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The design, synthesis, and characterization of a novel Ni(II) chelator

Two new Sm

The title metallacrown (MC) complexes Ln

A set of (Ln[14-MC(Zn(II)N(quinHA))-5])(2)Ln(2)Zn(2)(quinHA)(2)(ph)(2)(Hph)(4)(OH)(8)(H(2)O)(4) metallacrowns (Ln-1, Ln = Tb, Gd, or Yb; H(2)quinHA = quinaldic hydroxamic acid, H(2)ph = phthalic acid) have been synthesized via solution-state self-assembly. The metallacrowns possess an uncommon topology within the metallacrown family where two rarely seen 14-metallacrown-5 moieties are fused by a Yb(2)Zn(2)(quinHA)(2) bridge. Moreover, Yb-1 analyzed in the solid state exhibits a characteristic near-infrared luminescence signal arising from Yb(3+ 2)F(5/2)→(2)F(7/2) transition despite the proximity of high energy O−H oscillators.

Hypoxia is a prognostic biomarker of rapidly growing cancers, where the extent of hypoxia is an indication of tumor progression and prognosis; therefore, hypoxia is also used for staging while performing chemo- and radiotherapeutics for cancer. Contrast-enhanced MRI using Eu II -based contrast agents is a noninvasive method that can be used to map hypoxic tumors, but quantification of hypoxia using these agents is challenging due to the dependence of signal on the concentration of both oxygen and Eu II . Here, we report a ratiometric method to eliminate concentration dependence of contrast enhancement of hypoxia using fluorinated Eu II/III -containing probes. We studied three different Eu II/III couples of complexes containing 4, 12, or 24 fluorine atoms to balance fluorine signal-to-noise ratio with aqueous solubility. The ratio between the longitudinal relaxation time ( T 1 ) and 19 F signal of solutions containing different ratios of Eu II - and Eu III -containing complexes was plotted against the percentage of Eu II -containing complexes in solution. We denote the slope of the resulting curves as hypoxia indices because they can be used to quantify signal enhancement from Eu, that is related to oxygen concentration, without knowledge of the absolute concentration of Eu. This mapping of hypoxia was demonstrated in vivo in an orthotopic syngeneic tumor model. Our studies significantly contribute toward improving the ability to radiographically map and quantify hypoxia in real time, which is critical to the study of cancer and a wide range of diseases.

Objectives Two-dimensional measurements of acetabular geometry are widely used for the assessment of acetabular component orientation following total hip replacement (THR). With the increasing availability of computed tomography scans, there is an opportunity to develop three-dimensional (3D) planning to improve surgical accuracy. The aim of this study was to validate a 3D workflow for measuring angles of lateral opening (ALO) and version, and to establish reference values for dogs. Methods Pelvic computed tomography scans were obtained from 27 skeletally mature dogs with no radiographic evidence of hip joint pathology. Patient-specific 3D models were built, and ALO and version angles were measured for both acetabula. The validity of the technique was determined by calculating intra-observer coefficient of variation (CV, %). Reference ranges were calculated and data from left and right hemipelves were compared using a paired t-test and symmetry index. Results Measurements of acetabular geometry were highly repeatable (intra-observer CV 3.5–5.2%, inter-observer CV 3.3–5.2%). Mean (± standard deviation) values for ALO and version angle were 42.9 degrees (± 4.0 degrees) and 27.2 degrees (± 5.3 degrees) respectively. Left-right measurements from the same dog were symmetrical (symmetry index 6.8 to 11.1%) and not significantly different. Conclusions Mean values of acetabular alignment were broadly similar to clinical THR guidelines (ALO of 45 degrees, version angle of 15–25 degrees), but the wide variation in angle measurements highlights the potential need for patient-specific planning to reduce the risk of complications such as luxation.

Structural, spectroscopic, and electrochemical investigations of two new complexes of divalent Sm are presented.

