Polyanhydride Microcapsules Exhibiting a Sharp pH Transition at Physiological Conditions for Instantaneous Triggered Release.

Stimulus-responsive microcapsules pose an opportunity to achieve controlled release of the entire load instantaneously upon exposure to an external stimulus. Core-shell microcapsules based on the polyanhydride poly(bis(2-carboxyphenyl)adipate) as a shell were formulated in this work to encapsulate the model active substance pyrene and enable a pH-controlled triggered release. A remarkably narrow triggering pH interval was found where a change in pH from 6.4 to 6.9 allowed for release of the entire core content within seconds. The degradation kinetics of the shell were measured by both spectrophotometric detection of degradation products and mass changes by quartz crystal microbalance with dissipation monitoring and were found to correlate excellently with diffusion coefficients fitted to release measurements at varying pH values. The microcapsules presented in this work allow for an almost instantaneous triggered release even under mild conditions, thanks to the designed core-shell morphology.

Transport Properties of Protic Ionic Liquids Based on Triazolium and Imidazolium: Development of an Air-Free Conductivity Setup.

The dynamical properties of four protic ionic liquids, based on the ethyltriazolium ([C2HTr124]) and the ethylimidazolium ([C2HIm]) cation, were investigated. The associated anions were the triflate ([TfO]) and the bistriflimide ([TFSI]). Ionic conductivity values and self-diffusion coefficients were measured and discussed, extending the discussion to the concept of fragility. Furthermore, in order to allow the measurement of the ionic conductivity of very small volumes (<0.5 mL) of ionic liquid under an inert and dry atmosphere, a new setup was developed. It was found that the cation nature strongly affected the transport properties, the [C2HTr124] cation resulting in slower dynamics than the [C2HIm] one. This was concluded from both conductivity and diffusivity measurements while for both properties, the anion had a lesser effect. By fitting the conductivity data with the Vogel-Fulcher-Tammann (VFT) equation, we could also estimate the fragility of these ionic liquids, which all fell in the range of very fragile glass-forming materials. Finally, the slower dynamics observed in the triazolium-based ionic liquids can be rationalized by the stronger interactions that this cation establishes with both anions, as deduced from the frequency analysis of relevant Raman signatures and density functional theory (DFT) calculations.

Electroactive Covalent Organic Framework Enabling Photostimulus-Responsive Devices.

Two-dimensional covalent organic frameworks (2D COFs) feature graphene-type 2D layered sheets but with a tunable structure, electroactivity, and high porosity. If these traits are well-combined, then 2D COFs can be applied in electronics to realize functions with a high degree of complexity. Here, a highly crystalline electroactive COF, BDFamide-Tp, was designed and synthesized. It shows regularly distributed pores with a width of 1.35 nm. Smooth and successive films of such a COF were fabricated and found to be able to increase the conductivity of an organic semiconductor by 103 by interfacial doping. Upon encapsulation of a photoswitchable molecule (spiropyran) into the voids of the COF layer, the resulted devices respond differently to light of different wavelengths. Specifically, the current output ratio after UV vs Vis illumination reaches 100 times, thus effectively creating on and off states. The respective positive and negative feedbacks are memorized by the device and can be reprogrammed by UV/Vis illumination. The reversible photostimulus responsivity and reliable memory of the device are derived from the combination of electroactivity and porosity of the 2D COF. This work shows the capability of 2D COFs in higher-level electronic functions and extends their possible applications in information storage.

The role of chelating agent in the self-assembly of amphoteric surfactants.

