Laboratory Curiosities Research Articles

ChemInform Abstract: Lanthanide Amidinates and Guanidinates in Catalysis and Materials Science: A Continuing Success Story

AbstractReview: 72 refs.

Fighting cancer with nanoparticle medicines―The nanoscale matters

Abstract

Celebrating semiconductor lasers

Over the past five decades, breakthroughs in device design and advances in material and growth technologies have transformed semiconductor lasers from laboratory curiosities into practical devices with real-world applications.

Lanthanide amidinates and guanidinates in catalysis and materials science: a continuing success story

Today the rare-earth elements play a critical role in numerous high-tech applications. This is why various areas of rare-earth chemistry are currently thriving. In organolanthanide chemistry the search for new ligand sets which are able to satisfy the coordination requirements of the large lanthanide cations continues to be a hot topic. Among the most successful approaches in this field is the use of amidinate and guanidinate ligands of the general types [RC(NR')(2)](-) (R = H, alkyl, aryl; R' = alkyl, cycloalkyl, aryl, SiMe(3)) and [R(2)NC(NR')(2)](-) (R = alkyl, SiMe(3); R' = alkyl, cycloalkyl, aryl, SiMe(3)), which can both be regarded as steric cyclopentadienyl equivalents. Mono-, di- and trisubstituted lanthanide amidinate and guanidinate complexes are all readily available. Various rare earth amidinates and guanidinates have turned out to be very efficient homogeneous catalysts e.g. for the polymerization of olefins and dienes, the ring-opening polymerization of cyclic esters or the guanylation of amines. Moreover, certain alkyl-substituted lanthanide tris(amidinates) and tris(guanidinates) were found to be highly volatile and are thus promising precursors for ALD (= atomic layer deposition) and MOCVD (= metal-organic chemical vapor deposition) processes in materials science, e.g. for the production of lanthanide nitride thin layers. This tutorial review covers the continuing success story of lanthanide amidinates and guanidinates which have undergone an astonishing transition from mere laboratory curiosities to efficient homogeneous catalysts as well as ALD and MOCVD precursors within the past 10 years.

ChemInform Abstract: Homogeneous Catalysis Using Lanthanide Amidinates and Guanidinates

AbstractReview: 72 refs.

Filamentous members of cluster III Defluviicoccus have the in situ phenotype expected of a glycogen-accumulating organism in activated sludge

The in situ ecophysiology of alphaproteobacterial filamentous Cluster III Defluviicoccus present in enhanced biological phosphorus removal (EBPR)-activated sludge systems was evaluated using FISH-MAR and histochemical staining methods. These organisms, sharing the Nostocoida limicola morphotype, are known to be responsible for serious episodes of activated sludge bulking. The data presented here also demonstrate an ability to assimilate short-chain fatty acids and synthesize poly-β-hydroxyalkanoates (PHA) anaerobically, and then utilize this stored PHA under aerobic conditions, but with no corresponding synthesis of polyphosphate. These features are consistent with an in situ phenotype of glycogen-accumulating organisms (GAO), populations thought to lower the efficiency of EBPR systems by outcompeting polyphosphate-accumulating organisms (PAO) for substrates in their anaerobic feed phase. Survey data indicate that these GAO are as commonly seen as the known PAO in full-scale EBPR-activated sludge systems, which suggest that they might play important roles there, and therefore should not be viewed just as laboratory curiosities.

Development of a two‐joint robotic fish for real‐world exploration

AbstractResearch on biomimetic robotic fish has been undertaken for more than a decade. Various robotic fish prototypes have been developed around the world. Although considerable research efforts have been devoted to understanding the underlying mechanism of fish swimming and construction of fish‐like swimming machines, robotic fish have largely remained laboratory curiosities. This paper presents a robotic fish that is designed for application in real‐world scenarios. The robotic fish adopts a rigid torpedo‐shaped body for the housing of power, electronics, and payload. A compact parallel four‐bar mechanism is designed for propulsion and maneuvering. Based on the kinematic analysis of the tail mechanism, the motion control algorithm of joints is presented. The swimming performance of the robotic fish is investigated experimentally. The swimming speed of the robotic fish can reach 1.36 m/s. The turning radius is 1.75 m. Powered by the onboard battery, the robotic fish can operate for up to 20 h. Moreover, the advantages of the biomimetic propulsion approach are shown by comparing the power efficiency and turning performance of the robotic fish with that of a screw‐propelled underwater vehicle. The application of the robotic fish in a real‐world probe experiment is also presented. © 2010 Wiley Periodicals, Inc.

