Search

The title compounds, [Fe4(C2H3O2)6(C7H4O3)FO(C5H5N)3]·C5H5N·0.24H2O (1-F) and [Fe4(C2H3O2)6(C7H4O3)ClO(C5H5N)3]·H2O (1-Cl) were synthesized using a self-assembly reaction in methanol and pyridine with stoichiometric addition of salicylhydroxamic acid (H3shi), acetic acid (HOAc), and the appropriate ferric halide salt. The compounds crystallize as solvates, where 1-F has one pyridine molecule that is disordered about a twofold axis and one water molecule with an occupancy of 0.24 (2); and 1-Cl has one water molecule that is disordered over two sites with occupancies of 0.71 (1) and 0.29 (1). The space groups for each analog differ as 1-F crystallizes in Fdd2 while 1-Cl crystallizes in P21. The difference in packing is due to changes in the intermolecular interactions involving the different halides. The two molecules are mostly isostructural, differing only by the torsion of the pyrine ligands and slight orientation changes in the acetate ligands. All of the iron(III) ions are in six-coordinate octahedral ligand field geometries but each one exhibits a unique coordination environment with various numbers of O (four to six) and N (nought to two) atom donors. Bond-valence sums confirm each iron is trivalent. The hydroximate ligand is bound to three iron(III) ions using a fused chelate motif similar to those in metallacrown compounds.

The title metallacrown (MC) complexes LnIII[15-MCFeIIIN(shi)-5](OAc)2Cl(C5H5N)6 (Ln1), where OAc– is acetate, shi3− is salicylhydroximate, and Ln = Gd and Dy, were synthesized via a self-assembly reaction in methanol and pyridine. Single crystals were grown using slow evaporation and characterized using X-ray diffraction. Seven-coordinate capped octahedron geometries were observed for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species. The 15-MC-5 is a ruffled metallacrown archetype similar to previously reported mixed-valent manganese metallacrowns. The title metallacrown (MC) complexes LnIII[15-MCFeIIIN(shi)-5](OAc)2Cl(C5H5N)6 (Ln1), where OAc– is acetate, shi3− is salicylhydroximate, and Ln = Gd and Dy, contains seven-coordinate capped octahedron geometries for the lanthanide ion in both complexes, which is uncommon for trivalent lanthanide species.

We describe a systematic study of the influence of halides and solvents on the optical properties of EuII-containing complexes in solution starting from well-defined crystalline precursors. Anionic halides, chloride and bromide, blue-shift the spectroscopic properties of EuII, whereas neutral ligands, methanol and acetonitrile, cause a red shift. This system provides evidence that EuII has a stronger affinity for chloride, and to some extent bromide, relative to acetonitrile but not methanol. We also describe a simple procedure using an ion-exchange resin for the exchange of iodide counterions to hexafluorophosphate. These findings are a step toward designing ligands that can tune the optical properties of EuII-containing complexes for solution-based applications.

The dissociation rates of five EuII-containing cryptates in water were measured using UV–visible spectroscopy and murexide at pH 6.5, 7, 7.5, 8, and 9. Murexide was used as a coordinating dye for EuII. The results for a known cryptate were within experimental error of the value obtained using other methods and enabled the measurement of other cryptates. This validation of the use of murexide to study the dissociation of EuII-containing cryptates enables its use with other complexes of EuII.

The complexes described here serve as contrast agents for magnetic resonance imaging thermometry. The complexes differentially enhance contrast between 275 and 325 K. The basis of the temperature response of the fluorinated contrast complex is the modulation of water exchange caused by trifluoromethyl groups that can be chemically controlled.

Metal-based contrast agents for magnetic resonance imaging present a promising avenue to image hypoxia. EuII -based contrast agents have a unique biologically relevant redox couple, EuII/III , that distinguishes this metal for use in hypoxia imaging. To that end, we investigated a strategy to enhance the contrast-enhancing capabilities of EuII -based cryptates in magnetic resonance imaging by controlling the rotational dynamics. Two dimetallic, EuII -containing cryptates were synthesized to test the efficacy of rigid versus flexible coupling strategies. A flexible strategy to dimerization led to a modest (114 %) increase in contrast enhancement per Eu ion (60 MHz, 298 K), but a rigid linking strategy led to an excellent (186 %) increase in contrast enhancement despite this compound's having the smaller molecular mass of the two dimetallic complexes. We envision the rigid linking strategy to be useful in the future design of potent EuII -based contrast agents for magnetic resonance imaging.

