Reactions of isonitriles with [Fe₃(CO)₁₂] and [Ru₃(CO)₁₂] monitored by electrospray mass spectrometry: structural characterisation of [Fe₃(CO)₁₀(CNPh)₂] and [Ru₄(CO)₁₁(μ₃-η²-CNPh)₂(CNPh)]

The reactions of [Fe₃(CO)₁₂] or [Ru₃(CO) ₁₂] with RNC (R=Ph, C₆H₄OMe-p or CH₂SO₂C₆H₄Me-p) have been investigated using electrospray mass spectrometry. Species arising from substitution of up to six ligands were detected for [Fe₃(CO)₁₂], but the higher-substituted compounds were too unstable to be isolated. The crystal structure of [Fe₃(CO)₁₀(CNPh)₂] was determined at 150 and 298 K to show that both isonitrile ligands were trans to each other on the same Fe atom. For [Ru₃(CO)₁₂] substitution of up to three COs was found, together with the formation of higher-nuclearity clusters. [Ru₄(CO)₁₁(CNPh)₃] was structurally characterised and has a spiked-triangular Ru₄ core with two of the CNPh ligands coordinated in an unusual μ₃-η² mode. The substitution reactions of [M₃(CO)₁₂] by RNC have been investigated by electrospray mass spectrometry showing up to six COs can be replaced. [Fe₃(CO)₁₀(CNPh)₂] has both PhNC axially on the same Fe atom, and [Ru₄(CO)₁₁(μ₃-η²-CNPh)₂(CNPh)] has a spiked-triangular cluster core with two PhNC ligands in an unusual coordination mode

Platinum(II), palladium(II), nickel(II), and gold(I) complexes of the “electrospray-friendly” thiolate ligands 4-SC₅H₄N- and 4-SC₆H₄OMe-

The series of platinum(II), palladium(II), and nickel(II) complexes [ML₂(dppe)] [M = Ni, Pd, Pt; L = 4-SC₅H₄N or 4-SC₆H₄OMe; dppe = Ph₂PCH₂CH₂PPh₂] containing pyridine-4-thiolate or 4-methoxybenzenethiolate ligands, together with the corresponding gold(I) complexes [AuL(PPh3)], were prepared and their electrospray ionization mass spectrometric behavior compared with that of the thiophenolate complexes [M(SPh)₂(dppe)] (M = Ni, Pd, Pt) and [Au(SPh)(PPh₃)]. While the pyridine-4-thiolate complexes yielded protonated ions of the type [M + H]+ and [M + 2H]²+ ions in the Ni, Pd, and Pt complexes, an [M + H]+ ion was only observed for the platinum derivative of 4-methoxybenzenethiolate. Other ions, which dominated the spectra of the thiophenolate complexes, were formed by thiolate loss and aggregate formation. The X-ray crystal structure of [Pt(SC₆H₄OMe-4)₂(dppe)] is also reported

Deer, People, and Parks: Perspectives of Residents in Communities Near Valley Forge National Historical Park

Click on the PDF for an Executive Summary and the full report. Visit the HDRU website for a complete listing of HDRU publications at: http://hdru.dnr.cornell.edu

Applied Meteorology Unit (AMU) Quarterly Report First Quarter FY-14

NASA's LSP and other programs at Vandenberg Air Force Base (VAFB) use wind forecasts issued by the 30th Operational Support Squadron (30 OSS) to determine if they need to limit activities or protect property such as a launch vehicle due to the occurrence of warning level winds at VAFB in California. The 30 OSS tasked the AMU to provide a wind forecasting capability to improve wind warning forecasts and enhance the safety of their customers' operations. This would allow 30 OSS forecasters to evaluate pressure gradient thresholds between pairs of regional observing stations to help determine the onset and duration of warning category winds. Development of such a tool will require that solid relationships exist between wind speed and the pressure gradient of one or more station pairs. As part of this task, the AMU will also create a statistical climatology of meteorological observations from the VAFB wind towers

