Lauritsenzimmermann4130

A novel radiolabelling method exploiting 11C-dithiocarbamate ligands has been used to generate 11C-labelled Au(I), Au(III), Pd(II) and Pt(II) complexes in high radiochemical yields (71-99%). Labelled complexes were prepared in a rapid one-pot procedure via the substitution reaction of 11C-dithiocarbamate ligands with appropriate transition metal chloride precursors.Fibrous networks play an essential role in the structure and properties of a variety of biological and engineered materials, such as cytoskeletons, protein filament-based hydrogels, and entangled or crosslinked polymer chains. Therefore, insight into the structural features of these fibrous networks and their constituent filaments is critical for discovering the structure-property-function relationships of these material systems. In this paper, a fibrous network-deep learning system (FN-DLS) is established to extract fibrous network structure information from atomic force microscopy images. FN-DLS accurately assesses the structural and mechanical characteristics of fibrous networks, such as contour length, number of nodes, persistence length, mesh size and fractal dimension. As an open-source system, FN-DLS is expected to serve a vast community of scientists working on very diverse disciplines and pave the way for new approaches on the study of biological and synthetic polymer and filament networks found in current applied and fundamental sciences.Supramolecular stabilization of polyiodides and iodine-dense phases is of high interest this study explores the possibilities offered in this sense by diprotonated cyclen, affording two novel crystal structures. One of them contains at least one peculiar I⋯I interatomic distance (3.305(1) Å), falling well below the region commonly described by secondary bonding (3.4-3.7 Å) and essentially equal to the accepted limit for covalent bonding (3.30 Å) in other words, according to threshold distance values, we are relatively free to regard this interaction either as a bond or as contact. Lest the flip of a coin decides if we should or should not draw a bond in a polyiodide, statistical insights based on CSD surveys were used to put in perspective literature material and work out a meaningful assignment (as I82-). In doing so, we address how currently accepted threshold distance values came to be in the first place, their significance, soundness, and shortcomings in describing I82- and its formal fragments (I2, I3-, I5-). Discussion of the chemical meaning of the line representing bonding in I-I fragments in similar fringe cases, relating CSD data herein presented with the previous literature, is provided. Available information coincides quite well in supporting the necessity of a revision of broadly accepted threshold distance values.Selective radical addition to terminal alkynes is always a difficult task to achieve because it gives a mixture of stereo- and regioisomers. Herein we describe the selective addition of aliphatic thiols or alcohols to N-phenylpropiolamides (terminal alkynes) using lithium tert-butoxide (tBuOLi) in ethanol as a promoter. Mechanistically, it has been shown that the reaction proceeded through the generation of a thiyl radical intermediate, and the amide group in N-phenylpropiolamide could help in the activation of the alkyne, which led to thioacetalization via the formation of a (Z)-selective anti-Markovnikov vinyl sulfide. The (Z)-selectivity during the formation of vinyl sulfides was controlled by an intramolecular sulfur⋯oxygen interaction.We present a theoretical study of vibrationally resolved photoelectron angular distributions for ammonia in both laboratory and molecular frames, in the photon energy range up to 70 eV, where only valence and inner-valence ionization is possible. We focus on the band resulting from ionization of the 3a1 HOMO orbital leading to NH3+ in the electronic ground state, , for which the dominant vibrational progression corresponds to the activation of the umbrella inversion mode. We show that, at room temperature, the photoelectron angular distributions for randomly oriented molecules or molecules whose principal C3 symmetry axis is aligned along the light polarization direction are perfectly symmetric with respect to the plane that contains the intermediate D3h conformation connecting the pyramidal structures associated with the double-well potential of the umbrella inversion mode. These distributions exhibit symmetric, nearly perfect two-lobe shapes in the whole range of investigated photon energies. In contrast, fa and likely in other molecules containing a similar double-well potential, one could preferably work at ultracold temperatures, which is not the case for most molecules.The synthesis of new types of mono- and polynuclear ruthenium nitrosyl complexes is driving progress in the field of NO generation for a variety of applications. Light-induced Ru-NO bond dissociation in solution may involve transient linkage isomers MS1 (Ru-ON) and MS2 (Ru-η2-NO), which can be detected spectroscopically and analyzed computationally. The investigation of photoisomerization processes in the solid state may be useful for potential application of such complexes for data storage, photochromic or photomagnetic materials or even non-linear optics. Herein we describe the major developments in the synthesis of ruthenium nitrosyl complexes, their photoinduced linkage isomerization (PLI) processes, their NO release both in the solid state and in solution, and their application as potential anticancer drugs. Illustrative examples of such innovations made mainly in the last decade are provided.Anodic