The objective of this chapter is to function as a tutorial for those who are new to the field of divalent lanthanide luminescence and as a resource for those who desire access to an overview of the reported research. This chapter contains a discussion of the properties of divalent lanthanides and how those properties are relevant to luminescence. A representative sample of reports of the luminescence of divalent lanthanide complexes in solution is described and discussed. These reports span several decades of research, many coordination environments, and several lanthanides. Strategies based on the modulation of first coordination spheres for the enhancement of luminescence intensity and rational modulation of emission wavelength are discussed using empirical examples.

The excitation of lanthanides with visible light to promote photochemical reactions has garnered interest in recent years. Lanthanides serve as initiators for photochemical reactions because they exhibit visible-light-promoted 4f→5d transitions that lead to emissive states with electrochemical potentials that are more negative than the corresponding ground states. The lanthanides that have shown the most promising characteristics for visible-light promoted photoredox are SmII, EuII, and CeIII. By understanding the effects that ligands have on the 5d orbitals of SmII, EuII, and CeIII, luminescence and reactivity can be rationally modulated using coordination chemistry. This review briefly overviews the photochemical reactivity of SmII, EuII, and CeIII with visible light; the properties that influence the reactivity of these ions; and the research that has been reported towards modulating their photochemical-relevant properties using visible light and coordination chemistry.

Due to the importance of both visible-light luminescence and lanthanides in modern society, the influence of the ligand environment on complexes of YbII were studied and compared with analogous complexes of EuII. Four ligands with systematically varied electronic and steric characteristics were used to probe the coordination environment and electronic and redox properties of the corresponding YbII-containing complexes. Strong-field nitrogenous donors gave rise to bathochromic shifts, leading to visible-light absorption by YbII. Trends in properties across the series of YbII-containing complexes were compared to trends reported for the analogous EuII-containing complexes, revealing the translatability of coordination environment effects across the divalent lanthanide series. These studies provide valuable information regarding the behavior of small and medium-sized divalent lanthanides outside of the solid state.

We report a computational study of the photophysical properties of two divalent europium cryptates. Our calculations provide an explanation for the bright yellow luminescence of the Eu II -containing octaaza-cryptate compared to the less intense blue luminescence of the structurally similar Eu II -containing 222-cryptate. Calculations using time-dependent density functional theory with the B3PW91 functional, the Stuttgardt–Dresden relativistic core potential basis for europium, and SMD implicit solvation are used to compute the excitation and emission spectra of both complexes. Emission is also calculated with state-specific solvation. The results are compared with experimental luminescence data acquired in methanol. Natural-transition orbitals reveal similar spin-allowed transitions between the 4f and 5d orbitals on the europium ion in both complexes. For the 222-cryptate, the emissive state is hidden underneath the broad ultraviolet absorption; therefore, the state is not experimentally differentiated in the spectra, despite being present in the calculated spectra. For the octaaza-cryptate, the emissive state is observed as a separate band, shifted to lower energy than the broad ultraviolet absorption. Using ligand-field arguments, sharp differences in luminescence and the bathochromic shift of the emissive state can be attributed to a greater splitting of the 5d orbitals of the octaaza-cryptate relative to the 222-cryptate.

We report a new luminescent EuII-containing complex. The complex is excited with visible light, leading to emission centered at 447 nm with a lifetime of 1.25 μs. Computational studies suggest that the steric bulk of the ligand is a major factor influencing the wavelength of emission.

Divalent europium is used catalytically in visible-light-promoted photoredox bond-forming reactions., We report the first catalytic use of a divalent lanthanide in visible-light-promoted bond-forming reactions. Our new precatalyst uses europium in the +2 oxidation state and is active in the presence of blue light from light-emitting diodes. The use of low-energy visible light reduces the occurrence of potential side reactions that might be induced by higher-energy UV light. The system described here uses zinc metal as a sacrificial reductant and is tolerant to wet, protic solvents. The catalyst can be made in situ from relatively inexpensive and air-stable EuCl3·6H2O, and the ligand can be synthesized in large quantities in two steps. With 0.5% loading of precatalyst, an average of 120 turnovers was observed in six hours for reductive coupling of benzyl chloride. We expect that the results will initiate the study of visible-light-promoted photoredox catalysis using divalent europium in a variety of reactions.