Hypoxia is a hallmark of many diseases, including cancer, arthritis, heart and kidney diseases, and diabetes, and it is often associated with disease aggressiveness and poor prognosis. Consequently, there is a critical need for imaging hypoxia in a noninvasive and direct way to diagnose, stage, and monitor the treatment and development of new therapies for these diseases. Eu-containing contrast agents for magnetic resonance imaging have demonstrated potential for in vivo imaging of hypoxia via changes in metal oxidation state from +2 to +3, but rapid oxidation in blood limits Eu

We describe a study of the influence of amine-containing ligands on the photoredox-relevant properties of Eu

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.

OBJECTIVE: To report veterinarians' familiarity with and perceptions of owner/observer-reported outcome measures (OROMs) and their applications in routine clinical practice. STUDY DESIGN: Cross-sectional online survey. ANIMALS OR SAMPLE POPULATION: A total of 441 veterinarians with a caseload of companion animal orthopedic patients. METHODS: Respondents answered questions regarding their familiarity with and application of OROMs. Respondents provided opinions on statements related to reasons for using or not using OROMs in routine clinical practice, prerequisites to implement OROMs in routine clinical practice, and whether they would implement OROMs in routine clinical practice if adequate tools/technologies were available. RESULTS: Most (293/441, 66.4%) respondents felt familiarity with at least one OROM. Only 17.5% (77 out of the 440 answering the question about the application of OROMs) applied OROMs in routine clinical practice. The two main reasons for not using OROMs in routine clinical practice were the lack of opportunity/feasibility and the lack sufficient information/knowledge/experiences. User-friendliness, time efficiency, and interpretability were considered the most important prerequisites for implementing OROMs in routine clinical practice. If adequate tools/technologies were available, 266/439 (60.6%) respondents indicated that they would definitely implement OROMs in routine clinical practice. CONCLUSION: Although most respondents were familiar with at least one OROM, fewer than one-fifth applied them in routine clinical practice. Most respondents were willing to implement OROMs in routine clinical practice if adequate tools/technologies were available. CLINICAL SIGNIFICANCE: Our results justify further investigations to improve the application of OROMs in routine clinical practice in veterinary care of companion animal orthopedic patients.

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.

Supported lipid membranes are versatile biomimetic coatings for the chemical functionalization of inorganic surfaces. Developing simple and effective fabrication strategies to form supported lipid membranes with micropatterned geometries is a long-standing challenge. Herein, we demonstrate how the combination of chemical lift-off lithography (CLL) and easily prepared lipid bicelle nanostructures can yield micropatterned, supported lipid membranes on gold surfaces with high pattern resolution, conformal character, and biofunctionality. Using CLL, we functionalized gold surfaces with patterned arrays of hydrophilic and hydrophobic self-assembled monolayers (SAMs). Time-lapse fluorescence microscopy imaging revealed that lipid bicelles adsorbed preferentially onto the hydrophilic SAM regions, while there was negligible lipid adsorption onto the hydrophobic SAM regions. Functional receptors could be embedded within the lipid bicelles, which facilitated selective detection of receptor-ligand binding interactions in a model streptavidin-biotin system. Quartz crystal microbalance-dissipation measurements further identified that lipid bicelles adsorb irreversibly and remain intact on top of the hydrophilic SAM regions. Taken together, our findings indicate that lipid bicelles are useful lipid nanostructures for reproducibly assembling micropatterned, supported lipid membranes with precise pattern fidelity.

The use of extracorporeal shock wave therapy (ESWT) for the treatment of delayed or non-union of long bone fractures has been described in human patients with encouraging results. This case report describes the successful treatment of a mandibular fracture non-union with ESWT. To authors' knowledge, this is the first report of the clinical use of ESWT for the management of a non-union in a dog.

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.

