Sustainable Hues: Exploring the Molecular Palette of Biowaste Dyes through LC-MS Metabolomics

Underutilized biowaste materials are investigated for their potential as sustainable textile colorants through an approach based on mass spectrometry, bioinformatics, and chemometrics. In this study, colorful decoctions were prepared from the outer bark of Eucalyptus deglupta and fruit peels of Syzygium samarangense, Syzygium malaccense, Diospyros discolor, and Dillenia philippinensis. Textile dyeing was performed along with liquid chromatography–mass spectrometry (LC–MS)-based untargeted metabolomics to determine the small molecules responsible for the observed colors. Global Natural Products Social Molecular Networking (GNPS) guided the annotation of black-producing proanthocyanidins in D. philippinensis and E. deglupta through complexation with FeSO₄ mordant. Flavonoids from the yellow-colored D. philippinensis extracts were found to be similar to those in Terminalia catappa, a known traditional dye source. A higher intensity of epicatechin in E. deglupta produced a red-brown color in the presence of Cu²⁺. Furthermore, Syzygium fruit peels have poor wash-fastness in cotton fibers, but bioactive chalcone unique to S. samarangense samples may be a potential nutritional food colorant. Unsupervised PCA and supervised OPLS-DA chemometrics distinguished chemical features that affect dyeing properties beyond the observed color. These findings, along with growing data on natural dyes, could guide future research on sustainable colorants.     

An elasto-visco-plastic model for immortal foams or emulsions

A variety of complex fluids consists in soft, round objects (foams, emulsions, assemblies of copolymer micelles or of multilamellar vesicles--also known as onions). Their dense packing induces a slight deviation from their prefered circular or spherical shape. As a frustrated assembly of interacting bodies, such a material evolves from one conformation to another through a succession of discrete, topological events driven by finite external forces. As a result, the material exhibits a finite yield threshold. The individual objects usually evolve spontaneously (colloidal diffusion, object coalescence, molecular diffusion), and the material properties under low or vanishing stress may alter with time, a phenomenon known as aging. We neglect such effects to address the simpler behaviour of (uncommon) immortal fluids: we construct a minimal, fully tensorial, rheological model, equivalent to the (scalar) Bingham model. Importantly, the model consistently describes the ability of such soft materials to deform substantially in the elastic regime (be it compressible or not) before they undergo (incompressible) plastic creep--or viscous flow under even higher stresses.     

Stable Borepinium and Borafluorenium Heterocycles: A Reversible Thermochromic “Switch” Based on Boron–Oxygen Interactions

The first examples of N-heterocyclic carbene (NHC) and cyclic(alkyl)(amino) carbene (CAAC) stabilized borepinium and borafluorenium heterocycles are reported herein. The optical properties of the heterocyclic borenium cations were tuned by varying the Lewis base and by changing the number of atoms in the ring. More importantly, functionalizing the cationic boron ring system in the NHC-borafluorenium cation affords a temperature-sensitive molecule with reversible colorimetric “turn off/turn on” properties in solution. Notably, this is the first report of thermochromism in these cationic species. This property, which is mediated by an intermolecular boron–oxygen bond equilibrium, was examined in detail by X-ray crystallography, variable temperature-UV/Vis absorption spectroscopy (VT-UV/Vis), and density functional theory (DFT).     

The quartz crystal microbalance: a new tool for the investigation of the bioadhesion of diatoms to surfaces of differing surface energies

Diatoms are a major component of the biofoul layer found on modern low-surface-energy, 'foul release' coatings. While diatoms adhere more strongly to hydrophobic, as opposed to hydrophilic, surfaces, surprisingly little is known of the chemical composition of their adhesives. Even less is known about the underlying processes that characterize the interaction between the adhesive and a given surface, including those of differing wettability. Using the quartz crystal microbalance with dissipation monitoring (QCM-D), we examined differences in the viscoelastic properties of the extracellular adhesives produced by the marine diatoms Amphora coffeaeformis Cleve and Craspedostauros australis Cox interacting with surfaces of differing wettability; 11-mercaptoundecanoic acid (MUA) that is hydrophilic and 1-undecanethiol (UDT) that is hydrophobic. While the overall delta f/delta D ratios were slightly different, the trends were the same for both diatom species, with the layer secreted upon UDT to be more viscoelastic and far more consistent over several experiments, compared to that on MUA which was less viscoelastic and demonstrated far more variability between experiments. While the nature of the parameter shifts for C. australis were the same for both surfaces, A. coffeaeformis cells settling upon UDT illustrated significant positive f and D shifts during the initial stages of cell settlement and adhesion to the surface. Further experiments revealed the parameter shifts to occur only during the initial adhesion of cells upon the pristine virgin UDT surface. The mechanism behind these parameter responses was isolated to the actin-myosin/adhesion complex (AC), using the myosin inhibitor 2,3-butanedione 2-monoxime (BDM) to remove the cells ability to 'pull' on adhesive strands emanating from the cell raphe. The observations made herein have revealed that adhesives secreted by fouling diatoms differ significantly in their interaction with surfaces depending on their wettability, as well as illustrating the unique mechanics behind the adhesion of A. coffeaeformis upon hydrophobic surfaces, a mechanism that may contribute significantly to the cells success in colonizing hydrophobic surfaces.     

Asymmetric synthesis and absolute configuration of streptophenazine G

The asymmetric synthesis of the antibacterial natural product, streptophenazine G, has been achieved by employing asymmetric alkylation and asymmetric aldol reactions using chiral oxazolidinones as the key steps. The originally proposed structure for streptophenazine G has been revised, and its absolute configuration has been determined to be 1'S,2'R,6'S. The asymmetric total synthesis of 6'-epi-streptophenazine G is also described.     