The Eu3+/2+ redox couple provides a convenient design platform for responsive pO2 sensors for magnetic resonance imaging (MRI). Specifically the Eu2+ ion provides T1w contrast enhancement under hypoxic conditions in tissues, whereas, under normoxia, the Eu3+ ion can produce contrast from chemical exchange saturation transfer in MRI. The oxidative stability of the Eu3+/2+ redox couple for a series of tetraaza macrocyclic complexes was investigated in this work using cyclic voltammetry. A series of Eu-containing cyclen-based macrocyclic complexes revealed positive shifts in the Eu3+/2+ redox potentials with each replacement of a carboxylate coordinating arm of the ligand scaffold with glycinamide pendant arms. The data obtained reveal that the complex containing four glycinamide coordinating pendant arms has the highest oxidative stability of the series investigated.

EuII -containing complexes were studied with respect to properties relevant to their use as contrast agents for magnetic resonance imaging. The influences of molecular parameters and field strength on relaxivity were studied for a series of EuII -containing cryptates and their adducts with β-cyclodextrins, poly-β-cyclodextrins, and human serum albumin. Solid- and solution-phase characterization of EuII -containing complexes is presented that demonstrates the presence of inner-sphere molecules of water. Additionally, relaxivity, water-exchange rate, rotational correlation time, and electronic relaxation times were determined using variable-temperature 17 O NMR, nuclear magnetic relaxation dispersion, and electron paramagnetic resonance spectroscopic techniques. These results are expected to be instrumental in the design of future EuII -based contrast agents.

Magnetic resonance imaging (MRI) using redox-active, EuII-containing complexes is one of the most promising techniques for noninvasively imaging hypoxia in vivo. In this technique, positive (T1-weighted) contrast enhancement persists in areas of relatively low oxidizing ability, such as hypoxic tissue. Herein, we describe a fluorinated, EuII-containing complex in which the redox-active metal is caged by intramolecular interactions. The position of the fluorine atoms enables temperature-responsive contrast enhancement in the reduced form of the contrast agent and detection of the oxidized contrast agent via MRI in vivo. Positive contrast is observed in 1H-MRI with Eu in the +2 oxidation state, and chemical exchange saturation transfer and 19F-MRI signal are observed with Eu in the +3 oxidation state. Contrast enhancement is controlled by the redox state of Eu, and modulated by the fluorous interactions that cage a bound water molecule reduce relaxivity in a temperature-dependent fashion. Together, these advancements constitute the first report of in vivo, redox-responsive imaging using 19F-MRI.

Toward recovering rare-earth elements, we prepared a solid-phase media that binds and elutes metals for extraction and enrichment. We report the synthesis and methodology for a solid-phase media that exhibits pH-dependent binding of aqueous rare-earth elements. The media shows pH-dependent binding of NdIII and retains efficiency over at least six cycles of binding and elution. Mixed solutions of rare-earth elements demonstrated a preference for mid and heavy rare-earth elements based on thermodynamic binding preferences of the ligand, and selectivity for rare-earth elements over iron and aluminum were observed with coal fly ash leachate. We expect this new recovery method to be a significant step towards aqueous-based extraction and enrichment of critically important rare-earth elements.

Reliable methods of imaging myelin are essential to investigate the causes of demyelination and to study drugs that promote remyelination. Myelin-specific compounds can be developed into imaging probes to detect myelin with various imaging techniques. The development of multimodal myelin-specific imaging probes enables the use of orthogonal imaging techniques to accurately visualize myelin content and validate experimental results. Here, we describe the synthesis and application of multimodal myelin-specific imaging agents for light microscopy and magnetic resonance imaging. The imaging agents were synthesized by incorporating the structural features of luxol fast blue MBS, a myelin-specific histological stain, into texaphyrins coordinated to GdIII . These new complexes demonstrated absorption of visible light, emission of near-IR light, and relaxivity values greater than clinically approved contrast agents for magnetic resonance imaging. These properties enable the use of optical imaging and magnetic resonance imaging for visualization of myelin. We performed section- and en block-staining of ex vivo mouse brains to investigate the specificity for myelin of the new compounds. Images obtained from light microscopy and magnetic resonance imaging demonstrate that our complexes are retained in white matter structures and enable detection of myelin. Copyright © 2016 John Wiley & Sons, Ltd.