Immune evasion in cancer: mechanistic basis and therapeutic strategies

Cancer immune evasion is a major stumbling block in designing effective anticancer therapeutic strategies. Although considerable progress has been made in understanding how cancers evade destructive immunity, measures to counteract tumor escape have not kept pace. There are a number of factors that contribute to tumor persistence despite having a normal host immune system. Immune editing is one of the key aspects why tumors evade surveillance causing the tumors to lie dormant in patients for years through “equilibrium” and “senescence” before re- emerging. In addition, tumors exploit several immunological processes such as targeting the regulatory T cell function or their secretions, antigen presentation, modifying the production of immune suppressive mediators, tolerance and immune deviation. Besides these, tumor heterogeneity and metastasis also play a critical role in tumor growth. A number of potential targets like promoting Th1, NK cell, γδ T cell responses, inhibiting Treg functionality, induction of IL-12, use of drugs including phytochemicals have been designed to counter tumor progression with much success. Some natural agents and phytochemicals merit further study. For example, use of certain key polysaccharide components from mushrooms and plants have shown possess therapeutic impact on tumor-imposed genetic instability, anti-growth signaling, replicative immortality, deregulated metabolism etc. In this review, we will discuss the advances made towards understanding the basis of cancer immune evasion and summarize the efficacy of various therapeutic measures and targets that have been developed or are being investigated to enhance tumor rejection

Generation of Functional CLL-Specific Cord Blood CTL Using CD40-Ligated CLL APC

PMCID: PMC3526610This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited

NuSTAR ground calibration: The Rainwater Memorial Calibration Facility (RaMCaF)

The Nuclear Spectroscopic Telescope Array (NuSTAR) is a NASA Small Explorer mission that will carry the first focusing hard X-ray (5-80 keV ) telescope to orbit. The ground calibration of the three flight optics was carried out at the Rainwater Memorial Calibration Facility (RaMCaF) built for this purpose. In this article we present the facility and its use for the ground calibration of the three optics

Space Shuttle Orbiter Structures and Mechanisms

The Space Shuttle Orbiter has performed exceptionally well over its 30 years of flight experience. Among the many factors behind this success were robust, yet carefully monitored, structural and mechanical systems. From highlighting key aspects of the design to illustrating lessons learned from the operation of this complex system, this paper will attempt to educate the reader on why some subsystems operated flawlessly and why specific vulnerabilities were exposed in others. Specific areas to be covered will be the following: high level configuration overview, primary and secondary structure, mechanical systems ranging from landing gear to the docking system, and windows

Production and calibration of the first HEFT hard x-ray optics module

Complete hard X-ray optics modules are currently being produced for the High Energy Focusing Telescope (HEFT), a balloon born mission that will observe a wide range of objects including young supernova remnants, active galactic nuclei, and galaxy clusters at energies between 20 and 70 keV. Large collecting areas are achieved by tightly nesting layers of grazing incidence mirrors in a conic approximation Wolter-I design. The segmented layers are made of thermally-formed glass substrates coated with depth-graded multilayer films for enhanced reflectivity. Our novel mounting technique involves constraining these mirror segments to successive layers of precisely machined graphite spacers. We report the production and calibration of the first HEFT optics module

X-ray scatter measurements from thermally slumped thin glass substrates for the HEFT hard x-ray telescopes

We have performed x-ray specular reflectivity and scattering measurements of thermally slumped glass substrates on x-ray diffractometers utilizing a rotating anode x-ray source at the Danish Space Research Institute (DSRI) and synchrotron radiation at the European Synchrotron Radiation Facility (ESRF) optics Bending Magnet beamline. In addition, we tested depth graded W/Si multilayer-coated slumped glass using x-ray specular reflectivity measurements at 8.048 keV and 28 keV and energy-dispersive measurements in the 20-50 keV rang at a double-axis diffractometer at the Orsted Laboratory, University of Copenhagen. The thermally slumped glass substrates will be used to fabricate the hard x-ray grazing incidence optics for the High-Energy Focusing Telescope. We compared the measurements to the SODART- mirrors from the SRG telescope mission program. The surface scatter measurement of the thermally slumped glass substrates yields Half Power Diameters (HPD's) of single- bounce mirrors of full-illuminated lengths of ~ 40 arcseconds for typical substrates and as low as ~ 10 arcseconds for the best substrates, whereas the SODART mirrors yields HPD's of ~ 80 arcseconds with very little variation. Both free-standing glass substrates and prototype mounted and multilayer-coated optics were tested. The result demonstrate that the surface scatter contribution, plus any contribution from the mounting procedure, to the Half Power Diameter from a telescope using the slumped glass optics will be in the subarcminute range.In addition we measured low surface microroughness, yielding high reflectivity, from the glass substrates, as well as from the depth graded W/Si multilayer-coated glass glass (interfacial width 4.2 Å)