davis, School of Medicine, Sacramento, California 95817, United States Sotera Defense Solutions, Crofton, Maryland 21114, United States

Nanocarbons for the Development of Advanced Catalysts

Abstract: Dang Sheng Su,*,†,‡ Siglinda Perathoner, and Gabriele Centi* †Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Science, 72 Wenhua Road, Shenyang 110006, China ‡Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin, Germany Dipartimento di Ingegneria Elettronica, Chimica ed Ingegneria Industriale, University of Messina and INSTM/CASPE (Laboratory of Catalysis for Sustainable Production and Energy), Viale Ferdinando Stagno, D’Alcontres 31, 98166 Messina, Italy

SERS Tags: Novel Optical Nanoprobes for Bioanalysis

Abstract: CONTENTS 1. Introduction 1.1. Fundamental Theory of Surface-Enhanced Raman Scattering 1.2. Optical Properties of SERS Tags 2. Synthesis of SERS Tags 2.1. Noble Metal Nanosubstrates 2.1.1. Single Particle-Based SERS Substrates 2.1.2. Nanoparticle Cluster-Based Substrates 2.2. Raman Reporter Molecules 2.2.1. Selection Principles and Reporter Types 2.2.2. Self-Assembled Monolayer Coverage Strategy 2.3. Surface Coating for Protection 2.3.1. Biomolecule Coating 2.3.2. Polymer Coating 2.3.3. Liposome Coating 2.3.4. Silica Coating 2.4. Attachment of Targeting Molecules 3. Bioanalysis Applications 3.1. Ionic and Molecular Detection 3.2. Pathogen Detection 3.3. Live-Cell Imaging 3.3.1. Cancer Marker Detection 3.3.2. Intercellular Microenvironment Sensing 3.4. Tissue SERS Imaging 3.5. In Vivo SERS Imaging 4. Challenges and Perspectives 4.1. Reproducible Signal of SERS Tags 4.1.1. Precisely Controlled Hot Spots for Nanosubstrates 4.1.2. Calibration of SERS Intensities and Enhancements 4.2. Improving Multiplexing Capability 4.3. Reduced Size for Subcellular Imaging 4.4. Development of Multifunctional Nanoplatforms 4.4.1. Magnetic SERS Dots 4.4.2. Multimodal Imaging Dots 4.4.3. SERS Tag-Based Therapeutic Systems 4.5. Biocompatibility 5. Conclusions and Remarks

Polyanionic (phosphates, silicates, sulfates) frameworks as electrode materials for rechargeable Li (or Na) batteries.

Abstract: For more than 20 years, most of the technological achievements for the realization of positive electrodes for practical rechargeable Li battery systems have been devoted to transition metal oxides such as LixMO2 (M = Co, Ni, Mn), LixMn2O4, LixV2O5, or LixV3O8. The first two classes of materials built on close-packed oxygen stacking adopt bidimensional and tridimensional crystal structures, respectively (Figure 1), from which lithium ions may be easily intercalated or extracted in a reversible manner. These oxides are reasonably good ionic and electronic conductors, and lithium insertion/extraction proceeds while operating on the M4+/M3+ redox couple, located between 4 and 5 V versus Li+/Li...