The +3 and +2 oxidation states of europium have drastically different magnetic and spectroscopic properties. Electrochemical measurements are often used to probe EuIII/II oxidation state changes, but a full suite of spectroscopic characterization is necessary to demonstrate conversion between these two oxidation states in solution. Here, we report the facile conversion of a EuIII tetraglycinate complex into its EuII analogue. We present electrochemical, luminescence, electron paramagnetic resonance, UV–visible, and NMR spectroscopic data demonstrating complete reversibility from the reduction and oxidation of the +3 and +2 oxidation states, respectively. The EuII-containing analogue has kinetic stability within the range of clinically approved GdIII-containing complexes using an acid-catalyzed dissociation experiment. Additionally, we demonstrate that the +3 and +2 oxidation states provide redox-responsive behavior through chemical exchange saturation transfer or proton relaxation, respectively. These results will be applicable to a wide range of redox-responsive contrast agents and Eu-containing complexes.

Eu(II) -based contrast agents offer physiologically relevant, metal-based redox sensing that is unachievable with Gd(III) -based contrast agents. To evaluate the in vivo contrast enhancement of Eu(II) as a function of injection type, we performed intravenous, intraperitoneal, and subcutaneous injections in mice. Our data reveal a correlation between reported oxygen content and expected rates of diffusion with the persistence of Eu(II) -based contrast enhancement. Biodistribution studies revealed europium clearance through the liver and kidneys for intravenous and intraperitoneal injections, but no contrast enhancement was observed in organs associated with clearance. These data represent a step toward understanding the behavior of Eu(II) -based complexes in vivo. Copyright © 2016 John Wiley & Sons, Ltd.

The dynamics of ligand exchange on lanthanide ions is important for catalysis and organic reactions. Recent 17O-NMR experiments have shown that water-exchange rates of lanthanide ions in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO4]) increase as a function of increasing charge density. The trend of water-exchange rates in this solvent is opposite to that observed in water. Since the lanthanide ions and ionic liquids investigated in that work were highly charged, an advanced polarizable potential is desirable for accurate simulations. To this end, we have developed atomic multipole optimized energetics for biomolecular applications (AMOEBA) parameters for all lanthanides and [EMIm][EtSO4], and molecular dynamics simulations with the optimized parameters have been carried out to provide possible explanations for these observed behaviors from the experiments. In water, the association of a water molecule with the first hydration shell can lead to water exchange. Smaller lanthanide ions exhibit slower water-exchange rates than larger ones because they form smaller aqua complexes, preventing the binding of incoming water molecules from the outer hydration shells. By contrast, smaller lanthanide ions undergo faster water exchange in water/[EMIm][EtSO4] because the dissociation of a water molecule is a key step for water-exchange events in this solvent. The first shell [EtSO4]− anions bind closer to the smaller lanthanide ions, resulting in more steric crowding effects on the surrounding water and facilitating the release of water molecules.

Polyether ether ketone (PEEK) is a highly heat-resistant thermoplastic with excellent strength and elastic modulus similar to human bone, making it an attractive material for orthopedic implants. However, the hydrophobic surface of PEEK implants induces fibrous encapsulation which is unfavorable for stable implant anchorage. In this study, PEEK was coated via ion-beam-assisted deposition (IBAD) using a two-layer design of yttria-stabilized zirconia (YSZ) as a heat-protection layer, and hydroxyapatite (HA) as a top layer to improve osseointegration. Microstructural analysis of the coatings showed a dense, uniform columnar grain structure in the YSZ layer and no delamination from the substrate. The HA layer was found to be amorphous and free of porosities in its as-deposited state. Subsequent heat treatment via microwave energy followed by autoclaving crystallized the HA layer, confirmed by SEM and XRD analysis. An in vitro study using MC3T3 preosteoblast cells showed improved bioactivity in heat-treated sample groups. Cell proliferation, differentiation, and mineralization were analyzed by MTT assay and DNA content, osteocalcin expression, and Alizarin Red S (AR-S) content, respectively. Initial cell growth was increased, and osteogenic maturation and mineralization were accelerated most on coatings that underwent a combined microwave and autoclave heat treatment process as compared to uncoated PEEK and amorphous HA surfaces. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 560-567, 2017.

