Facile O-atom insertion into C-C and C-H bonds by a trinuclear copper complex designed to harness a singlet oxene

Two trinuclear copper [CuICuICuI(L)]1+ complexes have been prepared with the multidentate ligands (L) 3,3'-(1,4-diazepane-1,4-diyl)bis(1-((2-(dimethylamino)ethyl)(methyl)amino)propan-2-ol) (7-Me) and (3,3'-(1,4-diazepane-1,4-diyl)bis(1-((2-(diethylamino) ethyl)(ethyl) amino)propan-2-ol) (7-Et) as models for the active site of the particulate methane monooxygenase (pMMO). The ligands were designed to form the proper spatial and electronic geometry to harness a "singlet oxene," according to the mechanism previously suggested by our laboratory. Consistent with the design strategy, both [CuICuICuI(L)]1+ reacted with dioxygen to form a putative bis(µ3-oxo)CuIICuIICuIII species, capable of facile O-atom insertion across the central C-C bond of benzil and 2,3-butanedione at ambient temperature and pressure. These complexes also catalyze facile O-atom transfer to the C-H bond of CH3CN to form glycolonitrile. These results, together with our recent biochemical studies on pMMO, provide support for our hypothesis that the hydroxylation site of pMMO contains a trinuclear copper cluster that mediates C-H bond activation by a singlet oxene mechanism

Fibromyxoid Sarcoma of the Breast: An Atypical Presentation of a Rare Mesenchymal Tumor

Background: Low-grade Fibromyxoid Sarcoma (LGFMS) is a rare soft-tissue sarcoma with an incidence rate of 0.18 per million, first introduced into the literature by Harry L. Evans in 1987 [1]. This tumor, of mesenchymal origin, has a predilection for young adults and is most commonly found in the upper and lower extremities of deep soft tissues [1,2,3,4,5]. LGFMS has been described as having multiple variants, often presenting histologically as alternating fibrous and myxoid areas containing bland spindle and stellate cells arranged in a swirling, whorled appearance [6]. The predominant chromosomal abnormality of LGFMS has a FUS-CREB3L2 fusion gene with a t(7; 16)(q33; p11) translocation. While other fusion genes expressed by LGFMS are rare, the second most common variation seen is FUS-CREB3L1, which occurs due to a t(11;16)(p11;p11) chromosomal translocation [1,2]. Evans’ original report indicated that although slow-growing, this tumor had a high incidence of recurrence with a tendency to metastasize [7]. This insidious nature was highlighted in a 2011 study that showed after a mean follow-up of 14 years, 50% of the patients developed metastasis, and 42% died of the disease [8]. These prognostic factors associated with LGFMS make early detection and definitive management essential in reducing morbidity and mortality in this patient population [9]. This case study aims to highlight the presentation of primary LGFMS in a unique anatomical location within a demographic not commonly affected by this disease. Case presentation: A 28-year-old Hispanic female presented to the clinic for evaluation of a slow-growing mass present in the left upper chest for the past four years. Prior to arriving at the clinic, the patient received a diagnostic ultrasound that displayed a 1.8 x 1.5 x 1 cm solid mass in the upper chest. The patient stated that although the mass had not grown significantly, and she was overall asymptomatic, mild discomfort was present on direct palpation of the involved tissue. The patient denied any significant past medical history, family history, recent trauma, or other known risk factors, thus additional recommendations were made for an excisional biopsy. Subsequent histopathology of the mass demonstrated a soft tissue sarcoma positive for MUC-4. In addition to the biopsy findings seen in this mass, as well as the Federation of Cancer Centers Sarcoma Group (FNCLCC) grading system providing our patient’s tumor with a total score of 2 for parameters that determine a tumor\u27s grade, a diagnosis strongly favoring a LGFMS was made. Conclusions: LGFMS is a rare and insidious soft-tissue sarcoma with a high incidence of recurrence and metastasis. Its rarity and appearance make it challenging to diagnose and manage effectively. However, histologic examination and FISH can aid in diagnostic accuracy. This entails identifying the alternating fibrous and myxoid areas containing bland spindle and stellate cells arranged in a swirling, whorled appearance and the FUS-CREB3L2 fusion gene with a t(7;16) (q33;p11) translocation. This case highlights the importance of considering LGFMS in the differential diagnosis of soft-tissue tumors, even in atypical anatomical locations and demographics not commonly affected by this disease. Unfortunately, the rarity and benign appearance of LGFMS can delay diagnosis, potentially affecting the patient\u27s prognosis. Therefore, early detection and definitive management are crucial to improving outcomes for patients with LGFMS. Further research into the pathogenesis of LGFMS is needed to improve early detection, definitive management, and the prognosis of affected patients