aluminium oxide (AAO) membranes with self-ordered nanochannels have become promising candidates for applications in the aspects such as structural coloration, photonic crystals, upconversion luminescence and nanofluidic transport. Also, self-ordered AAO membranes have been extensively used for the fabrication of functional nanostructures such as nanowires, nanotubes, nanoparticles, nanorods and nanopillars. Geometries of nanochannels are crucial for the applications of AAO membranes as well as controlling growth (e.g., nucleation, direction and morphology) and in applications (e.g., optics, magnetics, thermoelectrics, biology, medicine, sensing, and energy conversion and storage) of the functional nanostructures fabricated via AAO template-based methods. However, observation of whole nanochannels with nanometer-resolution in thick AAO membranes remains a fundamental challenge, and the nanochannel geometry has not yet been sufficiently elucidated. Here, for the first time, we use depth-profiling transmission electron microscopy to reveal the truncated conical geometry of whole nanochannels of 70 μm in length. Such shape nonuniformity of the nanochannels leads to different reflectance properties of the different depths of the nanochannels along their long axis for one AAO membrane, which suggests that the nonuniformity result in some effects on applications of the nanostructures. Furthermore, we introduce a shape factor to evaluate the shape nonuniformity and demonstrate that the nonuniformity can be remarkably removed by an effective etching method based on a temperature gradient regime.The observation of ready deprotonation of the phenylogous enol of benzodifurantrione (BDT) to give a bright violet conjugate base has led to two follow up explorations. Extension of BDT enol by insertion of a p-phenylene unit into the enol C-O bond gives the known bright red 4-hydroxylated benzodifuranone dyes. Their deprotonation results in previously unreported near infrared-absorbing conjugate bases. These appear to aggregate in solution, the more so in less polar solvents. Ring-opened derivatives of BDT containing α-dicarbonyl substituents also give coloured conjugate bases, but α-keto-ester and -anilide derivatives differ substantially (ester yellow; anilide intense red). Investigation of this nonintuitive difference leads to the conclusion that while the anilide is essentially planar the ester is nonplanar. The contrast in conformation impacts on the auxochromic effects of the otherwise closely related α-dicarbonyl substituents and thus the variation in colour. Selleck AZD4547 The latter observation has potential across colour chemistry in general. In contrast to the readily observed BDT enol, no evidence has been adduced for enol tautomers amongst the ring-opened analogues.Mixed mercury(II) halogenides have been known for a long time as good NLO (non-linear optic) materials. The NLO properties are due to the halogen disposition in the solid state and the electron distribution among the bonds formed by soft elements. We investigated the possibility of using HgBrI as a asymmetric tecton in the preparation of noncentrosymmetric crystalline compounds, by exploiting the coordinating power of Hg(II) toward N-donor ligands, and seven coordination complexes have been obtained. To unravel the nature of these complex systems we combined the data from different techniques Raman spectroscopy, SC-XRD and Second Harmonic Generation, supported by a periodic DFT computational approach. In HgBrI crystalline products with low symmetry, the presence of substitutional disorder leads to a lack of the inversion center conferring NLO activity, which is absent in analogous complexes of Hg(II) halogenides. These results indicate HgBrI as an interesting tecton to obtain metallorganic NLO materials.Secreted proteins are critical for the coordination of potent immune defenses, such as in engineered T cell therapies, however, there are few widely accessible approaches to accurately analyze and sort large numbers of cells based on their secretory functions. We report a workflow for the rapid screening and sorting of single individual T cells based on IL-2 secretion accumulated at high concentrations in nanoliter droplets and encoded back onto the secreting cell's surface. In our method, droplets are used solely to partition cells, enabling rapid accumulation of signals onto cell surfaces, and eliminating diffusive crosstalk between neighbors. All downstream sorting leverages conventional high-throughput and readily accessible flow cytometry after the emulsion is disrupted. We achieve monodisperse droplet generation (CV less then 10%) at flow rates up to 200 μL min-1 using step emulsification, enabling processing of entire libraries of cells within tens of minutes without significant secretion crosstalk. In comparison to our approach, strong mitogenic activation overwhelmed the conventional bulk on-cell cytokine assay, rendering labeled, non-activated cells indistinguishable from actively secreting neighbors within one hour. Processing of identical cell mixtures following droplet encapsulation yielded no apparent crosstalk even after three hours. Instead, IL-2 production spanning several orders of magnitude was observed from roughly 20% of analyzed activated lymphocytes, representing an at least 10-fold increase in dynamic range compared to unencapsulated cells. Secreting cells could also be sorted using fluorescence activated cell sorting (FACS). The approach can ultimately enable sorting of cells based on functional properties with higher accuracy in a more accessible format to life science researchers.