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Of the proteins determined to be differentially degraded by both acquisition methods, we find known proteins that are degraded by the ubiquitin-proteasome pathway, such as HNRNPK, EIF3A, and IF4A1/EIF4A-1, and a slower turnover for CATD, a protein implicated in invasive breast cancer. With improved quantification from DIA, we anticipate that this workflow will make SILAC-based experiments like protein turnover more sensitive.Glioma is a malignant brain tumor. There is growing evidence that its progression involves altered metabolism. This study’s objective was to understand how those metabolic perturbations were manifested in plasma and urine. Metabolic signatures in blood and urine were characterized by liquid chromatography-tandem mass spectrometry. The results were linked to gene expression using data from the Gene Expression Omnibus database. Genes and pathways associated with the disease were thus identified. Forty metabolites were identified, which were differentially expressed in the plasma of glioma patients, and 61 were identified in their urine. Twenty-two metabolites and five disturbed pathways were found both in plasma and urine. Twelve metabolites in plasma and three in urine exhibited good diagnostic potential for glioma. Transcriptomic analyses revealed specific changes in the expression of 1437 genes associated with glioma. Seventeen differentially expressed genes were found to be correlated with four of the metabolites. Enrichment analysis indicated that dysregulation of glutamatergic synapse pathway might affect the pathology of glioma. Integration of metabolomics with transcriptomics can provide both a broad picture of novel cancer signatures and preliminary information about the molecular perturbations underlying glioma. These results may suggest promising targets for developing effective therapies.Chiral phonons were initially proposed and experimentally verified in two-dimensional (2D) systems. Their intriguing effects have generated profound impacts on multiple research fields. However, all chiral phonons reported to date are constrained to be local, in the sense that their group velocities vanish identically. Here, we propose the concept of propagating 3D chiral phonons, which can transport the information on chirality and angular momentum. Guided by the necessary conditions and using first-principles calculations, we demonstrate their existence in WN2. The chirality, group velocity, and pseudoangular momentum are analyzed. Based on their selective coupling with valley electrons and photons, we propose an experimental setup to detect the unique feature of propagating chiral phonons. Our work endows chiral phonons with a crucial character-the ability to propagate and transport quantized information, which creates a new research direction and opens up the possibility to design novel phononic quantum devices.Symmetry-breaking synthetic controls allow for nanostructure geometries that are counter to the underlying crystal symmetry of a material. If suitably applied, such controls provide the means to drive an isotropic metal along a growth pathway yielding a three-dimensional chiral geometry. Herein, we present a light-driven solution-based synthesis yielding helical gold spirals from substrate-bound seeds. The devised growth mode relies on three separate symmetry-breaking events ushered in by seeds lined with planar defects, a capping agent that severely frustrates early stage growth, and the Coulombic repulsion that occurs when identically charged growth fronts collide. Together they combine to advance a growth pathway in which planar growth emanates from one side of the seed, advances to encircle the seed from both clockwise and counterclockwise directions, and then, upon collision of the two growth fronts, sees one front rise above the other to realize a self-perpetuating three-dimensional spiral structure.Phonon modes play a vital role in the cooperative phenomenon of light-induced spin transitions in spin crossover (SCO) molecular complexes. Although the cooperative vibrations, which occur over several hundreds of picoseconds to nanoseconds after photoexcitation, are understood to play a crucial role in this phase transition, they have not been precisely identified. Therefore, we have performed a novel optical laser pump-nuclear resonance probe experiment to identify the Fe-projected vibrational density of states (pDOS) during the first few nanoseconds after laser excitation of the mononuclear Fe(II) SCO complex [Fe(PM-BiA)2(NCS)2]. Evaluation of the so obtained nanosecond-resolved pDOS yields an excitation of ∼8% of the total volume of the complex from the low-spin to high-spin state. Density functional theory calculations allow simulation of the observed changes in the pDOS and thus identification of the transient inter- and intramolecular vibrational modes at nanosecond time scales.Spectral hole burning has been employed for decades to study various amorphous solids and proteins. Triplet states and respective transient holes were incorporated into theoretical models and software simulating nonphotochemical spectral hole burning (NPHB) and including all relevant distributions, in particular the distribution of the angle between the electric field of light E and transient dipole moment of the chromophore μ. The presence of a chlorophyll a triplet state with a lifetime of several milliseconds explains the slowdown of NPHB (on the depth vs illumination dose scale) with the increase of the light intensity, as well as larger hole depths observed in weak probe beam experiments, compared to those deduced from the hole growth kinetics (HGK) measurements (signal collected at a fixed wavelength