Suture retention strength (SRS) is commonly used as a measure the ability of sutures to adhere implants to surrounding tissue. While SRS is widely employed, surprisingly its effects on graft microstructure have not been characterized. This is particularly germane to the broad utilization of electrospun implants in tissue engineering. These implants need to retain their initial nanoscale topography while simultaneously preserving clinically critical mechanical properties. We examined the suture-driven microstructural deformation of polycaprolactone electrospun to form both square and tubular SRS samples. The impact of fiber orientation (generally parallel or random orientation, orthogonally aligned) on the SRS of these vascular tissue equivalents was analyzed and compared to native and decellularized porcine vasculature. The initial state of the fiber clearly dictates the overall efficiency of scaffold utilization. SRS values for as-spun fibers at a thickness of 300 μm were found to be in the range of 1.59-4.78 N for the three orientations. Unexpectedly, random fibers provided the optimal SRS values based on both resistance to suture motion and the percentage of scaffold involvement. A "V-shaped" failure morphology is observed for both electrospun scaffolds and native tissue during SRS testing. Post-test fiber alignment in the tensile direction was visible in all initial fiber orientations similar to that of native tissue. These findings are significant as they allow us to employ new, counterintuitive biomimetic design criteria for nanofiber-based scaffolds in which reliable mechanical integration with the surrounding tissues via suture-based methods is important. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1525-1534, 2016.

When Alzheimer's disease (AD) progresses, several pathological features arise including accumulation of misfolded protein aggregates [e.g., amyloid-β (Aβ) plaques], metal ion dyshomeostasis, and oxidative stress. These characteristics are recently suggested to be interconnected through a potential factor, metal-associated Aβ (metal-Aβ) species. The role of metal-Aβ species in AD pathogenesis remains unclear, however. To elucidate the contribution of metal-Aβ species to AD pathology, as well as to develop small molecules as chemical tools and/or theranostic (therapeutic and diagnostic) agents for this disease, curcumin (Cur), a natural product from turmeric, and its derivatives have been studied towards both metal-free and metal-induced Aβ aggregation. Although Cur has indicated anti-amyloidogenic activities and antioxidant properties, its biological use has been hindered due to low solubility and stability in physiologically relevant conditions. Herein, we report the reactivity of Cur and its derivatives (Gd-Cur, a potential multimodal Aβ imaging agent; Cur-S, a water soluble derivative of Cur that has substitution at the phenolic hydroxyls) with metal-free Aβ and metal-Aβ species. Our results and observations indicate that Gd-Cur could modulate Cu(II)-triggered Aβ aggregation more noticeably over metal-free or Zn(II)-induced analogues; however, Cur-S was not observed to noticeably modulate Aβ aggregation with and without metal ions. Overall, our studies present information that could aid in optimizing the molecular scaffold of Cur for the development of chemical tools or theranostics for metal-Aβ species.

Responsive magnetic resonance imaging (MRI) contrast agents, those that change their relaxivity according to environmental stimuli, have promise as next generation imaging probes in medicine. While several of these are known based on covalent modification of the contrast agents, fewer are known based on controlling non-covalent interactions. We demonstrate here accentuated relaxivity of a T1-shortening contrast agent, Gd-DOTP5− based on non-covalent, hydrogen bonding of Gd-DOTP5− with a novel fluorous amphiphile. By contrast to the phosphonate-containing Gd-DOTP5− system, the relaxivity of the analogous clinically approved contrast agent, Gd-DOTA− is unaffected by the same fluorous amphiphile under similar conditions. Mechanistic studies show that placing the fluorous amphiphile in proximity of the gadolinium center in Gd-DOTP5− caused an increase in τm (bound-water residence lifetime or the inverse of water exchange rate, τm = 1/kex) and an increase in τR (rotational correlation time), with τR being the factor driving enhanced relaxivity. Further, these effects were not observed when Gd-DOTA− was treated with the same fluorous amphiphile. Thus, Gd-DOTP5− and Gd-DOTA− respond to the fluorous amphiphile differently, presumably because the former binds to the amphiphile with higher affinity. (DOTP = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraphosphonic acid; DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid).

Lanthanide ions have been widely studied in imaging and sensing applications, and they are also strong Lewis acids that have the ability to catalyze organic reactions. Here, we review the spectroscopic properties of lanthanides that enable the calculation of water-coordination numbers. Additionally, the application of these calculations to study the mechanism of lanthanide-catalyzed organic reactions is reviewed.

