Copper phosphide (Cu_3-xP) nanocrystals are promising materials for nanoplasmonics due to their substoichiometric composition, enabling the generation and stabilization of excess delocalized holes and leading to localized surface plasmon resonance (LSPR) absorption in the near-IR. We present three Cu-coupled redox chemistries that allow postsynthetic modulation of the delocalized hole concentrations and corresponding LSPR absorption in colloidal Cu_3-xP nanocrystals. Changes in the structural, optical, and compositional properties are evaluated by powder X-ray diffraction, electronic absorption spectroscopy, ³¹P magic-angle spinning solid-state nuclear magnetic resonance spectroscopy, and elemental analysis. The redox chemistries presented herein can be used to access nanocrystals with LSPR energies of 660-890 meV, a larger range than has been possible through synthetic tuning alone. In addition to utilizing previously reported redox chemistries used for copper chalcogenide nanocrystals, we show that the largest structural and LSPR modulation is achieved using a divalent metal halide and trioctylphosphine. Specifically, nanocrystals treated with zinc iodide and trioctylphosphine have the smallest unit-cell volume (295.2 ų) reported for P6₃cm Cu_3-xP, indicating more Cu vacancies than have been previously observed. Overall, these redox chemistries present valuable insight into controlling the optical and structural properties of Cu_3-xP.

We report a low-temperature colloidal synthesis of WSe2 nanocrystals from tungsten hexacarbonyl and diphenyl diselenide in trioctylphosphine oxide (TOPO). We identify TOPO-substituted intermediates, W(CO)5TOPO and cis-W(CO)4(TOPO)2 by infrared spectroscopy. To confirm these assignments, we synthesize aryl analogues of phosphine-oxide-substituted intermediates, W(CO)5TPPO (synthesized previously, TPPO = triphenylphosphine oxide) and cis-W(CO)4(TPPO)2 and fac-W(CO)3(TPPO)3 (new structures reported herein). Ligation of the tungsten carbonyl by either the alkyl or aryl phosphine oxides results in facile labilization of the remaining CO, enabling low-temperature decomposition to nucleate WSe2 nanocrystals. The reactivity in phosphine oxides is contrasted with syntheses containing phosphine ligands, where substitution results in decreased CO labilization and higher temperatures are required to induce nanocrystal nucleation.

We report a synthesis of WSe₂ nanocrystals in which the number of layers is controlled by varying the precursor concentration. By altering the ratios and concentrations of W(CO)₆ and Ph₂Se₂ in trioctylphosphine oxide, we show that high [Se] and large Se/W ratios lead to an increased number of layers per nanocrystal. As the number of layers per nanocrystal is increased, the nanocrystal ensembles show less phase-conversion from the metastable 2M phase to the thermodynamically favored 2H phase. Density functional theory calculations indicate that the interlayer binding energy increases with the number of layers, indicating that the stronger interlayer interactions in multilayered nanocrystals may increase the energy barrier to phase-conversion. The results presented herein provide insights for directing phase-conversion in solution-phase syntheses of transition metal dichalcogenides.

αIIbβ3 activation in platelets is followed by activation of the tyrosine kinase c-Src associated with the carboxyl terminus of the β3 cytosolic tail. Exogenous peptides designed to interact with the αIIb transmembrane (TM) domain activate single αIIbβ3 molecules in platelets by binding to the αIIb TM domain and causing separation of the αIIbβ3 TM domain heterodimer. Here we asked whether directly activating single αIIbβ3 molecules in platelets using the designed peptide anti-αIIb TM also initiates αIIbβ3-mediated outside-in signaling by causing activation of β3-associated c-Src. Anti-αIIb TM caused activation of β3-associated c-Src and the kinase Syk, but not the kinase FAK, under conditions that precluded extracellular ligand binding to αIIbβ3. c-Src and Syk are activated by trans-autophosphorylation, suggesting that activation of individual αIIbβ3 molecules can initiate αIIbβ3 clustering in the absence of ligand binding. Consistent with this possibility, incubating platelets with anti-αIIb TM resulted in the redistribution of αIIbβ3 from a homogenous ring located at the periphery of discoid platelets into nodular densities consistent with clustered αIIbβ3. Thus, these studies indicate that not only is resting αIIbβ3 poised to undergo a conformational change that exposes its ligand-binding site, but it is poised to rapidly assemble into intracellular signal-generating complexes as well.