Objective The aim of this study was to determine the biomechanical behaviour of a novel distraction–fusion system, consisting of an intervertebral distraction screw, pedicle locking screws and connecting rods, in the canine caudal cervical spine. Study Design Biomechanical study in cadaveric canine cervicothoracic (C3–T3) spines (n = 6). Cadaveric spines were harvested, stripped of musculature, mounted on a four-point bending jig, and tested using non-destructive four-point bending loads in extension (0–100 N), flexion (0–60 N) and lateral bending (0–40 N). Angular displacement was recorded from reflective optical trackers rigidly secured to C5, C6 and C7. Data for primary and coupled motions were collected from intact spines and following surgical stabilization (after ventral annulotomy and nucleotomy) with the new implant system. Results As compared with the intact spine, instrumentation significantly reduced motion at the operated level (C5-C6) with a concomitant non-significant increase at the adjacent level (C6-C7). Conclusion The combination of a locking pedicle screw-rod system and intervertebral spacer provides an alternative solution for surgical distraction–stabilization in the canine caudal cervical spine and supports the feasibility of using this new implant system in the management of disc-associated cervical spondylomyelopathy in dogs. The increase in motion at C6-C7 may suggest the potential for adjacent level effects and clinical trials should be designed to address this.

Background Pancarpal arthrodesis is purported to limit supination and pronation of the feline antebrachium. The objective of this study was to investigate whether plate fixation of the radius to the carpus and metacarpus limits supination and pronation of the ulna relative to the radius as a model for pancarpal arthrodesis in the cat. Eight feline cadaveric forelimbs were rotated from supination to pronation in a testing jig and CT (computed tomography) was performed in the neutral, supinated and pronated positions. A locking plate was then secured dorsally to the radius, radial carpal bone and metacarpal III of each of the limbs. CT was repeated in each of the testing positions following plate application. The radius and ulna of the control specimens, and the radius, ulna and plate of the plated specimens were then segmented using software. Alignment of the bones to the radius in the control specimens, and to the plate in the plated specimens was used to compare the changes in degrees of movement of the ulna relative to the radius in dorsal, sagittal and transverse planes. Results Based on the results of the paired t test, there was no significant difference in degrees of movement, or total range of motion between control and plated specimens in supinated and pronated testing conditions. Conclusion The results of this ex-vivo study indicate that under the testing conditions employed, plate fixation of the radius to the carpus and metacarpus does not limit supination and pronation of the feline antebrachium.

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.

Diffuse idiopathic skeletal hyperostosis (DISH) is a disorder of unknown cause, in which new bone forms in soft tissues attached to the skeleton. Originally described in humans, in whom it is quite common, it is usually asymptomatic. New bone may completely bridge across joints, especially in the spine. However, it can be difficult to distinguish from diseases such as spondyloarthritis and spondylosis. With safer and increased use of radiography in diagnosis, the unfamiliar skeletal changes of asymptomatic DISH may now be coincidentally revealed during investigation of other disorders and result in misdiagnosis and unnecessary treatment. There have been case reports of its occurrence in great apes, but this is the first study to illustrate its appearances in a series of 11 skeletons of western and eastern lowland gorillas (Gorilla gorilla gorilla and Gorilla beringei graueri) from zoos in Europe and the United States. The study combines a review of available clinical and postmortem records with examination of the skeletons and radiologic investigation, such as computed tomography (CT). The results indicate that the disorder is probably common in older (>30 yr) captive gorillas, but that it is asymptomatic. It was not symptomatic during life in any of these animals. Several cases had unexpected features, such as extensive involvement of the thorax and extra-articular sacroiliac and tibiofibular joint fusions that are not typical in humans. By illustrating these skeletons, the study should aid differentiation of DISH from spondylosis (syn spondylosis deformans) and spondyloarhritis. It illustrates those features that are atypical of human DISH. CT scanning is valuable in such cases for examining diagnostically important areas such as sacroiliac joints. Increased awareness of DISH should help with understanding its cause, both in gorillas and humans.