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Unveiling the Local Structure of Palladium Loaded into Imine‐Linked Layered Covalent Organic Frameworks for Cross‐Coupling Catalysis
No full textLayered covalent organic frameworks (2D‐COFs), composed of reversible imine linkages and accessible pores, offer versatility for chemical modifications towards the development of catalytic materials. Nitrogen‐enriched COFs are good candidates for binding Pd species. Understanding the local structure of reacting Pd sites bonded to the COF pores is key to rationalize interactions between active sites and porous surfaces. By combining advanced synchrotron characterization methods with periodic computational DFT modeling, the precise atomic structure of catalytic Pd sites attached to local defects is resolved within an archetypical imine‐linked 2D‐COF. This material was synthesized using an in situ method as a gel, under which imine hydrolysis and metalation reactions are coupled. Local defects formed in situ within imine‐linked 2D‐COF materials are highly reactive towards Pd metalation, resulting in active materials for Suzuki–Miyaura cross‐coupling reactions
Monitoring Nanocrystal Self-Assembly in Real Time Using In Situ Small-Angle X-Ray Scattering
No full textSelf‐assembled nanocrystal superlattices have attracted large scientific attention due to their potential technological applications. However, the nucleation and growth mechanisms of superlattice assemblies remain largely unresolved due to experimental difficulties to monitor intermediate states. Here, the self‐assembly of colloidal PbS nanocrystals is studied in real time by a combination of controlled solvent evaporation from the bulk solution and in situ small‐angle X‐ray scattering (SAXS) in transmission geometry. For the first time for the investigated system a hexagonal closed‐packed (hcp) superlattice formed in a solvent vapor saturated atmosphere is observed during slow solvent evaporation from a colloidal suspension. The highly ordered hcp superlattice is followed by a transition into the final body‐centered cubic superlattice upon complete drying. Additionally, X‐ray cross‐correlation analysis of Bragg reflections is applied to access information on precursor structures in the assembly process, which is not evident from conventional SAXS analysis. The detailed evolution of the crystal structure with time provides key results for understanding the assembly mechanism and the role of ligand–solvent interactions, which is important both for fundamental research and for fabrication of superlattices with desired properties
The E. coli HicB Antitoxin Contains a Structurally Stable Helix-Turn-Helix DNA Binding Domain
No full textThe E. coli hicAB type II toxin-antitoxin locus is unusual by being controlled by two promoters and by having the toxin encoded upstream of the antitoxin. HicA toxins contain a double-stranded RNA-binding fold and cleaves both mRNA and tmRNA in vivo, while HicB antitoxins contain a partial RNase H fold and either a helix-turn-helix (HTH) or ribbon-helix-helix domain. It is not known how an HTH DNA-binding domain affects higher-order structure for the HicAB modules. Here, we present crystal structures of the isolated E. coli HicB antitoxin and full-length HicAB complex showing that HicB forms a stable DNA-binding module and interacts in a canonical way with HicA despite the presence of an HTH-type DNA-binding domain. No major structural rearrangements take place upon binding of the toxin. Both structures expose well-ordered DNA-binding motifs allowing a model for DNA binding by the antitoxin to be generated
Zn-Al LDH growth on AA2024 and zinc and their intercalation with chloride: Comparison of crystal structure and kinetics
No full textThe dissimilarities and features of the crystal structure of ZnAl LDH-NO3 conversion layers grown directly on pure zinc and aluminum alloy 2024 were investigated in the present paper. Although the nature of the cations in the double hydroxides are the same in both cases (Al3+ and Zn2+), their sources differ according to the substrate. This leads to a difference in the cationic layers and interlayer structure, which consequently influences the anionic exchange reaction. In the frame of this work, the kinetics of the anion-exchange of nitrate by chloride was investigated as well as the crystal structure of the resulting ZnAl LDH-Cl on both substrates. Synchrotron high-resolution X-ray diffraction was the main method to obtain structural information and was supported by additional calculations and scanning electron microscopy.The current study revealed noticeable changes on the positioning of the interlayer atoms for the ZnAl-LDH-Cl on zinc in comparison with the ones on AA2024 substrate
Boron Phosphorus Nitride at Extremes: PN Octahedra in the High-Pressure Polymorph β-BPN
No full textThe high‐pressure behavior of non‐metal nitrides is of special interest for inorganic and theoretical chemistry as well as materials science, as these compounds feature intriguing elastic properties. The double nitride α‐BPN was investigated by in situ single‐crystal X‐ray diffraction (XRD) upon cold compression to a maximum pressure of about 42 GPa, and its isothermal bulk modulus at ambient conditions was determined to be 146(6) GPa. At maximum pressure the sample was laser‐heated, which resulted in the formation of an unprecedented high‐pressure polymorph, β‐BPN. Its structure was elucidated by single‐crystal XRD, and can be described as a decoration of a distorted hexagonal close packing of N with B in tetrahedral and P in octahedral voids. Hence, β‐BPN is the first nitride to contain PN6 octahedra, representing the much sought‐after proof of principle for sixfold N‐coordinated P that has been predicted for numerous high‐pressure phases of nitrides
Thin Films of Thermally Stable Ordered Mesoporous for Visible-Light Photocatalysis and Humidity Sensing
