Reactivity of a Cyclopentadienyl Containing Heterobimetallic Alkoxide

The synthesis of the new heteroleptic heterotrimetallic cluster, [(C₅H₅)Sn(μ-OBu^t)₂Ge(OBu^t)Mo(CO)₅] (1) has been achieved by a thermally induced CO substitution of the transition metal derivative, Mo(CO)₆, by the basic germanium atom of the cyclopentadienyl heterobimetallic alkoxide, [(C₅H₅)Sn(μ-OBu^t)₂Ge(OBu^t)]. The microanalysis, molecular weight (monomer in benzene), IR and multinuclear NMR data and X-ray diffraction study is consistent with the formulation of 1. The Sn atom has a trigonal pyramidal coordination environment formed by a aysmmterically π-bonded terminal C₅H₅ ring and two symmetrically bridged tert-butoxy groups. The four-coordinate Ge atom lies at the centre of a distorted tetrahedron and is terminally attached to a tert-butoxy group and a Mo(CO)₅5^? fragment.     

Synthesis and Biological Evaluation of a Class of Mitochondrially‐Targeted Gadolinium(III) Agents

A structure–activity relationship study of a library of novel bifunctional Gd^III complexes covalently linked to arylphosphonium cations is reported. Such complexes have been designed for potential application in binary cancer therapies such as neutron capture therapy and photon activation therapy. A positive correlation was found between lipophilicity and cytotoxicity of the complexes. Mitochondria uptake was determined by means of inductively coupled plasma mass spectrometry (ICP‐MS), and Gd uptake was determined by means of quantification using synchrotron X‐ray fluorescence (XRF) imaging. A negative correlation between lipophilicity and tumour selectivity of the Gd^III complexes was demonstrated. This study highlights the delicate balance required to minimise in vitro cytotoxicity and optimise in vitro tumour selectivity and mitochondrial localisation for this new class of mitochondrially‐targeted binary therapy agents. We also report the highest in vitro tumour selectivity for any Gd agent reported to date, with a T/N (tumour/normal cell) ratio of up to 23.5±6.6.     

Morphological changes in the cellulose and lignin components of biomass occur at different stages during steam pretreatment

Morphological changes to the different components of lignocellulosic biomass were observed as they occurred during steam pretreatment by placing a pressure reaction cell in a neutron beam and collecting time-resolved neutron scattering data. Changes to cellulose morphology occurred mainly in the heating phase, whereas changes in lignin morphology occurred mainly in the holding and cooling phases. During the heating stage, water is irreversibly expelled from cellulose microfibrils as the elementary fibrils coalesce. During the holding phase lignin aggregates begin to appear and they increase in size most noticeably during the cooling phase. This experiment demonstrates the unique information that in situ small angle neutron scattering studies of pretreatment can provide. This approach could be useful in optimizing the heating, holding and cooling stages of pretreatments to allow the exact size and nature of lignin aggregates to be controlled in order to enhance enzyme accessibility to cellulose and therefore the efficiency of biomass conversion.     

Shock Processing of Amino Acids Leading to Complex Structures—Implications to the Origin of Life

The building blocks of life, amino acids, are believed to have been synthesized in the extreme conditions that prevail in space, starting from simple molecules containing hydrogen, carbon, oxygen and nitrogen. However, the fate and role of amino acids when they are subjected to similar processes largely remain unexplored. Here we report, for the first time, that shock processed amino acids tend to form complex agglomerate structures. Such structures are formed on timescales of about 2 ms due to impact induced shock heating and subsequent cooling. This discovery suggests that the building blocks of life could have self-assembled not just on Earth but on other planetary bodies as a result of impact events. Our study also provides further experimental evidence for the ‘threads’ observed in meteorites being due to assemblages of (bio)molecules arising from impact-induced shocks.     

Validation of TPEN as a Zinc Chelator in Fluorescence Probing of Calcium in Cells with the Indicator Fura-2

Fura-2 is widely used as a fluorescent probe to monitor dynamic changes in cytosolic free calcium in cells, where Ca²⁺ can enter through several types of voltage-operated or ligand-gated channels. However, Fura-2 is also sensitive to other metal ions, such as zinc, which may be involved in ionic channels and receptors. There is interest, in particular, in studying the synapses between mossy fibers and CA3 pyramidal cells which contain both calcium and high quantities of free or loosely bound zinc. We have found, through fluorescence probing, that endogenous zinc inhibits mossy fiber calcium transients. However, since these results might be explained by an effect of the zinc chelator N,N,N’,N’-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) on the spectral properties of Fura-2, we have carried out a validation of the method through fluorescence excitation spectra of the complex Fura-2/calcium, and show that TPEN does not affect these spectra. This supports the idea that the observed calcium enhancement is related to a zinc inhibition of presynaptic calcium mechanisms, and confirms the use of the chelator TPEN as a general procedure for the biophysical study of Ca(II) in the presence of Zn(II) using Fura-2.     

Efficient Preparation of γ-Hydroxynitriles via Nitrile Enolate-Epoxide Reactions: Scope and Diastereoselectivity

The nucleophilic opening of epoxides by nitrile enolates using an efficient, convenient protocol is described. The diastereoselectivity of this reaction was explored and found to give syn:anti ratios ranging from 1.1:1.0 to 4.8:1.0.

     

A Bayesian approach to seafloor classification using multi-beam echo-sounder backscatter data

Seafloor classification using acoustic remote sensing techniques is an attractive approach due to its high-coverage capabilities and limited costs. The multi-beam echo-sounder (MBES) system provides high-resolution bathymetry and backscatter information with 100% coverage. In this paper, we present a seafloor classification method that employs the MBES backscatter data. The method uses the averaged backscatter data per beam. It, therefore, is independent on the quality of the MBES calibration. Also, its performance is insensitive to seafloor type variation along the MBES swathe and corrections for the angular dependence of the backscatter are not needed. The method accounts for the ping-to-ping variability of the backscatter intensity. It estimates both the number of seafloor types present in the survey area and the probability density function for the backscatter strength at a certain angle for each of the seafloor types. Application of the method to MBES backscatter data acquired in a well-known test area in the North Sea shows very good agreement with available ground truth. The method’s discriminatory performance for this area is demonstrated to be comparable to that of taking samples of the sediment. All seafloor types known to be present in the area are resolved for. Application of the method to the Stanton bank data set shows clearly separable areas that differ in seafloor composition.