HYPOTHESIS: Limited research has been conducted on the influence of chelating agents on the self-assembly process in surfactant solutions. The traditional approach assumes the chelating agent only interferes as a salting-out ion, therefore promoting surfactant separation. However, the opposite behavior has been observed for iminodipropionate based surfactants, in which the presence of chelating agents of the aminopolycarboxylate type increases solubility of nonionic ethoxylated surfactants in mixed micellar systems. Specific interaction between chelating agents-surfactants can be an important parameter in the self-assembly processes. EXPERIMENTS: Physicochemical properties of solutions containing amphoteric surfactant and tetrasodium glutamatediacetate have been investigated. Macroscopic properties, such as viscosity and cloud point, were evaluated in the presence of a non-water-soluble alkyl ethoxylated surfactant. Interactions between amphoteric surfactant and chelating agent were monitored by NMR spectroscopy, including 13C chemical shift and lineshape analysis as well as 1H diffusometry. FINDINGS: The study reveals that there is an interaction between the head group of the surfactant and the chelating agent forming oligomeric surfactant analogues with larger hydrophilic moieties, which results in smaller, more spherical micelles. The combined interactions provide possibilities for tuning the aggregation behavior of systems containing surfactants and chelating agents, and with that, the macroscopic properties of the system.

A unified thermodynamic and kinetic approach for prediction of microcapsule morphologies.

HYPOTHESIS: Microcapsule formation, following internal phase separation by solvent evaporation, is controlled by two main factors of thermodynamic and kinetic origin. Morphology prediction has previously focused on the final thermodynamical state in terms of spreading conditions, limiting the prediction accuracy. By additionally considering kinetic effects as the emulsion droplet evolves through the two-phase region of its ternary phase diagram during solvent evaporation, this should enhance prediction accuracy and explain a wider range of morphologies. EXPERIMENTS: Dynamical interfacial tensions, and thereby spreading coefficients, during the formation of poly(methyl methacrylate) and poly(d,l-lactic-co-glycolic acid) microcapsules were measured by first establishing the boundaries and tie-lines of the ternary system in the emulsion droplets. Kinetic effects during the formation were investigated by varying the solvent evaporation rate and hence the time for polymer shell formation equilibration. The theory was validated by comparing predicted morphologies to microscopic snapshots of intermediate and final morphologies. FINDINGS: The proposed theory explained both intermediate acorn and core-shell morphologies, where a late transition from acorn to core-shell produced microcapsules containing highly off-centered cores. By considering the kinetic factors, the formulation could be altered from yielding kinetically frozen acorns to core-shell and from yielding multicore to single core microcapsules.

Nanostructures of etherified arabinoxylans and the effect of arabinose content on material properties.

To further our understanding of a thermoplastic arabinoxylan (AX) material obtained through an oxidation-reduction-etherification pathway, the role of the initial arabinose:xylose ratio on the material properties was investigated. Compression molded films with one molar substitution of butyl glycidyl ether (BGE) showed markedly different tensile behaviors. Films made from low arabinose AX were less ductile, while those made from high arabinose AX exhibited elastomer-like behaviors. X-ray scattering confirmed the presence of nanostructure formation resulting in nano-domains rich in either AX or BGE, from side chain grafting. The scattering data showed variations in the presence of ordered structures, nano-domain sizes and their temperature response between AX with different arabinose contents. In dynamic mechanical testing, three transitions were observed at approximately -90 °C, -50 °C and 80 °C, with a correlation between samples with more structured nano-domains and those with higher onset transition temperatures and lower storage modulus decrease. The mechanical properties of the final thermoplastic AX material can therefore be tuned by controlling the composition of the starting material.

Liquid foams as sensors for the detection of biomarkers.

Bioassays are widely used in healthcare to detect and quantify biomarkers, such as molecules or enzymes, which are crucial in monitoring diseases and health conditions. In developed countries, healthcare professionals use specialized reagents and equipment's to perform these bioassays. However, in less-industrialized countries, the creation of low cost, fast, and technically simple bioassays is required. Herein, we propose a simple approach for detecting biochemical markers using host-guest complexes containing a surfactant. When the biochemical marker is present, the host-guest complex is disrupted, releasing the surfactant and producing foam. The read-out mechanism relies on the change of foam volume as function of biomarker concentration. This change is quantifiable by the naked eye and can be measured with a simple ruler. We claim that the use of foams as sensing tool is an attractive, inexpensive, fast, and easy to handle on-site detection method.

