Notes

Outcomes of metastasis-directed treatments associated with bone tissue oligometastatic prostate cancer.
Ionic liquids (IL) are valuable in a variety of applications due to their high electrochemical stability and physical properties. Using the cation 1-methyl-3-octylimidazolium, [OMIM]+, the bromidostannate RTIL [OMIM][Sn+IIBr3], "undercooled melt" [OMIM][Sn+IVBr5], and IL [OMIM]2[Sn+IVBr6] were synthesized. The uncommon solid state structure of [SnBr5]- was elucidated in the form of its RTIL salt. Additionally, the IL based on tribromine-monoanion [OMIM][Br3] was used to dissolve metallic Sn, selectively resulting in the formation of [SnBr3]- as confirmed by Raman spectroscopy. Subsequent cyclic voltammograms (CV) of [SnBr3]- confirmed the deposition potential of metallic Sn and renewal of the polybromide [Br3]-. The RTIL bromidostannates were stable compounds, making a selective electrochemical investigation of the deposition of metallic Sn(0) to Sn(+II)/Sn(+IV) redox process possible, via conductance and CV measurements. The CVs of the RTILs and of solutions in propylene carbonate had the redox couples of Sn(0)/[Sn+IIBr3]-/[Sn+IVBr5]-.In studies of tobacco toxicology, including comparisons of different tobacco products and exposure to secondhand or thirdhand smoke, exposure assessment using biomarkers is often useful. Some studies have indicated that most of the toxicity of tobacco smoke is due to gas-phase compounds. 3-Ethenylpyridine (3-EP) is a major nicotine pyrolysis product occurring in the gas phase of tobacco smoke. It has been used extensively as an environmental tracer for tobacco smoke. 5-Chloro-2'-deoxyuridine nmr 3-EP would be expected to be a useful tobacco smoke biomarker as well, but nothing has been published about its metabolism and excretion in humans. In this Article we describe a solid-phase microextraction (SPME) GC-MS/MS method for determination of 3-EP in human urine and its application to the determination of 3-EP in the urine of smokers and people exposed to secondhand smoke. We conclude that 3-EP is a promising biomarker that could be useful in studies of tobacco smoke exposure and toxicology. We also point out the paucity of data on 3-EP toxicity and suggest that additional studies are needed.Hybrid devices consisting of graphene or transition metal dichalcogenides (TMDs) and semiconductor quantum dots (QDs) were widely studied for potential photodetector and photovoltaic applications, while for photodetector applications, high internal quantum efficiency (IQE) is required for photovoltaic applications and enhanced carrier diffusion length is also desirable. Here, we reported the electrical measurements on hybrid field-effect optoelectronic devices consisting of compact QD monolayer at controlled separations from single-layer graphene, and the structure is characterized by high IQE and large enhancement of minority carrier diffusion length. While the IQE ranges from 10.2% to 18.2% depending on QD-graphene separation, ds, the carrier diffusion length, LD, estimated from scanning photocurrent microscopy (SPCM) measurements, could be enhanced by a factor of 5-8 as compared to that of pristine graphene. IQE and LD could be tuned by varying back gate voltage and controlling the extent of charge separation from the proximal QD layer due to photoexcitation. The obtained IQE values were remarkably high, considering that only a single QD layer was used, and the parameters could be further enhanced in such devices significantly by stacking multiple layers of QDs. Our results could have significant implications for utilizing these hybrid devices as photodetectors and active photovoltaic materials with high efficiency.A general aminoalkylation of aryl halides was developed, overcoming intolerance of free amines in nickel-mediated C-C coupling. This transformation features broad functional group tolerance and high efficiency. Taking advantage of the fast desilylation of α-silylamines upon single-electron transfer (SET) facilitated by carbonate, α-amino radicals are generated regioselectively, which then engage in nickel-mediated C-C coupling. The reaction displays high chemoselectivity for C-C over C-N bond formation. Highly functionalized pharmacophores and peptides are also amenable.Modifying molecular conjugation has been demonstrated as an effective strategy to enhance the photovoltaic performance of the non-fullerene small molecule acceptors (SMAs), which would regulate the molecular packing and nanoscale morphology in the active layer of organic solar cells (OSCs). Here, two novel SMAs PTIC-4Cl and PT2IC-4Cl are designed and synthesized by expanding the core unit of TB-4Cl in one or two directions. The effects of how to expand the conjugation length on the absorption property, energy levels, dipole moment, and solubility are studied via theoretical calculation and experiments. Compared to PT2IC-4Cl, PTIC-4Cl with a more asymmetric structure exhibits the larger dipole moment and enhanced intermolecular packing. The PTIC-4Cl-based OSCs exhibit a favorable morphology and balanced charge transport, thereby leading to the highest power conversion efficiencies. In addition, PTIC-4Cl-based devices show outstanding thermal and air stability. These results reveal that fine-tuning the dipole moment via rationally expanding the conjugation in asymmetric A-D1A'D2-A-type non-fullerene acceptors is critical to achieve high-performance OSCs.The study of ever more complex biomolecular assemblies implicated in human health and disease is facilitated by a suite of complementary biophysical methods. Pulse dipolar electron paramagnetic resonance spectroscopy (PDS) is a powerful tool that provides highly precise geometric constraints in frozen solutions; however, the drive toward PDS at physiologically relevant sub-μM concentrations is limited by the currently achievable concentration sensitivity. Recently, PDS using a combination of nitroxide- and