The mechanics of active clays circulated by salts, acids and bases: Comprehensive version

An elastic-plastic model that accounts for electro-chemo-mechanical couplings in clays, due to the presence of dissolved salts and acids and bases, is developed here for the first time. To the authors' best knowledge, no other comprehensive project to embody the effects of pH in the elastic-plastic behavior of geomaterials has been attempted so far. Chemically sensitive clays are viewed as two-phase multi-species saturated porous media circulated by an electrolyte. The developments are embedded in the framework of the thermodynamics of multi-phase multi-species porous media. This approach serves to structure the model, and to motivate constitutive equations. The present extension capitalize upon the earlier developments by Gajo et al. [2002] and Gajo and Loret [2004], which were devoted to modeling chemo-mechanical couplings at constant pH. Four transfer mechanisms between the solid and fluid phases are delineated in the model: (1) hydration, (2) ion exchange, (3) acidification, (4) alkalinization. Thus all fundamental exchanges at particle level are fully taken into account. Only mineral dissolution is neglected, since experimental observations indicates a negligible role of mineral dissolution for active clays at room temperature. In particular, the newly considered mechanisms of acidification and alkalinization directly affect the electrical charge of clay particles and thus have a key role in the electro-chemo-mechanical couplings. These four mechanisms are seen as controlling both elastic and elasto-plastic behaviors. Depending on concentrations and ionic affinities to the clay mineral, these mechanisms either compete or cooperate to modify the compressibility and strength of the clay and may induce swelling (volume expansion) or shrinking (volume contraction). The framework is rich enough to allow for the simulations of recently performed laboratory experiments on clay samples submitted to intertwined mechanical and chemical loading programmes, involving large changes in ionic strengths and pH. This work is the comprehensive version of the paper published on the Journal of the Mechanics and Physics of Solids, 55(8), 1762-180

Dual sensing-actuation artificial muscle based on polypyrrole-carbon nanotube composite

Dual sensing artificial muscles based on conducting polymer are faradaic motors driven by electrochemical reactions, which announce the development of proprioceptive devices. The applicability of different composites has been investigated with the aim to improve the performance. Addition of carbon nanotubes may reduce irreversible reactions. We present the testing of a dual sensing artificial muscle based on a conducting polymer and carbon nanotubes composite. Large bending motions (up to 127 degrees) in aqueous solution and simultaneously sensing abilities of the operation conditions are recorded. The sensing and actuation equations are derived for incorporation into a control system.The research was supported by European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No 641822

Spiropyran-based reversible, light-modulated sensing with reduced photofatigue

Switchable materials have tremendous potential for application in sensor development that could be applied to many fields. We are focusing on emerging area of wireless sensor networks due to the potential impact of this concept in society. Spiropyran-based sensors are probably the most studied type of photoswitchable sensing devices. They suffer from many issues but photofatigue, insufficient selectivity and lack of sensitivity are probably the most important characteristics that hinder their wider application. Here, we are address these issues and demonstrate that covalent attachment of modified spiropyran into a polymeric film significantly reduces photodegradation. The observed signal loss after 12th cycle of switching between the spiropyran and merocyanine forms is only about 27% compared to the loss of 57% of the initial signal in an equivalent experiment based on non-immobilized spiropyran. This has enabled us to demonstrate at least five reversible cycles of detection of an ion of interest (in our case H+) with minimal signal loss. Furthermore, we demonstrate that the sensitivity can be increased by incorporation of additional binding groups in the parent spiropyran molecule. Using molecular modelling to calculate the relevant bond lengths as a measure of interaction between MC and H+, the calculated increase of H-bond strength is approximately an order of magnitude for a derivative containing a methoxy group incorporated in the o-position of the parent spiropyran in comparison to the equivalent unsubstituted phenol. This theoretical result was found to correspond very well with experimental observation. As a result, we have increased the sensitivity to H+ by approximately one order of magnitude

Targeting Btk/Etk of prostate cancer cells by a novel dual inhibitor.

Btk and Etk/BMX are Tec-family non-receptor tyrosine kinases. Btk has previously been reported to be expressed primarily in B cells and has an important role in immune responses and B-cell malignancies. Etk has been shown previously to provide a strong survival and metastasis signal in human prostate cancer cells, and to confer androgen independence and drug resistance. While the role of Etk in prostate carcinogenesis is well established, the functions of Btk in prostate cancer have never been investigated, likely due to the perception that Btk is a hematopoietic, but not epithelial, kinase. Herein, we found that Btk is overexpressed in prostate cancer tissues and prostate cancer cells. The level of Btk in prostate cancer tissues correlates with cancer grades. Knockdown of Btk expression selectively inhibits the growth of prostate cancer cells, but not that of the normal prostate epithelial cells, which express very little Btk. Dual inhibition of Btk and Etk has an additive inhibitory effect on prostate cancer cell growth. To explore Btk and Etk as targets for prostate cancer, we developed a small molecule dual inhibitor of Btk and Etk, CTN06. Treatment of PC3 and other prostate cancer cells, but not immortalized prostate epithelial cells with CTN06 resulted in effective cell killing, accompanied by the attenuation of Btk/Etk signals. The killing effect of CTN06 is more potent than that of commonly used inhibitors against Src, Raf/VEGFR and EGFR. CTN06 induces apoptosis as well as autophagy in human prostate cancer cells, and is a chemo-sensitizer for docetaxel (DTX), a standard of care for metastatic prostate cancer patients. CTN06 also impeded the migration of human prostate cancer cells based on a 'wound healing' assay. The anti-cancer effect of CTN06 was further validated in vivo in a PC3 xenograft mouse model

