Convenient Synthesis of 2-Deoxy-D-Glucofuranosides

ABSTRACT

Methyl 2-deoxy-D-glucofuranoside has been conveniently prepared starting from 3-O-benzyl-1,2-O-isopropylidene-α-D-glucofuranose, involving the first described deoxygenation at the 2-position.     

Diffusion‐driven continuous‐wave‐pumped organic dye lasers

We report on the realisation of ultra‐small‐mode‐volume tunable dye lasers based on hemispherical open microcavities. The cavity mode volume is of the order of cubic micrometers, such that self‐diffusion of the dye molecules allows continuous wave operation over several minutes without the need for driven circulation. Such micro lasers could be integrated into lab‐on‐a‐chip devices. A rate‐equation model that incorporates the diffusion mechanism is used to predict the effect of the microcavity parameters on the lasing threshold.

     

Heavy‐Atom Tunneling in Organic Reactions

In the past few years, numerous investigations have been reported on the role of heavy‐atom tunneling in the area of pericyclic reactions, π‐bond‐shifting, and other processes. These studies illustrate unique strategies for the experimental detection of heavy‐atom tunneling and the increased use of calculations to predict it. This Minireview focuses primarily on carbon tunneling in ground‐state processes but also highlights nitrogen tunneling and the first example of excited‐state heavy‐atom tunneling. Salient features of these reactions along with potential limitations are discussed, as well as challenges and directions for future investigation.     

Diversity Oriented Clicking (DOC): Divergent Synthesis of SuFExable Pharmacophores from 2‐Substituted‐Alkynyl‐1‐Sulfonyl Fluoride (SASF) Hubs

Diversity Oriented Clicking (DOC) is a unified click‐approach for the modular synthesis of lead‐like structures through application of the wide family of click transformations. DOC evolved from the concept of achieving “diversity with ease”, by combining classic C?C π‐bond click chemistry with recent developments in connective SuFEx‐technologies. We showcase 2‐S ubstituted‐A lkynyl‐1‐S ulfonyl F luorides (SASFs) as a new class of connective hub in concert with a diverse selection of click‐cycloaddition processes. Through the selective DOC of SASFs with a range of dipoles and cyclic dienes, we report a diverse click‐library of 173 unique functional molecules in minimal synthetic steps. The SuFExable library comprises 10 discrete heterocyclic core structures derived from 1,3‐ and 1,5‐dipoles; while reaction with cyclic dienes yields several three‐dimensional bicyclic Diels–Alder adducts. Growing the library to 278 discrete compounds through late‐stage modification was made possible through SuFEx click derivatization of the pendant sulfonyl fluoride group in 96 well‐plates—demonstrating the versatility of the DOC approach for the rapid synthesis of diverse functional structures. Screening for function against MRSA (USA300) revealed several lead hits with improved activity over methicillin.     

Carbon–Carbon Bond Forming Reactions Promoted by Aluminyl and Alumoxane Anions: Introducing the Ethenetetraolate Ligand

[K{Al(NON^Dipp)}]₂ (NON^Dipp=[O(SiMe₂NDipp)₂]^2?, Dipp=2,6‐iPr₂C₆H₃) reacts with CS₂ to afford the trithiocarbonate species [K(OEt₂)][Al(NON^Dipp)(CS₃)] 1 or the ethenetetrathiolate complex, [K{Al(NON^Dipp)(S₂C)}]₂ [ 3 ]₂. The dimeric alumoxane [K{Al(NON^Dipp)(O)}]₂ reacts with carbon monoxide to afford the oxygen analogue of 3 , [K{Al(NON^Dipp)(O₂C)}]₂ [ 4 ]₂ containing the hitherto unknown ethenetetraolate ligand, [C₂O₄]^4?.     