Contact-free measurement of surface tension on single droplet using machine learning and acoustic levitation.

HYPOTHESIS: Acoustic levitation provides the possibility to deform levitated droplets in a controllable, and quantifiable manner, thus offering a means to measure the surface tension of a liquid droplet based on its deviation from sphericity. However, for new generation of multi-source and highly stable acoustic levitators, no model relates the acoustic pressure field to the deformation and surface tension. Utilizing a machine learning algorithm is expected to identify correlations between the experimental data without any set preconditions. EXPERIMENTS: A series of aqueous surfactant solutions with a large range of surface tensions were prepared, and evaporated under levitation, while the acoustic pressure was varied. A dataset of over 50,000 images was used for the training and evaluation of the machine learning algorithm. Prior to that, the machine learning approach was validated on in silico data that also included artificial noise. FINDINGS: We achieved high accuracy in predicting the surface tension of single standing droplets (±0.88 mN/m), and we surpassed certain physical conditions related to the size, and shape of the suspended samples that simpler theoretical models are subject to.

Microcapsule functionalization enables rate-determining release from cellulose nonwovens for long-term performance.

Functional textiles is a rapidly growing product segment in which sustained release of actives often plays a key role. Failure to sustain the release results in costs due to premature loss of functionality and resource inefficiency. Conventional application methods such as impregnation lead to an excessive and uncontrolled release, which - for biocidal actives - results in environmental pollution. In this study, microcapsules are presented as a means of extending the release from textile materials. The hydrophobic model substance pyrene is encapsulated in poly(D,L-lactide-co-glycolide) microcapsules which subsequently are loaded into cellulose nonwovens using a solution blowing technique. The release of encapsulated pyrene is compared to that of two conventional functionalization methods: surface and bulk impregnation. The apparent diffusion coefficient is 100 times lower for encapsulated pyrene compared to impregnated pyrene. This clearly demonstrates the rate-limiting barrier properties added by the microcapsules, extending the potential functionality from hours to weeks.

Arabinoxylan supplemented bread: From extraction of fibers to effect of baking, digestion, and fermentation.

The intake of dietary fibers is related with important benefits for human health. We produced two different arabinoxylan fibers with (FAX) and without ferulic acid linked (AX), 12.5 and 0.1 mg g-1 of ferulic acid respectively, by subcritical water extraction of wheat bran. Both FAX and AX fibers were used as supplement in bread production, while non-supplemented bread was used as control. Through an enzymatic deconstruction process we investigated the effect of bread making on the fibers, the preservation of their molecular structure (A/X ratio of 0.13 and Mw of 105 Da) and the interaction with other macromolecules in the bread. By mimicking the upper track digestion, we could confirm the non-digestability of the fibers and we used them for the fermentation with B. ovatus and B. adolescentis. The presence of AX fibers during fermentation showed specific substrate adaptation by the probiotic bacteria in correlation with its potential prebiotic effect.

Modification of xylan via an oxidation-reduction reaction.

Xylan is a biopolymer readily available from forest resources. Various modification methods, including oxidation with sodium periodate, have been shown to facilitate the engineering applications of xylan. However, modification procedures are often optimized for semicrystalline high molecular weight polysaccharide cellulose rather than for lower molecular weight and amorphous polysaccharide xylan. This paper elucidates the procedure for the periodate oxidation of xylan into dialdehyde xylan and its further reduction into a dialcohol form and is focused on the modification work up. The oxidation-reduction reaction decreased the molecular weight of xylan while increased the dispersity more than 50%. Unlike the unmodified xylan, all the modified grades could be solubilized in water, which we see essential for facilitating the future engineering applications of xylan. The selection of quenching and purification procedures and pH-adjustment of the reduction step had no significant effect on the degree of oxidation, molecular weight and only a minor effect on the hydrodynamic radius in water. Hence, it is possible to choose the simplest oxidation-reduction route without time consuming purification steps within the sequence.