Background Resorbable electrospun polycaprolactone (PCL) scaffolds for tissue reconstruction can provide physicians with an “off the shelf” product tailored to the patient's specific tissue architecture. However, many tissue-engineering platforms do not possess the necessary long-term mechanical stability needed to properly support tissue development. Objective Sintering has been explored as a means of altering the properties of electrospun PCL. However, crystallinity-driven changes in mechanical properties following thermal treatment have not been previously investigated. Methods PCL nanofibers were produced by electrospinning and subsequently thermally sintered (at 55, 56 and 58 °C) to enhance their long-term mechanical integrity in response to representative biological milieux. Results Scaffolds initially sintered at 56 °C displayed 6-fold increases in compressive strength and 3-fold increases in modulus, while displaying 10-fold increases in energy dissipation with increasing sintering temperature. Sintering just below the Tm resulted in amorphization of the 55 °C sample as indicated by the 20-fold lower XRD peak intensities. Although crystallinity is suppressed, the polymer chains likely retain chain alignment from electrospinning and are apparently highly susceptible to recrystallization. After only 1 d PBS exposure, the 55 °C samples recover a substantial fraction of the as-spun crystallinity; 7 d of exposure fully restores as-spun peak intensities. The mechanical properties of all three (55, 56, or 58 °C) scaffolds displayed peak values of compressive strength and modulus following 7 d exposure. Conclusion In contrast with the current state-of-the-art which assumes that tissue engineering scaffolds only grow weaker following exposure, in these scaffolds maximum values of compressive strength and modulus were observed after 7 d of aqueous immersion. This suggests that polymeric recrystallization can be used to increase or optimize mechanical properties in vitro/in vivo. Scaffolds that increase their mechanical integrity during biological exposures constitute a new pathway enabling clinical advances.

Thirty years ago, Schering filed the first patent application for a contrast agent for magnetic resonance imaging (MRI) covering the forefather of the gadolinium contrast agents and still the most widely used gadolinium probe: gadolinium(III) diethylenetriaminepentaacetate (Magnevist). To date, 11 contrast agents have been approved by the US Food and Drug Administration for intravenous use. Coordination chemists have done a great deal to move the field forward. Our understanding of lanthanide chemistry now makes possible the design of complexes with long rotational correlation times, fast or slow water-exchange rates, high thermodynamic stabilities, and kinetic inertness, leading to sensitive and nontoxic contrast agents. Chemists did not stop there. The last few decades has seen the development of novel classes of probes that yield contrast through different mechanisms, such as paramagnetic chemical exchange saturation transfer agents. Thirty years since the first patent, chemists are still leading the way. The development of high-sensitivity contrast agents for high magnetic fields, safe probes for patients with kidney disorders, and multimodal, targeted, and responsive agents demonstrates that the field of contrast agents for MRI still has much to offer.

Contrast agents are diagnostic tools that often complement magnetic resonance imaging. At ultra-high field strengths (≥7 T), magnetic resonance imaging is capable of generating desirable high signal-to-noise ratios, but clinically available contrast agents are less effective at ultra-high field strengths relative to lower fields. This gap in effectiveness demands the development of contrast agents for ultra-high field strengths. In this minireview, we summarize contrast agents reported during the last three years that focused on ultra-high field strengths.

The first ligand-exchange rate measurements of lanthanide ions in an ionic liquid are reported here. The trend of water-exchange rates in the ionic liquid is the opposite of the trend in water.

Enantioselective bond-forming reactions catalyzed by chiral lanthanide-based complexes are popular because of their Lewis acidity, solvent compatibility, reusability, and potential to catalyze reactions with high stereospecificity. The stereospecific outcomes of bond-forming reactions catalyzed by asymmetric lanthanide-based precatalysts depend on the coordination chemistry of the precatalysts that can be interrogated with X-ray crystal structures, luminescence measurements, NMR spectroscopy, and computational methods. This review is primarily focused on developments related to lanthanide-based precatalysts since the turn of the century and the techniques used to study coordination environments of lanthanide-based precatalysts for Mukaiyama aldol reactions in aqueous media.

This review describes recent advances in strategies for tuning the water-exchange rates of contrast agents for magnetic resonance imaging (MRI). Water-exchange rates play a critical role in determining the efficiency of contrast agents; consequently, optimization of water-exchange rates, among other parameters, is necessary to achieve high efficiencies. This need has resulted in extensive research efforts to modulate water-exchange rates by chemically altering the coordination environments of the metal complexes that function as contrast agents. The focus of this review is coordination-chemistry-based strategies used to tune the water-exchange rates of lanthanide(III)-based contrast agents for MRI. Emphasis will be given to results published in the 21st century, as well as implications of these strategies on the design of contrast agents.