Lanthanide amidinates and guanidinates: from laboratory curiosities to efficient homogeneous catalysts and precursors for rare-earth oxide thin films

For decades, the organometallic chemistry of the rare earth elements was largely dominated by the cyclopentadienyl ligand and its ring-substituted derivatives. A hot topic in current organolanthanide chemistry is the search for alternative ligand sets which are able to satisfy the coordination requirements of the large lanthanide cations. Among the most successful approaches in this field is the use of amidinate ligands of the general type [RC(NR')(2)](-) (R = H, alkyl, aryl; R' = alkyl, cycloalkyl, aryl, SiMe(3)) which can be regarded as steric cyclopentadienyl equivalents. Closely related are the guanidinate anions of the general type [R(2)NC(NR')(2)](-) (R = alkyl, SiMe(3); R' = alkyl, cycloalkyl, aryl, SiMe(3)). Two amidinate or guanidinate ligands can coordinate to a lanthanide ion to form a metallocene-like coordination environment which allows the isolation and characterization of stable though very reactive amide, alkyl, and hydride species. Mono- and trisubstituted lanthanide amidinate and guanidinate complexes are also readily available. Various rare earth amidinates and guanidinates have turned out to be very efficient homogeneous catalysts e.g. for ring-opening polymerization reactions. Moreover, certain alkyl-substituted lanthanide tris(amidinates) and tris(guanidinates) were found to be highly volatile and could thus be promising precursors for ALD (= Atomic Layer Deposition) and MOCVD (= Metal-Organic Chemical Vapor Deposition) processes in materials science and nanotechnology. This tutorial review covers the success story of lanthanide amidinates and guanidinates and their transition from mere laboratory curiosities to efficient homogeneous catalysts as well as ALD and MOCVD precursors.

Single-Crystal-to-Single-Crystal Topochemical Polymerizations by Design

The polymerization of simple conjugated dienes has long been of interest: polydienes occur throughout Nature, and polyisoprene and its analogues form the basis of entire industries. In contrast, the polymers of similar small conjugated compounds, diacetylenes, trienes, and triacetylenes, are either unknown or laboratory curiosities. For 40 years, the only viable synthetic method for the 1,4-polymerization of a diacetylene was a topochemical polymerization in a condensed phase. But such an approach is hit or miss: if the diacetylene monomers have a solid-state structure preorganized at distances matching the repeat distance in the final polymer, then thermal or photochemical energy can bring about the polymerization. However, most monomers lack the proper structural parameters and simply do not react. As discussed in this Account, we have developed a supramolecular host-guest strategy that imposes the necessary structural parameters upon a diacetylene monomer that otherwise does not polymerize. We apply this strategy in the synthesis of new types of conjugated polymers made from diacetylenes, triacetylenes, and trienes. To implement the host-guest strategy, we chose a host that would self-assemble into a supramolecular structure with the requisite intermolecular spacing. For diacetylenes, the ideal spacing is 4.9 A, and the oxalamides, which routinely crystallize with a spacing of 5 A, make ideal host molecules. We chose specific oxalamide host substituents that bind to the diacetylene guest molecule, typically through hydrogen bonding. We have focused upon the single-crystal-to-single-crystal polymerizations, allowing us to obtain and characterize the polymers in perfect crystalline form and to define and better understand the reaction trajectories. We have prepared several new classes of polydiacetylenes using this strategy, including the first terminal polydiacetylenes and an aryl-substituted diacetylene. Interestingly, to prepare poly(diiododiacetylene), we used halogen bonds to bind the host and guest. The simplest polydiacetylene known, poly(diiododiacetylene), lacks the side chains that complicate the structures of similar previous polymers. Future studies should provide insights into the role of such side chains in conjugated materials. We further demonstrated the strength of the host-guest strategy by moving from the polydiacetylenes to the polytriacetylenes. Although the structural requirements for a triacetylene polymerization had been stated decades ago, no one had ever found a triacetylene with the requisite spacing of 7.4 A. We designed a series of pyridine-substituted vinylogous amide hosts to achieve this spacing. Cocrystallization of these host molecules with a triacetylene dicarboxylic acid gave us the desired structure. Using thermal annealing, we completed the synthesis of the triacetylene polymer.