No full textThe preparation of highly ordered mesoporous thin films of rhodium sesquioxide (Rh2O3) on silicon and quartz glass substrates by dip-coating via solution-based block copolymer self-assembly is reported. Hydrated rhodium chloride is shown to be an effective precursor for sol−gel processing of Rh2O3. Heating in air to 600 °C crystallizes single-phase Rh2O3(I) while fully preserving the cubic symmetry 3D pore-solid architecture, whereas at 750 °C only the in-plane pore order is retained. Interestingly, there is no crystalline−crystalline transformation upon heating to 1000 °C, despite distinct microstructure coarsening. The thermal stability of the sol−gel-derived material in terms of mesostructure retention can be significantly enhanced by atomic layer deposition surface treatment, making the block copolymer-templated thin films interesting for demanding applications. Furthermore, the results of preliminary humidity sensing and photochemical activity measurements indicate that the nanocrystalline Rh2O3(I) shows promising properties as a sensor material and a visible-light photocatalyst
Determination of the Surface Facets of Gold Nanorods in Wet‐Coated Thin Films with Grazing‐Incidence Wide Angle X‐Ray Scattering
No full textThis work studies the surface facets of gold nanorods (AuNRs) in wet‐coated nanoparticle thin films with synchrotron‐light‐based grazing‐incidence wide angle X‐ray scattering (GIWAXS), which provides statistically relevant results on many nanoparticles. Air‐brush spraying deposits the monodisperse AuNRs into sparse monolayers where the long axis of rods is parallel to the substrate surface. It is found that the crystalline facets of individual AuNRs in the sparse monolayer are all in the same orientation, as indicated by narrow azimuthal widths of (200) reflections, over a macroscopic scale comparable to the substrate. This alignment is probably due to the rods' sitting on high‐index surface facets such as (520) and (250). A quantitative analysis of the angles between bulk facets and the surface facets leads to a “nested‐octagon” model for the cross sections of AuNRs: shell octagon with high‐index crystalline facets (520), (5‐20), (2‐50), (‐2‐50), (‐5‐20), (‐520), (‐250), and (250), and core octagon consisting of low‐index crystalline facets (100), (1‐10), (0‐10), (‐1‐10), (‐100), (‐110), (010), and (110
Investigations of albumin-insulin detemir complexes using molecular dynamics simulations and free energy calculations
No full textInsulin detemir is a lipidated insulin analogue that obtains a half-life extension by oligomerization and reversible binding to human serum albumin. In the present study, the complex between a detemir hexamer and albumin is investigated by an integrative approach combining molecular dynamics (MD) simulations, molecular mechanics Poisson–Boltzmann surface area (MM-PBSA) free energy calculations, and dynamic light scattering (DLS) experiments. Recent reported small-angle X-ray scattering data could not unambiguously resolve the exact binding site of detemir on albumin. We therefore applied MD simulations to deduce the binding site and key protein–protein interactions. MD simulations were started from initial complex structures based on the SAXS models, and free energies of binding were estimated from the simulations by using the MM-PBSA approach for the different binding positions. The results suggest that the overlapping FA3–FA4 binding site (named FA4) is the most favorable site with a calculated free energy of binding of −28 ± 6 kcal/mol and a good fit to the reported SAXS data throughout the simulations. Multiple salt bridges, hydrogen bonds, and favorable van der Waals interactions are observed in the binding interface that promote complexation. The binding to FA4 is further supported by DLS competition experiments with the prototypical FA4 ligand, ibuprofen, showing displacement of detemir by ibuprofen. This study provides information on albumin–detemir binding on a molecular level, which could be utilized in a rational design of future lipidated albumin-binding peptides
Comparative study of the influence of pulsed and continuous wave laser heating on the mobilization of carbon and its chemical reaction with iron in a diamond anvil cell
No full textLaser heating in a diamond anvil cell (DAC) is a common method for studying material behavior at high-pressure and high-temperature conditions. It has been previously proven that during continuous wave (CW) laser heating of a sample, carbon of the diamond anvils is mobilized, and its diffusion into the sample can lead to undesirable chemical reactions, which, if not detected, may cause misinterpretations of the results of the experiment. Minimizing the heating time with the use of a pulsed laser (PL) is thought to reduce the risk of possible carbon contamination of the sample; however, this has not been proven experimentally. Here, we report the results of our comparative study of the effect of pulsed and continuous wave (CW) laser heating on the mobilization of carbon and its chemical interaction with iron in a diamond anvil cell. Using X-ray absorption near edge structure spectroscopy, Synchrotron Mössbauer Source spectroscopy, and Synchrotron X-ray diffraction, we examined iron samples that were laser heated in DACs in various pressure transmitting media (neon, argon, and potassium chloride). According to our results, the use of the PL heating does not prevent the sample from carbon contamination. A reaction between carbon and iron happens within a few seconds even at moderate temperatures. We found that one analytical technique was generally insufficient to fully characterize the phase composition of the laser-heated samples
Search for light pseudoscalar boson pairs produced from decays of the 125 GeV Higgs boson in final states with two muons and two nearby tracks in pp collisions at 13 TeV
No full textA search is presented for pairs of light pseudoscalar bosons, in the mass range from 4 to 15 GeV, produced from decays of the 125 GeV Higgs boson. The decay modes considered are final states that arise when one of the pseudoscalars decays to a pair of tau leptons, and the other one either into a pair of tau leptons or muons. The search is based on proton-proton collisions collected by the CMS experiment in 2016 at a center-of-mass energy of 13 TeV that correspond to an integrated luminosity of 35.9 fb−1 . The 2μ2τ and 4 τ channels are used in combination to constrain the product of the Higgs boson production cross section and the branching fraction into 4 τ final state, σB , exploiting the linear dependence of the fermionic coupling strength of pseudoscalar bosons on the fermion mass. No significant excess is observed beyond the expectation from the standard model. The observed and expected upper limits at 95% confidence level on σB , relative to the standard model Higgs boson production cross section, are set respectively between 0.022 and 0.23 and between 0.027 and 0.19 in the mass range probed by the analysis