while a stronger burning beam is on) in cytochrome b6f and chemically modified LH2. We also considered the solvent deuteration effects on triplet lifetime and concluded that both triplet states and local heating likely play a role in slowing down the HGK with increasing burn intensity.Understanding the formation of nanomaterials down to the atomic level is key to rational design of advanced materials. Despite their widespread use and intensive study over the years, the detailed formation mechanism of platinum (Pt) nanoparticles remains challenging to explore and rationalize. Here, various in situ characterization techniques, and in particular X-ray total scattering with pair distribution function (PDF) analysis, are used to follow the structural and chemical changes taking place during a surfactant-free synthesis of Pt nanoparticles in alkaline methanol. Polynuclear structures form at the beginning of the synthesis, and Pt-Pt pair distances are identified before any nanoparticles are generated. The structural motifs best describing the species formed change with time, e.g., from [PtCl5-PtCl5] and [PtCl6-Pt2Cl6-PtCl6] to [Pt2Cl10-Pt3Cl8-Pt2Cl10]. The formation of these polynuclear structures with Pt-Pt coordination before the formation of the nanoparticles is suggested to account for the fast nucleation observed in the synthesis.Ion selective separators with the capability of conducting lithium ion and blocking polysulfides are critical and highly desired for high-performance lithium-sulfur (Li-S) batteries. Herein, we fabricate an ion selective film of covalent organic framework (denoted as TpPa-SO3Li) onto the commercial Celgard separator. The aligned nanochannels and continuous negatively charged sites in the TpPa-SO3Li layer can effectively facilitate the lithium ion conduction and meanwhile significantly suppress the diffusion of polysulfides via the electrostatic interaction. Consequently, the TpPa-SO3Li layer exhibits excellent ion selectivity with an extremely high lithium ion transference number of 0.88. When using this novel functional layer, the Li-S batteries with a high sulfur loading of 5.4 mg cm-2 can acquire a high initial capacity of 822.9 mA h g-1 and high retention rate of 78% after 100 cycles at 0.2 C. This work provides new insights into developing high-performance Li-S batteries via ion selective separator strategy.Ion pair receptors based on meso-octamethylcalix[4]pyrrole (CP) have been extensively investigated over recent years. However, the nature of their ion pair recognition has barely been reported, even for CP itself. Herein, cesium chloride was used as a guest ion pair to investigate the dynamic process of ion pair recognition by CP, and the “capture-bind” mechanism for this process is proposed for the first time. The results reveal that Cs+ can be first captured by Cl- at long distances, and then it is bound to the cavity through almost equal contributions of Cl- and CP. Smad inhibitor Although the effective charge of Cl- is obviously reduced by charge-transfer, the electrostatic interactions between Cl- and Cs+ are still strong even at long distances in the presence of CP.Herein, we present for the first time a general methodology for obtaining arbitrary-order nuclear coordinate derivatives of electronic energies derived from quantum chemistry methods. By leveraging modern advances in automatic differentiation software, we demonstrate that exact derivatives can be obtained for any method. This innovation completely bypasses the issues associated with the computational stability of applying numerical differentiation methods and dispenses the need to derive challenging formulae for analytic energy derivatives. We describe a freely available and open-source software implementation of our scheme and demonstrate its use in obtaining exact nuclear derivatives of energies from Hartree-Fock theory, second-order Møller-Plesset perturbation theory (MP2), and coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. Our sample computations include up to sextic derivatives and span a variety of test systems with up to 100 basis functions, confirming the viability of this scheme for a wide range of applications. Many of the results obtained have hitherto been unobtainable by exact means due to a lack of higher-order derivative formulae. The details of our implementation and possible further developments are discussed.We examined the uptake of Tl(I) by two hexagonal birnessites and related phase transformations in laboratory experiments over 12 sequential additions of 0.01 M Tl(I)/Mn at pH 4.0, 6.0, and 8.0. The Tl-reacted Mn oxides were characterized for their structure, Tl binding, and morphology using X-ray diffraction, X-ray photoelectron and X-ray absorption spectroscopies, and transmission electron microscopy. Very limited Tl oxidation was observed in contrast to previous works, where equal Tl(I)/Mn was added in a single step. Instead, both birnessites transformed into a 2 × 2 tunneled phase with dehydrated Tl(I) in its tunnels at pH 4, but only partially at pH 6, and at pH 8.0 they remained layered. The first four to nine sequential Tl(I)/Mn additions resulted in lower residual dissolved Tl+ concentrations than when the same amounts of Tl(I)/Mn were added in single steps. This study thus shows that the repeated reaction of hexagonal birnessites with smaller Tl(I)/Mn at ambient temperature triggers a complete phase conversion with Tl(I) as the sole reacting cation. The novel pathway found may be more relevant for contaminated environments and may help explain the formation of minerals like thalliomelane [Tl+(Mn7.54+Cu0.52+)O16]; it also points to the possibility that other reducing species trigger similar Mn oxide transformation reactions.