Amide-based molecular shuttles (2001-2006)

Stimuli-responsive molecular shuttles are rotaxanes in which the macrocycle can be translocated from one position on the thread to a second site in response to an external trigger. Here, we present a brief overview of the contributions of the Leigh group to the field from 2001 to 2006. In this short period of time, molecular shuttles have moved from little more than laboratory curiosities to truly functional molecular machines.

Solid acid proton conductors: from laboratory curiosities to fuel cell electrolytes

The compound CsH2PO4 has emerged as a viable electrolyte for intermediate temperature (200-300 degrees C) fuel cells. In order to settle the question of the high temperature behavior of this material, conductivity measurements were performed by two-point AC impedance spectroscopy under humidified conditions (p[H2O] = 0.4 atm). A transition to a stable, high conductivity phase was observed at 230 degrees C, with the conductivity rising to a value of 2.2 x 10(-2) S cm(-1) at 240 degrees C and the activation energy of proton transport dropping to 0.42 eV. In the absence of active humidification, dehydration of CsH2PO4 does indeed occur, but, in contradiction to some suggestions in the literature, the dehydration process is not responsible for the high conductivity at this temperature. Electrochemical characterization by galvanostatic current interrupt (GCI) methods and three-point AC impedance spectroscopy (under uniform, humidified gases) of CsH2PO4 based fuel cells, in which a composite mixture of the electrolyte, Pt supported on carbon, Pt black and carbon black served as the electrodes, showed that the overpotential for hydrogen electrooxidation was virtually immeasurable. The overpotential for oxygen electroreduction, however, was found to be on the order of 100 mV at 100 mA cm(-2). Thus, for fuel cells in which the supported electrolyte membrane was only 25 microm in thickness and in which a peak power density of 415 mW cm(-2) was achieved, the majority of the overpotential was found to be due to the slow rate of oxygen electrocatalysis. While the much faster kinetics at the anode over those at the cathode are not surprising, the result indicates that enhancing power output beyond the present levels will require improving cathode properties rather than further lowering the electrolyte thickness. In addition to the characterization of the transport and electrochemical properties of CsH2PO4, a discussion of the entropy of the superprotonic transition and the implications for proton transport is presented.

Microsaccades Counteract Visual Fading during Fixation

Our eyes move continually, even while we fixate our gaze on an object. If fixational eye movements are counteracted, our perception of stationary objects fades completely, due to neural adaptation. Some studies have suggested that fixational microsaccades refresh retinal images, thereby preventing adaptation and fading. However, other studies disagree, and so the role of microsaccades remains unclear. Here, we correlate visibility during fixation to the occurrence of microsaccades. We asked subjects to indicate when Troxler fading of a peripheral target occurs, while simultaneously recording their eye movements with high precision. We found that before a fading period, the probability, rate, and magnitude of microsaccades decreased. Before transitions toward visibility, the probability, rate, and magnitude of microsaccades increased. These results reveal a direct link between suppression of microsaccades and fading and suggest a causal relationship between microsaccade production and target visibility during fixation.

Thin-Membrane Solid-Acid Fuel Cell

Solid-acid fuel cells (SCFCs) utilize an anhydrous, nonpolymeric proton conducting electrolyte that can operate at slightly elevated temperatures. By supporting thin CsH2PO4 electrolyte membranes (25-36 µm), on porous stainless steel gas-diffusion electrodes, SAFCs with peak power densities as high as 415 mW/cm^2 were obtained. Cells were operated at ~240°C with humidified H2 supplied to the anode and humidified O2 supplied to the cathode. Despite the thinness of the membranes, the open-circuit voltages were high, 0.91-1.01 V. These results transform SAFCs from laboratory curiosities into highly competitive energy conversion devices.