Cysteine-Mediated Redox Signaling: Chemistry, Biology, and Tools for Discovery

Abstract: Reactive oxygen, nitrogen, and sulfur species, referred to as ROS, RNS, and RSS, respectively, are produced during normal cell function and in response to various stimuli. An imbalance in the metabolism of these reactive intermediates results in the phenomenon known as oxidative stress. If left unchecked, oxidative molecules can inflict damage on all classes of biological macromolecules and eventually lead to cell death. Indeed, sustained elevated levels of reactive species have been implicated in the etiology (e.g., atherosclerosis, hypertension, diabetes) or the progression (e.g., stroke, cancer, and neurodegenerative disorders) of a number of human diseases.1 Over the past several decades, however, a new paradigm has emerged in which the aforementioned species have also been shown to function as targeted, intracellular second messengers with regulatory roles in an array of physiological processes.2 Against this backdrop, it is not surprising that considerable ongoing efforts are aimed at elucidating the role that these reactive intermediates play in health and disease. Site-specific, covalent modification of proteins represents a prominent molecular mechanism for transforming an oxidant signal into a biological response. Amino acids that are candidates for reversible modification include cysteines whose thiol (i.e., sulfhydryl) side chain is deprotonated at physiological pH, which is an important attribute for enhancing reactivity. While reactive species can modify other amino acids (e.g., histidine, methionine, tryptophan, and tyrosine), this Review will focus exclusively on cysteine, whose identity as cellular target or “sensor” of reactive intermediates is most prevalent and established.3 Oxidation of thiols results in a range of sulfur-containing products, not just disulfide bridges, as typically presented in biochemistry textbooks. An overview of the most relevant forms of oxidized sulfur species found in vivo is presented in Chart 1. Open in a separate window Chart 1 Biologically Relevant Cysteine Chemotypesa aRed, irreversible modifications. Green, unique enzyme intermediates. Note: Additional modifications can form as enzyme intermediates including thiyl radicals, disulfides, and persulfides.

Nanoscaled metal borides and phosphides: recent developments and perspectives

Abstract: and Perspectives Sophie Carenco,†,‡,§,∥,⊥ David Portehault,*,†,‡,§ Ced́ric Boissier̀e,†,‡,§ Nicolas Meźailles, and Cleḿent Sanchez*,†,‡,§ †Chimie de la Matier̀e Condenseé de Paris, UPMC Univ Paris 06, UMR 7574, Colleg̀e de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France ‡Chimie de la Matier̀e Condenseé de Paris, CNRS, UMR 77574, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Chimie de la Matier̀e Condenseé de Paris, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Laboratory Heteroelements and Coordination, Chemistry Department, Ecole Polytechnique, CNRS-UMR 7653, Palaiseau, France

On the Versatility of Urethane/Urea Bonds: Reversibility, Blocked Isocyanate, and Non-isocyanate Polyurethane

