Rybergskov1408

ConspectusMetal nanoparticles have been utilized for a vast amount of plasmon enhanced spectroscopies and energy conversion devices. Their unique optical properties allow them to be used across the UV-vis-NIR spectrum tuned by their size, shape, and material. In addition to utility in enhanced spectroscopy and energy/charge transfer, the plasmon resonance of metal nanoparticles is sensitive to its surrounding environment in several ways. The local refractive index determines the resonance wavelength, but plasmon damping, as indicated by the homogeneous line width, also depends on the surface properties of the metal nanoparticles. Plasmon oscillations can decay through interband, intraband, radiation, and surface damping. While the first three damping mechanisms can be modeled based on bulk dielectric data using electromagnetic simulations, surface damping does not depend on the material properties of the nanoparticle alone but rather on the interface composition between the nanoparticle and its surrounding enise from an enhanced absorption, although charge transfer cannot be ruled out. From this body of research, we conclude that chemical interface damping is a major component of the total damping rate of the plasmon resonance and critically depends on the chemical interface of the metallic nanoparticles. Plasmon damping occurs through distinct mechanisms that are important to differentiate when considering the purpose of the plasmonic nanoparticle enhanced spectroscopy, energy conversion, or catalysis. It must also be noted that many of the mechanisms are currently indifferentiable, and thus, new single-particle spectroscopic methods are needed to further characterize the mechanisms underlying chemical interface damping.Since the advent of the first computers, chemists have been at the forefront of using computers to understand and solve complex chemical problems. As the hardware and software have evolved, so have the theoretical and computational chemistry methods and algorithms. Raphin1 manufacturer Parallel computers clearly changed the common computing paradigm in the late 1970s and 80s, and the field has again seen a paradigm shift with the advent of graphical processing units. This review explores the challenges and some of the solutions in transforming software from the terascale to the petascale and now to the upcoming exascale computers. While discussing the field in general, NWChem and its redesign, NWChemEx, will be highlighted as one of the early codesign projects to take advantage of massively parallel computers and emerging software standards to enable large scientific challenges to be tackled.The AMnO2 delafossites (A = Na, Cu) are model frustrated antiferromagnets, with triangular layers of Mn3+ spins. At low temperatures (TN = 65 K), a C2/m → P1̅ transition is found in CuMnO2, which breaks frustration and establishes magnetic order. In contrast to this clean transition, A = Na only shows short-range distortions at TN. Here, we report a systematic crystallographic, spectroscopic, and theoretical investigation of CuMnO2. We show that, even in stoichiometric samples, nonzero anisotropic Cu displacements coexist with magnetic order. Using X-ray/neutron diffraction and Raman scattering, we show that high pressures act to decouple these degrees of freedom. This manifests as an isostuctural phase transition at ∼10 GPa, with a reversible collapse of the c-axis. This is shown to be the high-pressure analogue of the c-axis negative thermal expansion seen at ambient pressure. Density functional theory (DFT) simulations confirm that dynamical instabilities of the Cu+ cations and edge-shared MnO6 layers are intertwined at ambient pressure. However, high pressure selectively activates the former, before an eventual predicted reemergence of magnetism at the highest pressures. Our results show that the lattice dynamics and local structure of CuMnO2 are quantitatively different from nonmagnetic Cu delafossites and raise questions about the role of intrinsic inhomogeneity in frustrated antiferromagnets.The monitoring of circulating tumor cells (CTCs) has recently served as a promising approach for assessing prognosis and evaluating cancer treatment. We have already developed a CTCs enrichment platform by EpCAM recognition peptide-functionalized magnetic nanoparticles (EP@MNPs). However, considering heterogeneous CTCs generated through epithelial-mesenchymal transition (EMT), mesenchymal CTCs would be missed with this method. Notably, N-cadherin, overexpressed on mesenchymal CTCs, can facilitate the migration of cancer cells. Hence, we screened a novel peptide targeting N-cadherin, NP, and developed a new CTCs isolation approach via NP@MNPs to complement EpCAM methods' deficiencies. NP@MNPs had a high capture efficiency (about 85%) of mesenchymal CTCs from spiked human blood. Subsequently, CTCs were captured and sequenced at the single-cell level via NP@MNPs and EP@MNPs, RNA profiles of which showed that epithelial and mesenchymal subgroups could be distinguished. Here, a novel CTCs isolation platform laid the foundation for mesenchymal CTCs isolation and subsequent molecular analysis.Nitrogen oxides (NOX) and methane impact air quality through the promotion of ozone formation, and methane is also a strong greenhouse gas. Despite the importance of these pollutants, emissions in urban areas are poorly quantified. We present measurements of NOX, CH4, CO, and CO2 made at Drexel University in Philadelphia along with NOX and CO observations at two roadside monitors. Because CO2 concentrations in the winter result almost entirely from combustion with negligible influence from photosynthesis and respiration, we are able to infer fleet-averaged fuel-based emission factors (EFs) for NOX and CO, similar in some ways to how EFs are determined from tunnel studies. Comparison of the inferred NOX and CO fuel-based EF to the National Emissions