Challenge 2005 and beyond: Recognition, Transformation, and profitable use of innovative thinking

In the opening years of the new millennium, we are witnessing the creation of a “cult of innovation”. The word is on everyone's lips, and nowhere more so than in board rooms and executive offices of the world's great business enterprises. Innovation is something that every business values and wishes to create; yet it is a concept that often defies definition. It is not uncommon for a group of knowledgeable individuals to disagree not only about the value of innovation, but also about the meaning of innovation. One person's “innovation” can be another's “product or process improvement” (e.g., Gillette's new M3 PowerTM vibrating blade razor—innovation or product improvement?) and the ensuing dialogue frequently raises questions not only about the nature and definition of innovation, but also about the way in which innovation is used to create something useful and market-friendly. The perceived value of new concepts and inventions quite often colors whether they are seen as innovations, or whether they are seen as intellectual and/or laboratory curiosities. Moreover, concepts and inventions that might be deemed to be “innovative” (i.e., having value) at “Point Y” in history may not have been seen that way at “Point X” 20 years earlier. Innovations, consequently, are often declared retrospectively—many years may pass between the initial cognitive output and the recognition that it either represented, or was transformed into, an innovation. There are periods of time, however, when the process of “innovative thinking” is much more important than the actual creation of true innovations, and we are in such a period. It is this broad concept—the recognition, transformation, and profitable use of innovative thinking—which is discussed in this article.

Evanescent wave fluorescence biosensors

Since discovery and first use in the mid-1970s, evanescent wave fluorescence biosensors have developed into a diverse range of instruments, each designed to meet a particular detection need. In this review, we provide a brief synopsis of what evanescent wave fluorescence biosensors are, how they work, and how they are used. In addition, we have summarized the important patents that have impacted the evolution from laboratory curiosities to fully automated commercial products. Finally, we address the critical issues that evanescent wave fluorescence biosensors will face in the coming years.

Lead-free tin alloys—laboratory curiosities or capable processes?

Lead-free tin alloys—laboratory curiosities or capable processes?

Applying mixed reality to entertainment

The lack of compelling content has relegated many promising entertainment technologies to laboratory curiosities. Although mixed-reality techniques show great potential, the entertainment business is not about technology. To penetrate these huge markets, MR technology must become transparent for the content to have full effect. To achieve this goal, we have devised a framework that lets us integrate concepts from disparate areas such as theme parks, theater, and film into a comprehensive research methodology. We believe that our framework, which has already helped us create content for MR entertainment systems, can provide these benefits to other developers as well.

ChemInform Abstract: Phosphorus Heterocycles: From Laboratory Curiosities to Ligands in Highly Efficient Catalysts.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Phosphorus Heterocycles: From Laboratory Curiosities to Ligands in Highly Efficient Catalysts

Phosphabenzenes and phosphaferrocenes were among the first compounds with P-C multiple bonds. For nearly 30 years the chemistry of these molecules was essentially a domain left to basic researchers. Recently, however, it was reported that transition metal complexes with phosphabenzene and phosphaferrocene ligands exhibit remarkable potential as catalysts. Catalysts based on rhodium (i) and various phosphabenzenes appear to be superior to classical systems in the hydroformylation of terminal and internal alkenes. In addition planar-chiral phosphaferrocene species display an excellent performance as directing ligands in a series of enantioselective asymmetric syntheses.

Novel agents to modulate oestrogen action.

As women enter the menopause, the majority suffers symptoms associated with a dramatic fall in circulating levels of 17 beta-oestradiol and oestrone. As a result, the oestrogen protective effect against coronary artery disease and osteoporosis is lost. To solve these problems, hormone replacement therapy is often used. However, there are a number of side-effects including increased risk from breast and uterine cancer that can limit compliance. New drugs, called selective oestrogen modulators (SERMs), have been developed to mimic oestrogen's effects on the liver, heart and bones but without its harmful effects on the breast and uterus. SERMs are structurally diverse compounds that bind to oestrogen receptors and elicit agonist or antagonist responses depending on the target tissue and hormonal milieu. The drugs are being used, or evaluated, for the prevention of hormone-responsive breast cancer, osteoporosis and cardiovascular disease in postmenopausal women. Tamoxifen is the endocrine treatment of choice for breast cancer, but it also has beneficial effects on bone density and serum lipids in postmenopausal women. Recently, tamoxifen was shown to decrease the risk of invasive breast cancer in women at high risk. However, tamoxifen has some stimulatory effects on the endometrium. Raloxifene is used to prevent osteoporosis and fractures. Raloxifene also lowers circulating cholesterol and the incidence of invasive breast cancer in postmenopausal women but does not stimulate the endometrium. The SERMs have evolved from mere laboratory curiosities into drugs that hold promise for preventing several major diseases associated with ageing in women.