Abstract: Isocyanate, and Non-isocyanate Polyurethane Etienne Delebecq,† Jean-Pierre Pascault,‡,§ Bernard Boutevin,† and Franco̧is Ganachaud*,†,‡,§ †Institut Charles Gerhardt, UMR 5253 CNRS, Ingeńierie et Architectures Macromolećulaires, Ecole Nationale Supeŕieure de Chimie de Montpellier, 8 rue de l’ećole normale, 34296 Montpellier, Cedex 05, France ‡INSA-Lyon, IMP, UMR5223, F-69621, Villeurbanne, France Universite ́ de Lyon, F-69622, Lyon, France

Transition Metal-Mediated Synthesis of Monocyclic Aromatic Heterocycles

Abstract: Heterocycles constitute the largest and the most diverse family of organic compounds Among them, aromatic heterocycles represent structural motifs found in a great number of biologically active natural and synthetic compounds, drugs, and agrochemicals Moreover, aromatic heterocycles are widely used for synthesis of dyes and polymeric materials of high value 1 There are numerous reports on employment of aromatic heterocycles as intermediates in organic synthesis 2 Although, a variety of highly efficient methodologies for synthesis of aromatic heterocycles and their derivatives have been reported in the past, the development of novel methodologies is in cuntinious demand Particlularly, development of new synthetic approaches toward heterocycles, aiming at achieving greater levels of molecular complexity and better functional group compatibilities in a convergent and atom economical fashions from readily accessible starting materials and under mild reaction conditions, is one of a major research endeavor in modern synthetic organic chemistry Transition metal-catalyzed transformations, which often help to meet the above criteria, are among the most attractive synthetic tools Several excellent reviews dealing with transition metal-catalyzed synthesis of heterocyclic compounds have been published in literature during recent years Many of them highlighted the use of a particular transition metal, such as gold,3 silver,4 palladium,5 copper,6 cobalt,7 ruthenium,8 iron,9 mercury,10 rare-earth metals,11 and others Another array of reviews described the use of a specific kind of transformation, for instance, intramolecular nucleophilic attack of heteroatom at multiple C–C bonds,12 Sonogashira reaction,13 cycloaddition reactions,14 cycloisomerization reactions,15 C–H bond activation processes,16 metathesis reactions,17 etc Reviews devoted to an application of a particular type of starting materials have also been published Thus, for example, applications of isocyanides,18 diazocompounds,19 or azides20 have been discussed In addition, a significant attention was given to transition metal-catalyzed multicomponent syntheses of heterocycles21 Finally, syntheses of heterocycles featuring formation of intermediates, such as nitrenes,22 vinylidenes,23 carbenes, and carbenoids24 have also been reviewed The main focus of the present review is a transition metal-catalyzed synthesis of aromatic monocyclic heterocycles The organization of the review is rather classical and is based on a heterocycle, categorized in the following order: (a) ring size of heterocycle, (b) number of heteroatoms, (c) type of heterocycle, and (d) a class of transformation involved A brief mechanistic discussion is given to provide information about a possible reaction pathway when necessary The review mostly discusses recent literature, starting from 200425 until the end of 2011, however, some earlier parent transformations are discussed when needed