Flow in micellar cubic crystals

 We investigate and compare the mechanical properties of two micellar cubic crystals. Both are obtained from aqueous triblock-copolymer solutions of similar block structure, (PEO)₇₆(PPO)₂₉(PEO)₇₆ and (PEO)₁₂₇(PPO)₄₈(PEO)₁₂₇, designated Pluronic F68 and F108 respectively. Extensive small angle X-ray scattering experiments under shear and common rheometry provide the following results: (i) the solid phases of the two polymeric solutions are constituted of micelles that are ordered in a bcc (F68) and fcc (F108) structure. The overall appearance of both unsheared samples is polycrystalline; (ii) SAXS showed that both systems undergo a structural reorientation under shear, with the dense planes arranged parallel to the velocity - vorticity plane, thus facilitating flow; (iii) F68 showed a clear transition in the flow curve, associated with a textural change, but the F108 system exhibited a continuous evolution; (iv) the bcc crystal appears to have no measurable yield stress and flows even for low applied stresses. This was in contrast to the fcc sample which showed a clear yield stress, separating creep and flow regimes. Received: 30 November 1999/Accepted: 30 November 1999     

Correlation between the viscoelastic properties of a soft crystal and its microstructure

We investigate the rheological properties of a cubic fcc phase of micelles obtained by aggregation of a triblock copolymer (PEO)₁₂₇(PPO)₄₈(PEO)₁₂₇ in water as selective solvent. The resulting soft solid is submitted to a range of stresses varying from 20 to 800Pa in Couette geometry. Creep and flow behaviour can be distinguished and interpreted in terms of structural changes previously observed by SAXS under flow. Contrasting with other systems, no discontinuity in the flow behaviour is associated with the structural changes. The strong shear thinning is interpreted from the scattering data, as resulting from the nucleation of a new structure of hexagonal compact planes parallel to the Couette walls. This creates a lubricating domain in the gap, whose size grows with the applied shear rate. We argue moreover that the very existence of flow (as a steady state opposed to creep) is associated with this so-called layer-sliding structure in a fraction, however small, of the sample. Received on 4 June 1999 and Received in final form 6 September 1999     

Stereoselectivity in the Hydroboration of C4-C-Methylene Groups

Abstract

Conditions for the hydroxylation of an exocyclic methylene group at C4 of a pyranoside ring via hydroboration have been examined with a view to determining the optimum procedure for obtaining the axially-oriented C4-CH₂OH group. The regio- and stereochemical outcome of the reactions rely not only on the hydroborating reagent used, but, to a surprising degree, on the nature of the protecting group at the “remote” C6-OH. Silyl ethers are preferred because the only by-product formed is the tertiary alcohol, which can be recycled through dehydration to the starting alkene by treatment with thionyl chloride.     

Rapid Plateau border size variations expected in three simple experiments on 2D liquid foams<Superscript>⋆</Superscript>

Up to a global scaling, the geometry of foams squeezed between two solid plates (2D GG foams) essentially depends on two independent parameters: the liquid volume fraction and the degree of squeezing (bubble thickness to diameter ratio). We describe it in two main asymptotic regimes: fully dry floor tiles, where the Plateau border radius is smaller than the distance between the solid plates, and dry pancakes, where it is larger. We predict a rapid variation of the Plateau border radius in one part of the pancake regime, namely when the Plateau border radius is larger than the inter-plate distance but smaller than the geometric mean of that distance and the bubble perimeter. This rapid variation is not related to any topological change in the foam: in all the regimes we consider, the bubbles remain in mutual lateral contact through films located at mid-height between both plates. We provide asymptotic predictions in different types of experiments on such 2D GG foams: when foam is being progressively dried or wetted, when it is being squeezed further or stretched, when it coarsens through film breakage or through inter-bubble gas diffusion. Our analysis is restricted to configurations close to equilibrium, as we do not include stresses resulting from bulk viscous flow or from non-homogeneous surfactant concentrations. We also assume that the inter-plate distance is sufficiently small for gravity to be negligible. The present work does not provide a method for measuring small Plateau border radii experimentally, but it indicates that large (and easily observable) Plateau borders should appear or disappear rather suddenly in some types of experiments with small inter-plate gaps. It also gives expected orders of magnitude that should be helpful for designing experiments on 2D GG foams.     

Approaching Dianionic Tetraoxadiborecine Macrocycles: 10-Membered Bora-Crown Ethers Incorporating Borafluorenate Units

The addition of non-benzenoid quinones, acenapthenequinone or aceanthrenequinone, to the 9-carbene-9-borafluorene monoanion ( 1 ) affords the first examples of dianionic 10-membered bora-crown ethers ( 2 – 5 ), which are characterized by multi-nuclear NMR spectroscopy (¹H, ¹³C, ¹¹B), X-ray crystallography, elemental analysis, and UV/Vis spectroscopy. These tetraoxadiborecines have distinct absorption profiles based on the positioning of the alkali metal cations. When compound 4 , which has a vacant C₄B₂O₄ cavity, is reacted with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, a color change from purple to orange serves as a visual indicator of metal binding to the central ring, whereby the Na⁺ ion coordinates to four oxygen atoms. A detailed theoretical analysis of the calculated reaction energetics is provided to gain insight into the reaction mechanism for the formation of 2 – 5 . These data, and the electronic structures of proposed intermediates, indicate that the reaction proceeds via a boron enolate intermediate.