Green Topochemical Esterification Effects on the Supramolecular Structure of Chitin Nanocrystals: Implications for Highly Stable Pickering Emulsions.

In nature, chitin is organized in hierarchical structures composed of nanoscale building blocks that show outstanding mechanical and optical properties attractive for nanomaterial design. For applications that benefit from a maximized interface such as nanocomposites and Pickering emulsions, individualized chitin nanocrystals (ChNCs) are of interest. However, when extracted in water suspension, their individualization is affected by ChNC self-assembly, requiring a large amount of water (above 90%) for ChNC transport and stock, which limits their widespread use. To master their individualization upon drying and after regeneration, we herein report a waterborne topochemical one-pot acid hydrolysis/Fischer esterification to extract ChNCs from chitin and simultaneously decorate their surface with lactate or butyrate moieties. Controlled reaction conditions were designed to obtain nanocrystals of a comparable aspect ratio of about 30 and a degree of modification of about 30% of the ChNC surface, under the rationale to assess the only effect of the topochemistry on ChNC supramolecular organization. The rheological analysis coupled with polarized light imaging shows how the nematic structuring is hindered by both surface ester moieties. The increased viscosity and elasticity of the modified ChNC colloids indicate a gel-like phase, where typical ChNC clusters of liquid crystalline phases are disrupted. Pickering emulsions have been prepared from lyophilized nanocrystals as a proof of concept. Our results demonstrate that only the emulsions stabilized by the modified ChNCs have excellent stability over time, highlighting that their individualization can be regenerated from the dry state.

Disassociated molecular orientation distributions of a composite cellulose-lignin carbon fiber precursor: A study by rotor synchronized NMR spectroscopy and X-ray scattering.

Cellulose-lignin composite carbon fibers have shown to be a potential environmentally benign alternative to the traditional polyacrylonitrile precursor. With the associated cost reduction, cellulose-lignin carbon fibers are an attractive light-weight material for, e.g. wind power and automobile manufacturing. The carbon fiber tenacity, tensile modulus and creep resistance is in part determined by the carbon content and the molecular orientation distribution of the precursor. This work disassociates the molecular orientation of different components in cellulose-lignin composite fibers using rotor-synchronized solid-state nuclear magnetic resonance spectroscopy and X-ray scattering. Our results show that lignin is completely disordered, in a mechanically stretched cellulose-lignin composite fiber, while the cellulose is ordered. In contrast, the native spruce wood raw material displays both oriented lignin and cellulose. The current processes for fabricating a cellulose-lignin composite fiber cannot regain the oriented lignin as observed from the native wood.

CO2 induced phase transition on a self-standing droplet studied by X-ray scattering and magnetic resonance.

HYPOTHESIS: Acoustic levitation is a suitable approach for studying processes occurring at the gas-liquid interfaces, as it allows its investigation in a contact-free manner while providing control over the gas phase. Here, we hypothesize that phase transitions induced by a CO2 rich atmosphere can be examined, at different length scales, in a contact-free manner. EXPERIMENTAL: A system consisting of 12-hydroxysteric acid (HSA) soaps mixed with different ratios of monoethanolamine (MEA) and choline hydroxide, was prepared. Microliter droplets of the samples were acoustically levitated and monitored with a camera, while exposed to CO2 to modify the pH through diffusion at the air-liquid interface and inside the droplet. The phase transition and water mobility in the levitated droplets were evaluated through X-ray scattering (SAXS/WAXS) and magnetic resonance studies, in real-time. Finally, the droplets were collected and examined under the microscope. FINDINGS: The introduction of CO2 gas induced a phase transition from micelles to multi-lamellar tubes, resulting in a gel-like behavior both in the bulk and at the interface. The high stability of the acoustic levitator allowed the investigation of this dynamic phenomenon, in real-time, in a contact-free environment. This study showcases the suitability of acoustic levitation as a tool to investigate complex chemical processes at interfaces.