X-ray-Computed Tomography Contrast Agents

Abstract: X-ray computed tomography (CT) is a well-established tissue imaging technique employed in a variety of research and clinical settings.1 Specifically, CT is a non-invasive clinical diagnostic tool that allows for 3D visual reconstruction and segmentation of tissues of interest. High resolution CT systems can be used to perform non-destructive 3D imaging of a variety of tissue types and organ systems, such as: the gastrointestinal tract, cardiovascular system, renal tract, liver, lungs, bone, cartilage, tumorous tissue, etc. CT is one of the most prevalent diagnostic tools in terms of frequency-of-use and hospital availability.2 The use of CT is on the rise and the number of clinical CT scanners in operation worldwide is estimated at over 45,000.1b Today, over 70 million clinical CT scans are performed yearly in the U.S. alone. For a recent detailed analysis of the use of clinical CT imaging and data regarding the number of regular and contrast-enhanced CT scans performed annually in the U.S. we refer the reader to the “Nationwide Evaluation of X-ray Trends” survey published by the Conference for Radiation Control Program Directors (CRCPD).3 The idea of using tomography (Greek: tomos = slice, graphein = draw) as a diagnostic tool in medicine was adopted soon after the discovery of X-rays by W. C. Roentgen in 1895. However, several more decades passed before the technology advanced sufficiently to bring those ideas to fruition. The first successful CT imaging device was built in 1972 by G. N. Hounsfield, at Electric and Musical Industries Ltd. In 1979, G. N. Hounsfield and South African physicist A. M. Cormack shared a Nobel Prize in medicine for their contributions to the field of X-ray CT imaging and diagnostics.4 X-rays are a form of electromagnetic radiation with wavelengths roughly between 0.01 nm and 10 nm. Traditionally, X-rays are generated by a vacuum tube using high voltage to accelerate electrons from a cathode to a (usually) tungsten-alloy anode. In the process, the accelerated electrons release electromagnetic radiation in the form of X-rays and the maximum energy of the radiation is limited by the energy of the incident electron. Operating voltages of modern clinical CT scanners differ among instrument models and manufacturers, but generally fall between 80 kVp to 150 kVp. As a rule, materials possessing higher density (ρ) or high atomic number (Z) tend to better absorb X-rays. The relationship is best expressed in the formula for X-ray absorption coefficient (μ): μ≈ρZ4AE3 (1) where “A” is the atomic mass and “E” is the X-ray energy. The strong relationship between absorption and atomic number is of significant importance in clinical applications. The Z4 factor allows for contrast levels of several orders of magnitude between different tissues and types of contrast agents. When an incident X-ray has energy equal or slightly greater than the binding energy of the K-shell electron of the atom, a large sudden increase in absorption coefficient is observed. This energy value is known as absorption edge (k), and the k value increases with atomic number of the element. Consequently, X-ray attenuating contrast media containing atoms of high atomic number (most commonly iodine or barium), are frequently used in clinical settings to obtain images of soft tissues. To generate images with the highest contrast to the surrounding tissue, the energy of the X-ray source can be adjusted to closely match the absorption edge value (k) of the relevant imaging-agent atoms (i.e., iodine, barium, gold, etc.). Thus, it is also possible to do selective X-ray imaging and to differentiate between attenuating materials by fine tuning the energy source to the appropriate absorption edge value. A CT image is obtained by rotating an X-ray source around an object, with a detector positioned directly opposite the radiation source. Alternatively, in many preclinical CT scanners the object sometimes is rotated around its own axis. Such preclinical scanners are often being used for small animal in vivo imaging. Generally, X-ray scans are taken at small angular increments during rotation around the object over 360°. A series of attenuation profiles or projections is thus obtained. The projections are then processed mathematically to create a 3D rendition of the scanned object. An in depth description of the engineering principles underlying modern CT imaging instruments is beyond the scope of this manuscript, and the reader is referred to other published works.1c,5 A diagnostic imaging method related to CT is X-ray fluoroscopy. Fluoroscopy allows for the acquisition of real-time, continuous images of the internal organs. Like in CT, imaging agents are often used in fluoroscopy for better contrast resolution. Small iodinated agents are commonly injected into blood vessels for use in fluoroscopic angiography, allowing for the evaluation of blood flow and visualization of the vasculature system, while barium contrast media are introduced orally or with an enema to investigate the anatomy (and pathology) of the gastrointestinal tract. The introduction of magnetic resonance imaging (MRI) resulted in a loss of interest and reduction in CT contrast agent development throughout the 1980s. However, advances in computer technology, and the introduction and widespread adoption of spiral-CT in the mid-1990s have sparked a revival of interest in CT imaging and CT contrast media. Current clinical CT scanners are capable of acquiring high resolution 3D isotropic images of the body within several minutes. CT imaging today is less time consuming, less expensive, and more readily available than other medical imaging technologies such as MRI and positron emission tomography (PET). In the last several years, the emergence of novel technologies such as dual-source CT, and multi-detector CT has advanced the field of CT imaging even further. As a comparison to X-ray imaging diagnostic methods, PET imaging employs gamma-ray emitting radioactive nuclei “tracers” as contrast agents while MRI takes advantage of nuclear magnetic resonance principles by applying high magnetic fields to align magnetization of certain atomic nuclei. In contrast to CT and PET imaging, MRI uses no ionizing radiation and it is therefore often deemed safer than the other two.