CuII-based spin labels allowed measuring a 500 nM concentration of a model protein. Using commercial instrumentation and spin labels, we demonstrate CuII-CuII and nitroxide-nitroxide PDS measurements at protein concentrations below previous examples reaching 500 and 100 nM, respectively. These results demonstrate the general feasibility of sub-μM PDS measurements at short to intermediate distances (∼1.5 to 3.5 nm), and are of particular relevance for applications where the achievable concentration is limiting.Both decabromodiphenyl ether (BDE 209) and decabromodiphenyl ethane (DBDPE) are still produced in large quantities in China, especially in the Shandong Province closed to the Bohai Sea (BS). This study conducted a comprehensive investigation of the distribution and budget of brominated flame retardants (BFRs) in the BS. BDE 209 was the predominant BFR in most of the investigated rivers flowing into the BS, although DBDPE exceeded BDE 209 in certain rivers as a result of the replacement of BDE 209 with DBDPE in North China. The spatial distributions of BFRs in the rivers were controlled by the proximity of the BFR manufacturing base and the extent of urbanization. BFRs' spatial distribution in the BS was influenced by a combination of land-based pollution sources, environmental parameters (e.g., suspended particulate matter, particulate organic carbon, and particulate black carbon), and hydrodynamic conditions. The spatial variation trend of BDE 209/DBDPE ratios in various environmental media provided useful information. Vertically, the BDE 209/DBDPE ratio decreased from the seawater surface layer to the sediment, indicating their differential transport in the BS. A multi-box mass balance model and analysis of BDE 209 showed that degradation was the primary sink of BFRs in seawater (∼68%) and surface sediment (∼72%) in the BS.Electrostatic interactions play crucial roles in protein function. Measuring pKa value perturbations upon complex formation or self-assembly of e.g. amyloid fibrils gives valuable information about the effect of electrostatic interactions in those processes. Site-specific pKa value determination by solution NMR spectroscopy is challenged by the high molecular weight of amyloid fibrils. Here we report a pH increase during fibril formation of α-synuclein, observed using three complementary experimental methods pH electrode measurements in water; colorimetric changes of a fluorescent indicator; and chemical shift changes for histidine residues using solution state NMR spectroscopy. A significant pH increase was detected during fibril formation in water, on average by 0.9 pH units from 5.6 to 6.5, showing that protons are taken up during fibril formation. The pH upshift was used to calculate the average change in the apparent pKaave value of the acidic residues, which was found to increase by at least 1.1 unit due to fibril formation. Metropolis Monte Carlo simulations were performed on a comparable system that also showed a proton uptake due to fibril formation. Fibril formation moreover leads to a significant change in proton binding capacitance. Parallel studies of a mutant with five charge deletions in the C-terminal tail revealed a smaller pH increase due to fibril formation, and a smaller change (0.5 units on average) in the apparent pKaave values of the acidic residues. We conclude that the proton uptake during the fibril formation is connected to the high density of acidic residues in the C-terminal tail of α-synuclein.Extracellular electrical stimulation (ES) can provide electrical potential from outside the cell membrane, but it is often ineffective due to interference from external factors such as culture medium resistance and membrane capacitance. To address this, we developed a vertical nanowire electrode array (VNEA) to directly provide intracellular electrical potential and current to cells through nanoelectrodes. Using this approach, the cell membrane resistivity and capacitance could be excluded, allowing effective ES. Human fetal neural stem cells (hfNSCs) were cultured on the VNEA for intracellular ES. Combining the structural properties of VNEA and VNEA-mediated ES, transient nanoscale perforation of the electrode was induced, promoting cell penetration and delivering current to the cell. Intracellular ES using VNEA improved the neuronal differentiation of hfNSCs more effectively than extracellular ES and facilitated electrophysiological functional maturation of hfNSCs because of the enhanced voltage-dependent ion-channel activity. The results demonstrate that VNEA with advanced nanoelectrodes serves as a highly effective culture and stimulation platform for stem-cell neurogenesis.Targeting the genetic material without destruction is a priority to develop safe anticancer drugs. Histone deacetylase 8 (HDAC8), which is proved to be involved in carcinogenesis, is an enzyme associated with the chromatin for post-translational deacetylation of acetylated lysine. In this study, HDAC8 co-crystallized with the intermediate state tetrapeptide Trapoxin A (TA) inhibitor and the holoenzyme are utilized to find their conformational ensembles. Furthermore, the co-crystallized intermediate gem-diolate TA was used to find optimum interactions with the active site residues by conventional molecular dynamics (MD) simulation and QM/MM umbrella sampling. Finally, the intermediate state of the acetyl-l-lysine substrate was explored by QM/MM steered MD and compared to the binding of the intermediate state of the inhibitor. This research showed that HDAC8 is flexible and exists in conformational ensembles in its holoenzyme state. Binding of the intermediate state TA stabilizes its conformation. The optimum binding to the active site of HDAC8 for structures of gem-diolate TA (intermediate state) and acetyl-l-lysine (intermediate state) was determined according to the corresponding energy profiles.
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