Suppression of eukaryotic initiation factor 4E prevents chemotherapy-induced alopecia

BACKGROUND: Chemotherapy-induced hair loss (alopecia) (CIA) is one of the most feared side effects of chemotherapy among cancer patients. There is currently no pharmacological approach to minimize CIA, although one strategy that has been proposed involves protecting normal cells from chemotherapy by transiently inducing cell cycle arrest. Proof-of-concept for this approach, known as cyclotherapy, has been demonstrated in cell culture settings. METHODS: The eukaryotic initiation factor (eIF) 4E is a cap binding protein that stimulates ribosome recruitment to mRNA templates during the initiation phase of translation. Suppression of eIF4E is known to induce cell cycle arrest. Using a novel inducible and reversible transgenic mouse model that enables RNAi-mediated suppression of eIF4E in vivo, we assessed the consequences of temporal eIF4E suppression on CIA. RESULTS: Our results demonstrate that transient inhibition of eIF4E protects against cyclophosphamide-induced alopecia at the organismal level. At the cellular level, this protection is associated with an accumulation of cells in G1, reduced apoptotic indices, and was phenocopied using small molecule inhibitors targeting the process of translation initiation. CONCLUSIONS: Our data provide a rationale for exploring suppression of translation initiation as an approach to prevent or minimize cyclophosphamide-induced alopecia.1U01 CA168409 - NCI NIH HHS; P01 CA 87497 - NCI NIH HHS; P30 CA008748 - NCI NIH HHS; MOP-106530 - Canadian Institutes of Health Research; P01 CA013106 - NCI NIH HH

Schizophrenic molecules and materials with multiple personalities - how materials science could revolutionise how we do chemical sensing

Molecular photoswitches like spiropyrans derivatives offer exciting possibilities for the development of analytical platforms incorporating photo-responsive materials for functions such as light-activated guest uptake and release and optical reporting on status (passive form, free active form, guest bound to active form). In particular, these switchable materials hold tremendous promise for microflow-systems, in view of the fact that their behaviour can be controlled and interrogated remotely using light from LEDs, without the need for direct physical contact. We demonstrate the immobilisation of these materials on microbeads which can be incorporated into a microflow system to facilitate photoswitchable guest uptake and release. We also introduce novel hybrid materials based on spiropyrans derivatives grafted onto a polymer backbone which, in the presence of an ionic liquid, produces a gel-like material capable of significant photoactuation behaviour. We demonstrate how this material can be incorporated into microfluidic platforms to produce valve-like structures capable of controlling liquid movement using light

Molecules with multiple personalities: how switchable materials could revolutionise chemical sensing

Worldwide, the demand for sensing devices that can conform with the requirements of large-scale wireless sensor network (WSN) deployments is rising exponentially. Typically, sensors should be very low cost, low power (essentially self-sustaining), yet very rugged and reliable. At present, functioning WSN deployments involve physical transducers only, such as thermistors, accelerometers, photodetectors, or flow meters, to monitor quantities like temperature, movement, light level and liquid level/flow. Remote, widely distributed monitoring of molecular targets remains relatively unexplored, except in the case of targets that can be detected directly using ‘non-contact’ techniques like spectroscopy. This paper will address the issues inhibiting the close integration of chemical sensing with WSNs and suggest strategies based on fundamental materials science that may offer routes to new sensing surfaces that can switch between different modes of behaviour (e.g. active-passive, expand-contract)

Chromoionophores in optical ion sensors

The feasibility of surface plasmon resonance (SPR) for ion sensing has been investigated. Emphasis is laid on a simulation-based optimization of the SP carrying structure, as well as the applicability of a specific chemo—optical interface we have developed. A preliminary result is presented

The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations.

The effect of host structure on the selectivity and mechanism of intramolecular Prins reactions is evaluated using K12Ga4L6 tetrahedral catalysts. The host structure was varied by modifying the structure of the chelating moieties and the size of the aromatic spacers. While variation in chelator substituents was generally observed to affect changes in rate but not selectivity, changing the host spacer afforded differences in efficiency and product diastereoselectivity. An extremely high number of turnovers (up to 840) was observed. Maximum rate accelerations were measured to be on the order of 105, which numbers among the largest magnitudes of transition state stabilization measured with a synthetic host-catalyst. Host/guest size effects were observed to play an important role in host-mediated enantioselectivity