Management of Pasture Quality for Sheep on New Zealand Hill Country

The control of pasture quality over spring is central to the achievement of high levels of sheep performance on hill country. Despite this, with the exception of the work of Lambert et al. (2000), little is known about how farmers actually manage pasture quality. The purpose of this research was to describe how a high performing hill country farmer manages pasture quality on their sheep area over spring and from this develop a framework that will assist other farmers improve their pasture management

A special simplex in the state space for entangled qudits

Focus is on two parties with Hilbert spaces of dimension d, i.e. "qudits". In the state space of these two possibly entangled qudits an analogue to the well known tetrahedron with the four qubit Bell states at the vertices is presented. The simplex analogue to this magic tetrahedron includes mixed states. Each of these states appears to each of the two parties as the maximally mixed state. Some studies on these states are performed, and special elements of this set are identified. A large number of them is included in the chosen simplex which fits exactly into conditions needed for teleportation and other applications. Its rich symmetry - related to that of a classical phase space - helps to study entanglement, to construct witnesses and perform partial transpositions. This simplex has been explored in details for d=3. In this paper the mathematical background and extensions to arbitrary dimensions are analysed.Comment: 24 pages, in connection with the Workshop 'Theory and Technology in Quantum Information, Communication, Computation and Cryptography' June 2006, Trieste; summary and outlook added, minor changes in notatio

Face-space: A unifying concept in face recognition research

The concept of a multidimensional psychological space, in which faces can be represented according to their perceived properties, is fundamental to the modern theorist in face processing. Yet the idea was not clearly expressed until 1991. The background that led to the development of face-space is explained, and its continuing influence on theories of face processing is discussed. Research that has explored the properties of the face-space and sought to understand caricature, including facial adaptation paradigms, is reviewed. Face-space as a theoretical framework for understanding the effect of ethnicity and the development of face recognition is evaluated. Finally, two applications of face-space in the forensic setting are discussed. From initially being presented as a model to explain distinctiveness, inversion, and the effect of ethnicity, face-space has become a central pillar in many aspects of face processing. It is currently being developed to help us understand adaptation effects with faces. While being in principle a simple concept, face-space has shaped, and continues to shape, our understanding of face perception

Transformation Optics for Plasmonics

A new strategy to control the flow of surface plasmon polaritons at metallic surfaces is presented. It is based on the application of the concept of Transformation Optics to devise the optical parameters of the dielectric medium placed on top of the metal surface. We describe the general methodology for the design of Transformation-Optical devices for surface plasmons and analyze, for proof-of-principle purposes, three representative examples with different functionalities: a beam shifter, a cylindrical cloak and a ground-plane cloak.Comment: 15 pages, 3 figure

Defective Erythrocyte Pyruvate Kinase with Impaired Kinetics and Reduced Optimal Activity

A unique mutant form of erythrocyte pyruvate kinase has been found associated with chronic haemolytic anaemia in a child who is apparently doubly heterozygous for the mutant isoenzyme and for pyruvate kinase deficiency of the classical quantitative type. Clinical and laboratory findings conformed closely to those typically observed in homozygous pyruvate kinase deficiency anaemia. Assayed in fresh haemolysates, the isoenzyme exhibited reduced optimal activity ( c 45% of normal) and an increased Michaelis constant for phosphoenolpyruvate (four to five times greater than normal). The kinetic anomaly was only partially corrected by activation with fructose-1,6-disphosphate. Despite some common characteristics, this isoenzyme appears distinct from others reported in the literature and lends support to the polymorphous nature of heritable baemolytic anaemias secondary to defective pyruvate kinase.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/73844/1/j.1365-2141.1972.tb05713.x.pd

Molecular and morphometric variation in European populations of the articulate brachiopod <i>Terebeatulina retusa</i>

Molecular and morphometric variation within and between population samples of the articulate brachiopod &lt;i&gt;Terebratulina&lt;/i&gt; spp., collected in 1985-1987 from a Norwegian fjord, sea lochs and costal sites in western Scotland, the southern English Channel (Brittany) and the western Mediterranean, were measured by the analysis of variation in the lengths of mitochondrial DNA (mtDNA) fragments produced by digestion with nine restriction endonucleases and by multivariate statistical analysis of six selected morphometric parameters. Nucleotide difference within each population sample was high. Nucleotide difference between population samples from the Scottish sites, both those that are tidally contiguous and those that appear to be geographically isolated, were not significantly different from zero. Nucleotide differences between the populations samples from Norway, Brittany, Scotland and the western Mediterranean were also very low. Morphometric analysis confirmed the absence of substantial differentiation