Christie Borch (spykey45)

A neutral Ac(H2O)6 (1)(O2CMe)3 (1) compound was the major species in solution for the large Ac3+. In contrast, smaller Cm3+ preferred forming an anion. There were approximately four bound O2CMe1- ligands and one to two inner sphere H2O ligands. The conclusion that increasing acetic acid/acetate concentrations increased acetate complexation was corroborated by characterizing (NH4)2M(O2CMe)5 (M = Eu3+, Am3+ and Cm3+) using single crystal X-ray diffraction and optical spectroscopy (absorption, emission, excitation, and excited state lifetime measurements).We explore how to encode more than a qubit in vanadyl porphyrin molecules hosting a S = 1/2 electronic spin coupled to a I = 7/2 nuclear spin. The spin Hamiltonian and its parameters, as well as the spin dynamics, have been determined via a combination of electron paramagnetic resonance, heat capacity, magnetization and on-chip magnetic spectroscopy experiments performed on single crystals. We find low temperature spin coherence times of micro-seconds and spin relaxation times longer than a second. For sufficiently strong magnetic fields (B > 0.1 T, corresponding to resonance frequencies of 9-10 GHz) these properties make vanadyl porphyrin molecules suitable qubit realizations. The presence of multiple equispaced nuclear spin levels then merely provides 8 alternatives to define the '1' and '0' basis states. For lower magnetic fields (B less then 0.1 T), and lower frequencies ( less then 2 GHz), we find spectroscopic signatures of a sizeable electronuclear entanglement. This effect generates a larger set of allowed transitions between different electronuclear spin states and removes their degeneracies. Under these conditions, we show that each molecule fulfills the conditions to act as a universal 4-qubit processor or, equivalently, as a d = 16 qudit. These findings widen the catalogue of chemically designed systems able to implement non-trivial quantum functionalities, such as quantum simulations and, especially, quantum error correction at the molecular level.o-Carboryne (1,2-dehydro-o-carborane) is a very useful synthon for the synthesis of a variety of carborane-functionalized molecules. With 1-Li-2-OTf-o-C2B10H10 as the precursor, o-carboryne undergoes an efficient [4 + 2] cycloaddition with various conjugated enynes, followed by a subsequent [2 + 2] cycloaddition at room temperature, generating a series of carborane-fused tricyclo[6.4.0.02,7]dodeca-2,12-dienes in moderate to high isolated yields. This reaction is compatible with many functional groups and has a broad substrate scope. A reactive carborane-fused 1,2-cyclohexadiene intermediate is involved, which is supported by experimental results and DFT calculations. This protocol offers a convenient strategy for the construction of complex carborane-functionalized tricyclics.The tau protein is a highly soluble and natively unfolded protein. Under pathological conditions, tau undergoes multiple post-translational modifications (PTMs) and conformational changes to form insoluble filaments, which are the proteinaceous signatures of tauopathies. To dissect the crosstalk among tau PTMs during the aggregation process, we phosphorylated and ubiquitylated recombinant tau in vitro using GSK3β and CHIP, respectively. The resulting phospho-ub-tau contained conventional polyubiquitin chains with lysine 48 linkages, sufficient for proteasomal degradation, whereas unphosphorylated ub-tau species retained only one-three ubiquitin moieties. Mass-spectrometric analysis of in vitro reconstituted phospho-ub-tau revealed seven additional ubiquitylation sites, some of which are known to stabilize tau protofilament stacking in the human brain with tauopathy. When the ubiquitylation reaction was prolonged, phospho-ub-tau transformed into insoluble hyperubiquitylated tau species featuring fibrillar morphology and in vitro seeding activity. We developed a small-molecule inhibitor of CHIP through biophysical screening; this effectively suppre