The influence of albumin on the efficacy of a Eu(2+)-containing complex capable of interacting with human serum albumin (HSA) was investigated at different field strengths (1.4, 3, 7, 9.4, and 11.7 T). Relaxometric measurements indicated that the presence of albumin at higher field strengths (3 T) did not result in an increase in the relaxivity of the Eu(2+) complex, but a relaxation enhancement of 171 ± 11% was observed at 1.4 T. Titration experiments using different percentages (2, 4.5, 6, 10, 15, and 25% w/v) of HSA and variable-temperature (17)O NMR measurements were performed to understand the effect of albumin on the molecular properties of the biphenyl-functionalized Eu(2+) complex that are relevant to magnetic resonance imaging.

The EuII/III redox couple offers metal-based oxidation-sensing with magnetic resonance imaging making the study of EuII oxidation chemistry important in the design of new probes. Accordingly, we explored oxidation reactions with a set of EuII -containing complexes. Superoxide formation from the reaction between EuII and dioxygen was observed using electron paramagnetic resonance spectroscopy. Additionally, oxidation kinetics of three EuII -containing complexes with bromate and glutathione disulfide at pH values, including 5 and 7, is reported. In the reaction with bromate, the oxidation rate of two of the complexes increased by 7.3 and 6.7 times upon decreasing pH from 7 to 5, but the rate increased by 17 times for a complex containing amide functional groups over the same pH range. The oxidation rate of a fluorobenzo-functionalized cryptate was relatively slow, indicating that the ligand used to impart thermodynamic oxidative stability might also be useful for controlling oxidation kinetics.

Two new Eu(II)-containing cryptates were prepared with a new nitrogenous cryptand functionalized with three benzo groups. The introduction of three aromatic rings into the ligand backbone imparts lopsided geometrical features on the resulting Eu(II) coordination environments. In both complexes, the interactions between Eu and the amines on the aromatic side of the molecule are weaker than those on the nonaromatic side, resulting in one discrete unit with two distinct faces. One of the new complexes is, to the best of our knowledge, the first direct observation of a bis-aquo Eu(II)-containing cryptate with two nonadjacent inner-sphere water molecules. In addition to solid-phase structure, the electronic UV-visible and emission spectra of the new complexes were studied in acetonitrile. Experimental results show that the decreased Lewis basicity of the aromatic face hypsochromically shifts absorbances and emissions from a structurally related compound without the benzo groups.

This account describes lanthanide coordination chemistry with a focus on the similarities between lanthanide complexes used in catalysis and those used as contrast agents in magnetic resonance imaging.

This account describes lanthanide coordination chemistry with a focus on the similarities between lanthanide complexes used in catalysis and those used as contrast agents in magnetic resonance imaging.

Molecules containing multiple lanthanide ions have unique potential in applications for medical imaging including the areas of magnetic resonance imaging (MRI) and fluoresence imaging. The study of multilanthanide complexes as contrast agents for MRI and as biologically responsive fluorescent probes has resulted in an improved understanding of the structural characteristics that govern the behavior of these complexes. This review will survey the last five years of progress in multinuclear lanthanide complexes with a specific focus on the structural parameters that impact potential medical imaging applications. The patents cited in this review are from the last five years and describe contrast agents that contain multiple lanthanide ions.

The development of efficient methods for the asymmetric Mukaiyama aldol reaction in aqueous solution has received great attention. We have developed a new series of chiral lanthanide-containing complexes that produce Mukaiyama aldol products with outstanding enantioselectivities. In this paper, we describe an optimized ligand synthesis, trends in stereoselectivity that result from changing lanthanide ions, and an exploration of substrate scope that includes aromatic and aliphatic aldehydes and silyl enol ethers derived from aromatic and aliphatic ketones.

Recent advances in the coordination chemistry of Eu(2+) are reviewed. Common synthetic routes for generating discrete Eu(2+)-containing complexes reported since 2000 are summarized, followed by a description of the reactivity of these complexes and their applications in reduction chemistry, polymerization, luminescence, and as contrast agents for magnetic resonance imaging. Rapid development of the coordination chemistry of Eu(2+) has led to an upsurge in the utilization of Eu(2+)-containing complexes in synthetic chemistry, materials science, and medicine.