Advances in microfluidic materials, functions, integration, and applications.

Abstract: Microfluidics consist of microfabricated structures for liquid handling, with cross-sections in the 1–500 μm range, and small volume capacity (fL-nL) Capillary tubes connected with fittings,1 although utilizing small volumes, are not considered microfluidics for the purposes of this paper since they are not microfabricated Likewise, millifluidic systems, made by conventional machining tools, are excluded due to their larger feature sizes (>500 μm) Though micromachined systems for gas chromatography were introduced in the 1970’s,2 the field of microfluidics did not gain much traction until the 1990’s3 Silicon and glass were the original materials used, but then the focus shifted to include polymer substrates, and in particular, polydimethylsiloxane (PDMS) Since then the field has grown to encompass a wide variety of materials and applications The successful demonstration of electrophoresis and electroosmotic pumping in a microfluidic device provided a nonmechanical method for both fluid control and separation4 Laser induced fluorescence (LIF) enabled sensitive detection of fluorophores or fluorescently labeled molecules The expanded availability of low-cost printing allowed for cheaper and quicker mask fabrication for use in soft lithography5 Commercial microfluidic systems are now available from Abbott, Agilent, Caliper, Dolomite, Micralyne, Microfluidic Chip Shop, Micrux Technologies and Waters, as a few prominent examples For a more thorough description of the history of microfluidics, we refer the reader to a number of comprehensive, specialized reviews,3, 6–11 as well as a more general 2006 review12 The field of microfluidics offers many advantages compared to carrying out processes through bulk solution chemistry, the first of which relates to a lesson taught to every first-year chemistry student Simply stated, diffusion is slow! Thus, the smaller the distance required for interaction, the faster it will be Smaller channel dimensions also lead to smaller sample volumes (fL-nL), which can reduce the amount of sample or reagents required for testing and analysis Reduced dimensions can also lead to portable devices to enable on-site testing (provided the associated hardware is similarly portable) Finally, integration of multiple processes (like labeling, purification, separation and detection) in a microfluidic device can be highly enabling for many applications Microelectromechanical systems (MEMS) contain integrated electrical and mechanical parts that create a sensor or system Applications of MEMS are ubiquitous, including automobiles, phones, video games and medical and biological sensors13 Micro-total analysis systems, also known as labs-on-a-chip, are the chemical analogue of MEMS, as integrated microfluidic devices that are capable of automating multiple processes relevant to laboratory sciences For example, a typical lab-on-a-chip system might selectively purify a complex mixture (through filtering, antibody capture, etc), then separate target components and detect them Microfluidic devices consist of a core of common components Areas defined by empty space, such as reservoirs (wells), chambers and microchannels, are central to microfluidic systems Positive features, created by areas of solid material, add increased functionality to a chip and can consist of membranes, monoliths, pneumatic controls, beams and pillars Given the ubiquitous nature of negative components, and microchannels in particular, we focus here on a few of their properties Microfluidic channels have small overall volumes, laminar flow and a large surface-to-volume ratio Dimensions of a typical separation channel in microchip electrophoresis (μCE) are: 50 μm width, 15 μm height and 5 cm length for a volume of 375 nL Flow in these devices is normally nonturbulent due to low Reynolds numbers For example, water flowing at 20°C in the above channel at 1 μL/min (222 cm/s) results in a Reynolds number of ~05, where <2000 is laminar flow Since flow is nonturbulent, mixing is normally diffusion-limited Small channel sizes also have a high surface-to-volume ratio, leading to different characteristics from what are commonly found in bulk volumes The material surface can be used to manipulate fluid movement (such as by electroosmotic flow, EOF) and surface interactions For a solution in contact with a charged surface, a double layer of charge is created as oppositely charged ions are attracted to the surface charges This electrical double layer consists of an inner rigid or Stern Layer and an outer diffuse layer An electrostatic potential known as the zeta potential is formed, with the magnitude of the potential decreasing as distance from the surface increases The electrical double layer is the basis for EOF, wherein an applied voltage causes the loosely bound diffuse layer to move towards an electrode, dragging the bulk solution along Charges on the exposed surface also exert a greater influence on the fluid in a channel as its size decreases Larger surface-to-volume ratios are more prone to nonspecific adsorption and surface fouling In particular, non-charged and hydrophobic microdevice surfaces can cause proteins in solution to denature and stick We focus our review on advances in microfluidic systems since 2008 In doing this, we occasionally must cover foundational work in microfluidics that is considerably less recent We do not focus on chemical synthesis applications of microfluidics although it is an expanding area, nor do we delve into lithography, device fabrication or production costs Our specific emphasis herein is on four areas within microfluidics: properties and applications of commonly used materials, basic functions, integration, and selected applications For each of these four topics we provide a concluding section on opportunities for future development, and at the end of this review, we offer general conclusions and prospective for future work in the field Due to the considerable scope of the field of microfluidics, we limit our discussion to selected examples from each area, but cite in-depth reviews for the reader to turn to for further information about specific topics We also refer the reader to recent comprehensive reviews on advances in lab-on-a-chip systems by Arora et al10 and Kovarik et al14

Nanobio Silver: Its Interactions with Peptides and Bacteria, and Its Uses in Medicine

Abstract: Silver, known in metallic form since antiquity, has very early been recognized by mankind for its antimicrobial properties, a phenomenon observed, for example, in the context of drinking water (a silver coin in a well), food (silver cutlery, water storage recipients), and medicine (silver skull plates, teeth). Silver compounds were also shown to be useful. For example, dilute solutions of silver nitrate served long, and still do in some countries, as antimicrobial ointment to be instilled into Published in \" \" which should be cited to refer to this work.