Liquid Marble Photosensor

A liquid marble is a liquid droplet coated by a hydrophobic powder. The liquid marble does not wet adjacent surfaces and therefore can be manipulated as a dry soft body. A Belousov-Zhabotinsky (BZ) reaction is an oscillatory chemical reaction exhibiting waves of oxidation. We demonstrate how to make a photo-sensor from BZ medium liquid marbles. We insert electrodes into a liquid marble, prepared from BZ solution and coated with polyethylene powder. The electrodes record a potential difference which oscillates due to oxidation wave-fronts crossing the electrodes. When the BZ marble is illuminated by a light source, the oxidation wave-fronts are hindered and, thus, the electrical potential recorded ceases to oscillate. We characterise several types of responses of BZ marble photosensors to various stimuli, and provide explanations of the recorded activity. BZ liquid marble photosensors may find applications in the fields of liquid electronics, soft robotics and unconventional computing.     

A Stable Calcium Alumanyl

A seven-membered N,N′-heterocyclic potassium alumanyl nucleophile is introduced and utilised in the metathetical synthesis of Mg−Al and Ca−Al bonded derivatives. Both species have been characterised by experimental and theoretical means, allowing a rationalisation of the greater reactivity of the heavier group 2 species implied by an initial assay of their reactivity.     

Bright Infrared-to-Ultraviolet/Visible Upconversion in Small Alkaline Earth-Based Nanoparticles with Biocompatible CaF2 Shells

Upconverting nanoparticles (UCNPs) are promising candidates for photon-driven reactions, including light-triggered drug delivery, photodynamic therapy, and photocatalysis. Herein, we investigate the NIR-to-UV/visible emission of sub-15 nm alkaline-earth rare-earth fluoride UCNPs (M_1−xLn_xF_2+x, MLnF) with a CaF₂ shell. We synthesize 8 alkaline-earth host materials doped with Yb³⁺ and Tm³⁺, with alkaline-earth (M) spanning Ca, Sr, and Ba, MgSr, CaSr, CaBa, SrBa, and CaSrBa. We explore UCNP composition, size, and lanthanide doping-dependent emission, focusing on upconversion quantum yield (UCQY) and UV emission. UCQY values of 2.46 % at 250 W cm⁻² are achieved with 14.5 nm SrLuF@CaF₂ particles, with 7.3 % of total emission in the UV. In 10.9 nm SrYbF:1 %Tm³⁺@CaF₂ particles, UV emission increased to 9.9 % with UCQY at 1.14 %. We demonstrate dye degradation under NIR illumination using SrYbF:1 %Tm³⁺@CaF₂, highlighting the efficiency of these UCNPs and their ability to trigger photoprocesses.     

Synergistic effect of the simultaneous chemometric analysis of H NMR spectroscopic and stable isotope (SNIF-NMR,O, C) data: Application to wine analysis

It is known that ¹H NMR spectroscopy represents a good tool for predicting the grape variety, the geographical origin, and the year of vintage of wine. In the present study we have shown that classification models can be improved when ¹H NMR profiles are fused with stable isotope (SNIF-NMR, ¹⁸O, ¹³C) data. Variable selection based on clustering of latent variables was performed on ¹H NMR data. Afterwards, the combined data of 718 wine samples from Germany were analyzed using linear discriminant analysis (LDA), partial least squares-discriminant analysis (PLS-DA), factorial discriminant analysis (FDA) and independent components analysis (ICA). Moreover, several specialized multiblock methods (common components and specific weights analysis (ComDim), consensus PCA and consensus PLS-DA) were applied to the data.     

A Huge PVDF Adsorption Difference Between Resveratrol and ε-Viniferin Allows to Quantitatively Purify Them and to Assess Their Anti-Tyrosinase Property

Repeated chromatographic analyses of polyphenolic vine stalks extracts allowed us to note a huge adsorption difference on polyvinylidene fluoride (PVDF), between trans-resveratrol 1 and (+)-trans-ε-viniferin 2. We could optimize the conditions (solvent, saturation of the process), for this polymer to adsorb very selectively 2, with regard to the monomer 1 that remains in solution. Since membrane filters made of PVDF are quite often used for HPLC samples filtration, this observation prompted us to inform phytochemists studying plant stilbenoid contents. Based on this background information, we developed a straightforward and inexpensive enrichment process for either 1 and/or 2, from crude Vitis vinifera stalks extracts, allowing to get them in a pure form. Having at hand large amounts of these two pure compounds, they were tested and compared to a set of other relevant molecules for some biological properties: trans-ε-viniferin 2 was shown to be the most powerful tyrosinase inhibitor, among all samples tested.