The kinetic stabilities and relaxivities of a series of Eu(2+)-containing cryptates have been investigated. Transmetallation studies that monitored the change in the longitudinal relaxation rate of water protons in the presence of Ca(2+), Mg(2+), and Zn(2+) demonstrated that cryptate structure influences stability, and two of the cryptates studied were inert to transmetallation in the presence of these endogenous ions. The efficacy of these cryptates was determined at different magnetic field strengths, temperatures, and pH values. Cryptate relaxivity was found to be higher at ultra-high field strengths (7 and 9.4 T) relative to clinically relevant field strengths (1.4 and 3 T), but the efficiency of these cryptates decreased as temperature increased. In addition, variation in pH did not yield significant changes in the efficacy of the cryptates. These studies establish a foundation of important properties that are necessary to develop effective positive contrast agents for magnetic resonance imaging from Eu(2+)-containing cryptates.

Luminescence-decay measurements were studied as a simple and fast technique to determine inner-sphere water coordination numbers of LnIII-based complexes in binary solvent systems that are useful for catalysis. The luminescence-decay rates of EuIII-containing complexes were used to elucidate the coordination environment of EuIII in these solvent systems. Our findings were used to empirically derive easy-to-use equations to determine the average number of inner-sphere water and solvent molecules in binary aqueous solvent systems. The increased knowledge of the inner-sphere coordination environment of catalysts that our equations enable can be used to study lanthanide-catalyzed reactions and new precatalysts.

The atomic structure of graphene on polycrystalline copper substrates has been studied using scanning tunneling microscopy. The graphene overlayer maintains a continuous pristine atomic structure over atomically flat planes, monatomic steps, edges, and vertices of the copper surface. We find that facets of different identities are overgrown with graphene's perfect carbon honeycomb lattice. Our observations suggest that growth models including a stagnant catalytic surface do not apply to graphene growth on copper. Contrary to current expectations, these results reveal that the growth of macroscopic pristine graphene is not limited by the underlying copper structure.

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO4]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lantha...

The electronic properties of graphene, such as high charge carrier concentrations and mobilities, make it a promising candidate for next-generation nanoelectronic devices. In particular, electrons and holes can undergo ballistic transport on the sub-micrometre scale in graphene and do not suffer from the scale limitations of current MOSFET technologies. However, it is still difficult to produce single-layer samples of graphene and bulk processing has not yet been achieved, despite strenuous efforts to develop a scalable production method. Here, we report a versatile solution-based process for the large-scale production of single-layer chemically converted graphene over the entire area of a silicon/SiO(2) wafer. By dispersing graphite oxide paper in pure hydrazine we were able to remove oxygen functionalities and restore the planar geometry of the single sheets. The chemically converted graphene sheets that were produced have the largest area reported to date (up to 20 x 40 microm), making them far easier to process. Field-effect devices have been fabricated by conventional photolithography, displaying currents that are three orders of magnitude higher than previously reported for chemically produced graphene. The size of these sheets enables a wide range of characterization techniques, including optical microscopy, scanning electron microscopy and atomic force microscopy, to be performed on the same specimen.

The Eu(II) ion rivals Gd(III) in its ability to enhance contrast in magnetic resonance imaging. However, all reported Eu(II)-based complexes have been studied in vitro largely because the tendency of Eu(II) to oxidize to Eu(III) has been viewed as a major obstacle to in vivo imaging. Herein, we present solid- and solution-phase characterization of a Eu(II)-containing cryptate and the first in vivo use of Eu(II) to provide contrast enhancement. The results indicate that between one and two water molecules are coordinated to the Eu(II) core upon dissolution. We also demonstrate that Eu(II)-based contrast enhancement can be observed for hours in a mouse.

Eu(II)-containing materials have unique luminescence, redox, and magnetic properties that have potential applications in optoelectronics, sensors, and imaging. Here, we report the synthesis and characterization of Eu(II)-containing aza-222 cryptate that displays yellow luminescence and a quantum yield of 26% in aqueous media. The crystal structure reveals a staggered hula-hoop geometry. Both solid-state and solution-phase data are presented that indicate that the high quantum yield is a result of the absence of OH oscillators in the inner sphere of the complex. We expect that Eu(II)-containing aza-222 cryptate is a step toward Eu(II)-containing luminescent materials that can be used in a variety of applications including biological imaging.

In magnetic resonance imaging, contrast agents are molecules that increase the contrast-to-noise ratio of non-invasively acquired images. The information gained from magnetic resonance imaging can be increased using responsive contrast agents that undergo chemical changes, and consequently changes to contrast enhancement, for example in response to specific biomarkers that are indicative of diseases. A major limitation with modern responsive contrast agents is concentration-dependence that requires the concentration of contrast agent to be known: an extremely challenging task in vivo. Here, we review advances in several strategies aimed at overcoming the concentration-dependent nature of responsive contrast agents.