Nickelmodifiedlarge poremesoporoussilicas ascatalysts for methanol decomposition

Summary Ni-modifiedlarge poremesoporous silicasarecharacterized by XRD, N₂physisorption and TPR with H₂. Theeffectof the supportpore structure on their catalytic behaviorin methanol decomposition to H₂, CO and CH₄is studied.     

Synthetic and computational assessment of a chiral metal–organic framework catalyst for predictive asymmetric transformation

Understanding and controlling molecular recognition mechanisms at a chiral solid interface is a continuously addressed challenge in heterogeneous catalysis. Here, the molecular recognition of a chiral peptide-functionalized metal–organic framework (MOF) catalyst towards a pro-chiral substrate is evaluated experimentally and in silico. The MIL-101 metal–organic framework is used as a macroligand for hosting a Noyori-type chiral ruthenium molecular catalyst, namely (benzene)Ru@MIL-101-NH-Gly-Pro. Its catalytic perfomance toward the asymmetric transfer hydrogenation (ATH) of acetophenone into R- and S-phenylethanol are assessed. The excellent match between the experimentally obtained enantiomeric excesses and the computational outcomes provides a robust atomic-level rationale for the observed product selectivities. The unprecedented role of the MOF in confining the molecular Ru-catalyst and in determining the access of the prochiral substrate to the active site is revealed in terms of highly face-specific host–guest interactions. The predicted surface-specific face differentiation of the prochiral substrate is experimentally corroborated since a three-fold increase in enantiomeric excess is obtained with the heterogeneous MOF-based catalyst when compared to its homogeneous molecular counterpart.

Understanding and controlling molecular recognition mechanisms at a chiral solid interface has been addressed in metal–organic framework catalysts for the asymmetric transfer hydrogenation reaction.     

A Diverse Assemblage of Indole-3-Acetic Acid Producing Bacteria Associate with Unicellular Green Algae

Microalgae have tremendous potential as a renewable feedstock for the production of liquid transportation fuels. In natural waters, the importance of physical associations and biochemical interactions between microalgae and bacteria is generally well appreciated, but the significance of these interactions to algal biofuels production have not been investigated. Here, we provide a preliminary report on the frequency of co-occurrence between indole-3-acetic acid (IAA)-producing bacteria and green algae in natural and engineered ecosystems. Growth experiments with unicellular algae, Chlorella and Scenedesmus, revealed IAA concentration-dependent responses in chlorophyll content and dry weight. Importantly, discrete concentrations of IAA resulted in cell culture synchronization, suggesting that biochemical priming of cellular metabolism could vastly improve the reliability of high density cultivation. Bacterial interactions may have an important influence on algal growth and development; thus, the preservation or engineered construction of the algal–bacterial assembly could serve as a control point for achieving low input, reliable production of algal biofuels.     

Influence of measurement parameters of laser flash analysis on the observed thermal diffusivity and the choice of parameters to get repeatable measurements

Journal of Thermal Analysis and Calorimetry - This work is a continuation of our researches on the study of thermodynamic properties of organic compound mixtures and made...     

Molecular and crystal structure of Cp2Mo(mto), mto=monothiooxalate

Compoundl, Cp₂Mo(mto) is obtained by the reaction of Cp₂MoCl₂ with methanol solutions of potassium dithiooxalate in air. Red platelike crystals of Cp₂Mo(mto) were grown by the slow diffusion of pentane into a CH₂Cl₂ solution ofl and have been studied by X-ray crystallography: space group, P2₁/n,a=7.578(1),b=10.551(2),c=14.090(3) Å, =94.38(2)°,V=1123.1(4) ų,Z=4. The mto ligand chelates to the Mo atom through one oxygen atom and the sulfur atom. The two Cp rings form dihedral angles of 24° with the least-squares plane of the mto ligand. The Mo–O and Mo–S bond distances are 2.193(5) and 2.449(2) Å, respectively.     

Highly Coherent Spectroscopy of Ultracold Atoms and Molecules in Optical Lattices

Cooling and trapping of neutral atoms using laser techniques has enabled extensive progress in precise, coherent spectroscopy. In particular, trapping ultracold atoms in optical lattices in a tight confinement regime allows us to perform high‐resolution spectroscopy unaffected by atomic motion. We report on the recent developments of optical lattice atomic clocks that have led to optical spectroscopy coherent at the one second timescale. The lattice clock techniques also open a promising pathway toward trapped ultracold molecules and the possible precision measurement opportunities such molecules offer.     

Pd(II) phthalocyanine-sensitized triplet-triplet annihilation from rubrene

Upconverted yellow singlet fluorescence from rubrene (5,6,11,12-tetraphenylnapthacene) was generated from selective excitation (lambdaex = 725 nm) of the red light absorbing triplet sensitizer palladium(II) octabutoxyphthalocyanine, PdPc(OBu)8, in vacuum degassed toluene solutions using a Nd:YAG/OPO laser system in concert with gated iCCD detection. The data are consistent with upconversion proceeding from triplet-triplet annihilation (TTA) of rubrene acceptor molecules. The TTA process was confirmed by the quadratic dependence of the upconverted delayed fluorescence intensity with respect to incident light, measured by integrating the corresponding kinetic traces as a function of the incident excitation power. In vacuum degassed toluene solutions, the red-to-yellow upconversion process is stable under continuous long wavelength irradiation and is readily visualized by the naked eye even at modest laser fluence (0.6 mJ/pulse). In aerated solutions, however, selective excitation of the phthalocyanine sensitizer leads to rapid decomposition of rubrene into its corresponding endoperoxide as evidenced by UV-vis (in toluene), 1H NMR (in d6-benzene), and MALDI-TOF mass spectrometry, consistent with the established reactivity of rubrene with singlet dioxygen. The upconversion process in this triplet sensitizer/acceptor-annihilator combination was preliminarily investigated in solid polymer films composed of a 50:50 mixture of an ethyleneoxide/epichlorohydrin copolymer, P(EO/EP). Films that were prepared under an argon atmosphere and maintained under this inert environment successfully achieve the anticipated quadratic incident power dependence, whereas air exposure causes the film to deviate somewhat from this dependence. To the best of our knowledge, the current study represents the first example of photon upconversion using a phthalocyanine triplet sensitizer, furthering the notion that anti-Stokes light-producing sensitized TTA appears to be a general phenomenon as long as proper energy criteria are met.     

Cover Picture: Supramolecular Self-Assembly as a Tool To Preserve the Electronic Purity of Perylene Diimide Chromophores (Angew. Chem. Int. Ed. 12/2023)

Organic semiconductors are promising for efficient, printable optoelectronics. However, strong excited-state quenching due to uncontrolled aggregation limits their use in devices. We report on the self-assembly of a supramolecular pseudo-cube formed from six perylene diimides (PDIs). The rigid, shape-persistent cage sets the distance and orientation of the PDIs and suppresses intramolecular rotations and vibrations, leading to non-aggregated, monomer-like properties in solution and the solid state, in contrast to the fast fluorescence quenching in the free ligand. The stabilized excited state and electronic purity in the cage enables the observation of delayed fluorescence due to a bright excited multimer, acting as excited-state reservoir in a rare case of benign inter-chromophore interactions in the cage. We show that self-assembly provides a powerful tool for retaining and controlling the electronic properties of chromophores, and to bring molecular electronics devices within reach.