Alloys of tungsten tetraboride (WB4) with the addition of C and Si were prepared by arc-melting of the constituent elements. The phase purity was established by powder X-ray diffraction (PXRD) and surface morphology by scanning electron microscopy (SEM) analysis. Vickers hardness measurements showed hardness enhancement for alloys with a nominal composition of (W0.98Si0.02):11.6B and (W0.95C0.05):11.6B of 52.2 ± 3.0 and 50.5 ± 2.5 GPa, respectively, compared to 41.2 ± 1.4 GPa for pure WB4. (W0.92Zr0.08):11.6B was determined in previous work to have a hardness of 55.9 ± 2.8 GPa. Bulk moduli were calculated following analysis of high-pressure radial diffraction data and were determined to be 329 ± 4 (K0′ = 2) and 390 ± 9 (K0′ = 0.6) GPa for 8 atom % Zr and 5 atom % C-doping, respectively, compared to 326-339 GPa for pure WB4. Computational analysis was used to determine the dopant positions in the crystal structure, and it was found that Zr primarily substitutes W in the 2c position, Si substitutes for the entire B3 trimers, and C inserts in the Bhex-layer. The hardness enhancement in the case of Zr-doping is attributed primarily to extrinsic hardness effects (nanograin morphology), in the case of C─to intrinsic effects (interlayer bond strengthening), and in the intermediate case of Si─to both intrinsic and extrinsic effects (bond strengthening and fine surface morphology).

Cytochrome P450c17 (P450 17A1, CYP17A1) is a critical enzyme in the synthesis of androgens and is now a target enzyme for the treatment of prostate cancer. Cytochrome P450c17 can exhibit either one or two physiological enzymatic activities differentially regulated by cytochrome b5. How this is achieved remains unknown. Here, comprehensive in silico, in vivo and in vitro analyses were undertaken. Fluorescence Resonance Energy Transfer analysis showed close interactions within living cells between cytochrome P450c17 and cytochrome b5. In silico modeling identified the sites of interaction and confirmed that E48 and E49 residues in cytochrome b5 are essential for activity. Quartz crystal microbalance studies identified specific protein-protein interactions in a lipid membrane. Voltammetric analysis revealed that the wild type cytochrome b5, but not a mutated, E48G/E49G cyt b5, altered the kinetics of electron transfer between the electrode and the P450c17. We conclude that cytochrome b5 can influence the electronic conductivity of cytochrome P450c17 via allosteric, protein-protein interactions.

The last decade has seen a sharp increase in the number of scientific publications describing physiological and pathological functions of extracellular vesicles (EVs), a collective term covering various subtypes of cell-released, membranous structures, called exosomes, microvesicles, microparticles, ectosomes, oncosomes, apoptotic bodies, and many other names. However, specific issues arise when working with these entities, whose size and amount often make them difficult to obtain as relatively pure preparations, and to characterize properly. The International Society for Extracellular Vesicles (ISEV) proposed Minimal Information for Studies of Extracellular Vesicles ("MISEV") guidelines for the field in 2014. We now update these "MISEV2014" guidelines based on evolution of the collective knowledge in the last four years. An important point to consider is that ascribing a specific function to EVs in general, or to subtypes of EVs, requires reporting of specific information beyond mere description of function in a crude, potentially contaminated, and heterogeneous preparation. For example, claims that exosomes are endowed with exquisite and specific activities remain difficult to support experimentally, given our still limited knowledge of their specific molecular machineries of biogenesis and release, as compared with other biophysically similar EVs. The MISEV2018 guidelines include tables and outlines of suggested protocols and steps to follow to document specific EV-associated functional activities. Finally, a checklist is provided with summaries of key points.