Palladium(II) and platinum(II) bind strongly to an engineered blue copper protein

Studies of palladium(II) and platinum(II) binding to well-characterized proteins contribute to understanding the influence of these metals in the environment and body. The well-characterized apoprotein of azurin has a soft-metal binding site that may be exposed to solvent by mutation of a coordinating His-117 residue to glycine (H117G). Palladium(II) and platinum(II) form strong 1:1 adducts with the apo form of H117G azurin. A combination of UV-vis, circular dichroism, and inductively coupled plasma mass spectrometry techniques suggests that the metal binds specifically at His-46 and Cys-112 of the protein.     

Tuning Tetrazole Photochemistry for Protein Ligation and Molecular Imaging

Photochemistry provides a wide range of alternative reagents that hold potential for use in bimolecular functionalisation of proteins. Here, we report the synthesis and characterisation of metal ion binding chelates derivatised with disubstituted tetrazoles for the photoradiochemical labelling of monoclonal antibodies (mAbs). The photophysical properties of tetrazoles featuring extended aromatic systems and auxochromic substituents to tune excitation toward longer wavelengths (365 and 395 nm) were studied. Two photoactivatable chelates based on desferrioxamine B (DFO) and the aza-macrocycle NODAGA were functionalised with a tetrazole and developed for protein labelling with ⁸⁹Zr, ⁶⁴Cu and ⁶⁸Ga radionuclides. DFO-tetrazole ( 1 ) was assessed by direct conjugation to formulated trastuzumab and subsequent radiolabelling with ⁸⁹Zr. Radiochemical studies and cellular-based binding assays demonstrated that the radiotracer remained stable in vitro retained high immunoreactivity. Positron emission tomography (PET) imaging and biodistribution studies were used to measure the tumour specific uptake and pharmacokinetic profile in mice bearing SK-OV-3 xenografts. Experiments demonstrate that tetrazole-based photochemistry is a viable approach for the light-induced synthesis of PET radiotracers.     

Broadband Multidimensional Spectroscopy Identifies the Amide II Vibrations in Silkworm Films

We used two-dimensional infrared spectroscopy to disentangle the broad infrared band in the amide II vibrational regions of Bombyx mori native silk films, identifying the single amide II modes and correlating them to specific secondary structure. Amide I and amide II modes have a strong vibrational coupling, which manifests as cross-peaks in 2D infrared spectra with frequencies determined by both the amide I and amide II frequencies of the same secondary structure. By cross referencing with well-known amide I assignments, we determined that the amide II (N-H) absorbs at around 1552 and at 1530 cm^–1 for helical and β-sheet structures, respectively. We also observed a peak at 1517 cm⁻¹ that could not be easily assigned to an amide II mode, and instead we tentatively assigned it to a Tyrosine sidechain. These results stand in contrast with previous findings from linear infrared spectroscopy, highlighting the ability of multidimensional spectroscopy for untangling convoluted spectra, and suggesting the need for caution when assigning silk amide II spectra.     

Baer ordered *-fields of the first kind

We construct examples of Baer ordered *-fields of the first kind of every dimension 4 ⁿ ,n=1,2,….     

Predicting transport properties without adjustable parameters: A test application of the Hulburt-Hirschfelder potential to argon

Accurate estimates of the transport properties of gaseous systems under conditions where experimental transport data are sparse of unavailable are important in a number of applications. The Hulburt-Hirschfelder (HH) potential for monatomic gas interactions, which is determined entirely by spectroscopic constants of diatomic molecules, provides a basis for calculating transport properties without adjustable parameters. In this paper we report test calculations of the viscosity, thermal conductivity and self-diffusion coefficients for argon. Comparison with the comprehensive correlation of thermophysical properties for argon by Kestin and co-workers shows very reasonable agreement for the transport properties at moderate and high temperatures. Deviations at lower temperatures may be attributed to inaccuracies in the long-range part of the HH potential, whereas the core and well of the potential appear to be adequately represented. These results strongly support the use of the HH potential for estimating the transport properties of monatomic gases at high t     

Alkyl ketoximes as analytical reagents. IX

Summary A method is outlined for the determination of trace amounts of palladium in a standard nickel-copper reference matte using the 4-heptanone oxime extraction procedure. The average result of 0.259 oz/ton agrees favourably with the recommended value of 0.24 oz/ton.

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Zusammenfassung Ein Verfahren zur Bestimmung von Palladiumspuren in einer standardisierten Nickel-Kupfer-Bezugsprobe mit Hilfe der Extraktion mit 4-Heptanonoxim wurde angegeben. Das durchschnittliche Ergebnis von 0,259 Unzen/Tonne stimmt mit dem statistisch ermittelten Wert von 0,24 Unzen/Tonne sehr gut überein.