Inventory (NEI) suggests errors in NEI emissions of either NOX, CO, or both. From the measurements of CH4 and CO2, which are not emitted by the same sources, we infer the ratio of CH4 emissions (from leaks in the natural gas infrastructure) to CO2 emissions (from fossil fuel combustion) in Philadelphia. Comparison of the CH4/CO2 emission ratios to emission inventories from the Environmental Protection Agency suggests underestimates in CH4 emissions by almost a factor of 4. These results demonstrate the need for the addition of long-term observations of CH4 and CO2 to existing monitoring networks in urban areas to better constrain emissions and complement existing measurements of NOX and CO.Oligomerization of aggregation-prone intrinsically disordered proteins (IDPs), such as α-synuclein, amyloid β, and tau, has been shown to be associated with the pathogenesis of several neurodegenerative diseases, including Parkinson's and Alzheimer's disease. The proteasome is charged with regulating cellular levels of IDPs, but this degradation pathway can become dysregulated leading to their accumulation and subsequent aggregation. Although the pathogenesis of these neurodegenerative diseases is still under intense investigation, it has been shown that the oligomeric forms of IDPs, including α-synuclein and amyloid β, can impair proteasome function. This leads to additional accumulation of the IDPs, further promoting disease progression. Herein, we report the use of small molecule activators of the 20S subcomplex of the proteasome to restore impaired 20S proteasome activity and prevent IDP accumulation and oligomerization. We found that fluspirilene and its new synthetic analog (16) show strong 20S proteasome enhancement (doubling 20S proteolytic activity at ∼2 μM, with maximum fold enhancement of ∼1000%), overcome impaired proteasome function, and prevent the accumulation of pathogenic IDPs. These findings provide support for the use of 20S enhancers as a possible therapeutic strategy to combat neurodegenerative diseases.Ever since the first β-lactam antibiotic, penicillin, was introduced into the clinic over 70 years ago, resistance has been observed because of the presence of β-lactamase enzymes, which hydrolyze the β-lactam ring of β-lactam antibiotics. Early β-lactamase enzymes were all of the serine β-lactamase (SBL) type, but more recently, highly resistant Gram-negative strains have emerged in which metallo-β-lactamase (MBL) enzymes are responsible for resistance. The two types of β-lactamase enzymes are structurally and mechanistically different but serve the same purpose in bacteria. The SBLs use an active serine group as a nucleophile to attack the β-lactamase ring, forming a covalent intermediate that is subsequently hydrolyzed. In contrast, the MBLs use a zinc ion to activate the β-lactam toward nucleophilic attack by a hydroxide anion held between two zinc ions. In this Account, we review our recent contribution to the field of β-lactamase inhibitor design in terms of both SBL and MBL inhibitors. We describe how would not be the case, and in practice the compound is remarkably stable. Both examples serve to illustrate the importance of scientific insight and the necessity to explore speculative hypotheses as part of the creative medicinal chemistry process.Electrochromic (EC) materials and devices provide a user-controlled, dynamic way of displaying information using low power, making them interesting for a range of applications in numerous markets, including logistics, retail, consumer goods, and health care. To optimize the cost while simplifying the production, expanding the color space, and enhancing the contrast and vibrancy of EC displays aimed for cost-sensitive products, we sought to reduce the number of layers as well as remove the underlying conducting layer that accounts for a substantial fraction of the cost of a printed label. Here, we show how conjugated electrochromic polymers, which are inherently semiconducting, can be used to accomplish this goal and afford printable EC displays with a flexible form factor. Using a combination of electrochemical probes, in situ spectroscopy, solid-state conductivity, and in situ conductance measurements, we have studied and compared five different EC polymers with conductivities spanning multiple orders of magnitude and colors that span most of the visible range, identifying polymers and properties that allow for switching from the colored to the clear state without an underlying conducting layer. Finally, we incorporate these EC polymers into optimized flexible devices without an underlying conductor and demonstrate that they are able to provide on-demand, reversible colored-to-clear switching on the order of seconds to minutes, with operating voltages below ±1 V, optical memories exceeding 60 min, and a shelf-life exceeding 12 months.Flow cytometry is a powerful tool with applications in diverse fields such as microbiology, immunology, virology, cancer biology, stem cell biology, and metabolic engineering. It rapidly counts and characterizes large heterogeneous populations of cells in suspension (e.g., blood cells, stem cells, cancer cells, and microorganisms) and dissociated solid tissues (e.g., lymph nodes, spleen, and solid tumors) with typical throughputs of 1,000-100,000 events per second (eps). By measuring cell size, cell granularity, and the expression of cell surface and intracellular molecules, it provides systematic insights into biological processes. Flow cytometers may also include cell sorting capabilities to enable subsequent additional analysis of the sorted sample (e.g., electron microscopy and DNA/RNA sequencing), cloning, and directed evolution. Unfortunately, traditional flow cytometry has several critical limitations as it mainly relies on fluorescent labeling for cellular phenotyping, which is an indirect measure of intracellular molecules and surface antigens.