The First Photochemical In Situ Production of Ti‐Based Nanoparticles: A SH2 Strategy Using Bis(cyclopentadienyl)titanium Dichloride (Cp2TiCl2)

Bis(cyclopentadienyl)titanium dichloride (Cp₂TiCl₂) is a high performance additive under UV light activation for both i) radical photopolymerization reactions (when added to a Type I photo­initiator such as 2,2‐dimethoxy‐2‐phenylacetophenone, the oxygen inhibition is reduced) and ii) a concomitant in situ photoinduced and oxygen mediated formation of Ti‐based nanoparticles (diameters ranging from 45 to 220 nm). The photochemical properties of Cp₂TiCl₂ are investigated by steady state photolysis and electron spin resonance, and its photoinitiation ability checked. The nanoparticles (NPs) are well characterized by transmission electron microscopy. The high reactivity of Cp₂TiCl₂ under air is ascribed to a bimolecular homolytic substitution (the S_H2 process is clearly demonstrated by density functional theory calculations and ESR experiments), which converts the peroxyls into new efficient initiating radicals. The photochemical in situ incorporation of Ti NPs has never previously been reported. The synthesis of metal nanoparticles by a S_H2 approach instead of the reduction of a metal salt appears to be a promising original method.

     

Anomalous kinetics in diffusion limited reactions linked to non-Gaussian concentration probability distribution function

We investigate anomalous reaction kinetics related to segregation in the one-dimensional reaction-diffusion system A + B → C. It is well known that spatial fluctuations in the species concentrations cause a breakdown of the mean-field behavior at low concentration values. The scaling of the average concentration with time changes from the mean-field t(-1) to the anomalous t(-1/4) behavior. Using a stochastic modeling approach, the reaction-diffusion system can be fully characterized by the multi-point probability distribution function (PDF) of the species concentrations. Its evolution is governed by a Fokker-Planck equation with moving boundaries, which are determined by the positivity of the species concentrations. The concentration PDF is in general non-Gaussian. As long as the concentration fluctuations are small compared to the mean, the PDF can be approximated by a Gaussian distribution. This behavior breaks down in the fluctuation dominated regime, for which anomalous reaction kinetics are observed. We show that the transition from mean field to anomalous reaction kinetics is intimately linked to the evolution of the concentration PDF from a Gaussian to non-Gaussian shape. This establishes a direct relationship between anomalous reaction kinetics, incomplete mixing and the non-Gaussian nature of the concentration PDF.     

Evaluation of various chromatographic approaches for the retention of hydrophilic compounds and MS compatibility

The goal of this study was to compare the performance of three separation techniques for the analysis of 57 hydrophilic compounds. RPLC, hydrophilic interaction liquid chromatography (HILIC) and subcritical fluid chromatography (SFC) were tested. The comparison was based on the retention, selectivity, peak shape (asymmetry and peak width) and MS sensitivity. As expected, RPLC had some obvious limitations for such classes of compounds, and on average the %ACN required to elute these hydrophilic substances was 4, 7, and 11% ACN at pH 3, 6, and 9, respectively. However, a hybrid polar‐embedded C₁₈ phase with an appropriate mobile phase could represent a viable strategy for hydrophilic basic compounds with log D greater than –2 on average. HILIC and SFC were found to be more appropriate for analyzing a large majority of these hydrophilic analytes (～60 and 70% of compounds eluted during the gradient in HILIC and SFC), while maintaining good MS sensitivity. Finally, this work demonstrated the complementarity of the three analytical techniques and showed that the selection of a suitable strategy should mostly be based on physicochemical properties of the analytes (pK_a, log D, H‐bonding capability, etc.).     

Probing Long-Range Anisotropic Interactions: a General and Sign-Sensitive Strategy to Measure 1H–1H Residual Dipolar Couplings as a Key Advance for Organic Structure Determination

Residual dipolar couplings (RDCs) are amongst the most powerful NMR parameters for organic structure elucidation. In order to maximize their effectiveness in increasingly complex cases such as flexible compounds, a maximum of RDCs between nuclei sampling a large distribution of orientations is needed, including sign information. For this, the easily accessible one-bond ¹H–¹³C RDCs alone often fall short. Long-range ¹H–¹H RDCs are both abundant and typically sample highly complementary orientations, but accessing them in a sign-sensitive way has been severely obstructed due to the overflow of ¹H–¹H couplings. Here, we present a generally applicable strategy that allows the measurement of a large number of ¹H–¹H RDCs, including their signs, which is based on a combination of an improved PSYCHEDELIC method and a new selective constant-time β-COSY experiment. The potential of ¹H–¹H RDCs to better determine molecular alignment and to discriminate between enantiomers and diastereomers is demonstrated.     

Single-Crystalline Optical Microcavities from Luminescent Dendrimers

Microcrystallites are promising minute mirrorless laser sources. A variety of luminescent organic compounds have been exploited along this line, but dendrimers have been inapplicable owing to their fragility and extremely poor crystallinity. Now, a dendrimer family that overcomes these difficulties is presented. First-, second-, and third-generation carbazole (Cz) dendrimers with a carbon-bridged oligo(phenylenevinylene) (COPV2) core (GnCOPV2, n=1–3) assemble to form microcrystals. The COPV2 cores align uni/bidirectionally in the crystals while the Cz units in G2- and G3COPV2 align omnidirectionally. The dendrons work as light-harvesting antennas that absorb non-polarized light and transfer it to the COPV2 core, from which a polarized luminescence radiates. Furthermore, these crystals act as laser resonators, where the lasing thresholds are strongly coupled with the crystal morphology and the orientation of COPV2, which is in contrast with the conventional amorphous dendrimers.     

Serial Femtosecond Zero Dose Crystallography Captures a Water-Free Distal Heme Site in a Dye-Decolorising Peroxidase to Reveal a Catalytic Role for an Arginine in FeIV=O Formation

Obtaining structures of intact redox states of metal centers derived from zero dose X-ray crystallography can advance our mechanistic understanding of metalloenzymes. In dye-decolorising heme peroxidases (DyPs), controversy exists regarding the mechanistic role of the distal heme residues aspartate and arginine in the heterolysis of peroxide to form the catalytic intermediate compound I (Fe^IV=O and a porphyrin cation radical). Using serial femtosecond X-ray crystallography (SFX), we have determined the pristine structures of the Fe^III and Fe^IV=O redox states of a B-type DyP. These structures reveal a water-free distal heme site that, together with the presence of an asparagine, imply the use of the distal arginine as a catalytic base. A combination of mutagenesis and kinetic studies corroborate such a role. Our SFX approach thus provides unique insight into how the distal heme site of DyPs can be tuned to select aspartate or arginine for the rate enhancement of peroxide heterolysis.     

Die Nitroprussidverbindungen der Alkaloide

Ohne Zusammenfassung     

Gehaltsbestimmung von Alkaloiden in Drogen und Tinkturen

Ohne Zusammenfassung