Supramolecular polymer networks based on cucurbit[8]uril host-guest interactions as aqueous photo-rheological fluids

A low-mass fraction (≤0.75 wt%) supramolecular polymer network is fabricated as an aqueous photo-rheological fluid (PRF) via cucurbit[8]uril mediated host–guest interactions. UV irradiation can induce the transition from a highly viscous and rigid gel into a Newtonian-like fluid.C.S.Y.T. thanks Ministry of Education of Malaysia and MARA University of Technology for their financial supports. J. L. is financially supported by the Marie Curie FP7 SASSYPOL ITN programme. J.d.B. is grateful for a Marie Curie Intra-European Fellowship (Project 273807). O.A.S thanks the ERC for their funding.This is the final version of the article. It first appeared from RSC via http://dx.doi.org/10.1039/C5PY01115

Preparation and Supramolecular Recognition of Multivalent Peptide-Polysaccharide Conjugates by Cucurbit[8]uril in Hydrogel Formation.

Supramolecular hydrogels were fabricated by physically cross-linking phenylalanine functionalized polysaccharides with cucurbit[8]uril in water. We report a facile 2-step method of functionalization of the polysaccharides hyaluronic acid (HA), carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), and guar with the dipeptide Phe-Cys. Addition of cucurbit[8]uril to the functional polysaccharides initiated physical cross-linking on account of strong 1:2 "homoternary" complexes with the pendant Phe residues. In particular, HA and CMC based soft hydrogels displayed impressive viscoelastic behavior which was characterized using rheology, demonstrating accessibility to an array of material properties which would find broad applicability in many fields.M.J.R. thanks the University of Cambridge Chemical Biology and Molecular Medicine PhD Training Programme for funding. OAS thanks ERC Starting Investigator Grant (ASPiRe). The authors would also like to thank Silvia Sonzini for her assistance with collecting ITC data.This is the author accepted manuscript. The final version is available from ACS via http://dx.doi.org/10.1021/acs.biomac.5b0068

Patterned Arrays of Supramolecular Microcapsules

Micropatterning of hydrogel has brought innovative outcomes in fundamental and applied material sciences. Previous approaches have mainly been dedicated to fabricate arrays of bulk hydrogel beads, which have inherent challenges including loading ability, scalability, specificity and versatility. Here we present a methodology to create hollow microcapsule arrays from sessile microdroplets. The difference in wettability between hydrophilic and hydrophobic surfaces enables self-partitioning of liquid into microdroplet arrays, serving as microreservoirs to load complementarily-functionalized host-guest polymers, cucurbit[8]uril-threaded highly-branched polyrotaxanes (HBP-CB[8]) and naphthyl-functionalized hydroxyethyl cellulose (HEC-Np). The interfacial dynamic complexation between positively-charged HBP-CB[8] and HECNp occurred in the presence of negatively-charged surfactants, resulting in condensed supramolecular hydrogel skins. The hydrogel microcapsules were uniform in size, and were developed to encapsulate target cargos in a robust and well-defined manner. Moreover, the microcapsule substrates were further used for surface enhanced Raman spectroscopy (SERS) sensing upon loading of gold nanoparticles. This facile assembly of microcapsule arrays has potential applications in controlled cargo delivery, bio-sensing, high throughput analysis and sorting

Electromagnetically induced transparency in inhomogeneously broadened Lambda-transition with multiple excited levels

Electromagnetically induced transparency (EIT) has mainly been modelled for three-level systems. In particular, a considerable interest has been dedicated to the Lambda-configuration, with two ground states and one excited state. However, in the alkali-metal atoms, which are commonly used, hyperfine interaction in the excited state introduces several levels which simultaneously participate in the scattering process. When the Doppler broadening is comparable with the hyperfine splitting in the upper state, the three-level Lambda model does not reproduce the experimental results. Here we theoretically investigate the EIT in a hot vapor of alkali-metal atoms and demonstrate that it can be strongly reduced due to the presence of multiple excited levels. Given this model, we also show that a well-designed optical pumping enables to significantly recover the transparency

Optical imaging of luminescence for in vivo quantification of gene electrotransfer in mouse muscle and knee

BACKGROUND: Optical imaging is an attractive non-invasive way to evaluate the expression of a transferred DNA, mainly thanks to its lower cost and ease of realization. In this study optical imaging was evaluated for monitoring and quantification of the mouse knee joint and tibial cranial muscle electrotransfer of a luciferase encoding plasmid. Optical imaging was applied to study the kinetics of luciferase expression in both tissues. RESULTS: The substrate of luciferase (luciferin) was injected either intraperitonealy (i.p.) or in situ into the muscle or the knee joint. Luminescence resulting from the luciferase-luciferin reaction was measured in vivo with a cooled CCD camera and/or in vitro on tissue lysate. Maximal luminescence of the knee joint and muscle after i.p. (2.5 mg) or local injection of luciferin (50 μg in the knee joint, 100 μg in the muscle) were highly correlated. With the local injection procedure adopted, in vivo and in vitro luminescences measured on the same muscles significantly correlated. Luminescence measurements were reproducible and the signal level was proportional to the amount of plasmid injected. In vivo luciferase activity in the electrotransfered knee joint was detected for two weeks. Intramuscular electrotransfer of 0.3 or 3 μg of plasmid led to stable luciferase expression for 62 days, whereas injecting 30 μg of plasmid resulted in a drop of luminescence three weeks after electrotransfer. These decreases were partially associated with the development of an immune response. CONCLUSION: A particular advantage of the i.p. injection of substrate is a widespread distribution at luciferase production sites. We have also highlighted advantages of local injection as a more sensitive detection method with reduced substrate consumption. Besides, this route of injection is relatively free of uncontrolled parameters, such as diffusion to the target organ, crossing of biological barriers and evidencing variations in local enzymatic kinetics, probably related to the reaction medium in the targeted organ. Optical imaging was shown to be a sensitive and relevant technique to quantify variations of luciferase activity in vivo. Further evaluation of the effective amount of luciferase in a given tissue by in vivo optical imaging relies on conditions of the enzymatic reaction and light absorption and presently requires in vitro calibration for each targeted organ

Controlling Spatiotemporal Mechanics of Supramolecular Hydrogel Networks with Highly Branched Cucurbit[8]uril Polyrotaxanes

Attempts to rationally tune the macroscopic mechanical performance of supramolecular hydrogel networks through noncovalent molecular interactions have led to a wide variety of supramolecular materials with desirable functions. While the viscoelastic properties are dominated by temporal hierarchy (crosslinking kinetics), direct mechanistic studies on spatiotemporal control of supramolecular hydrogel networks, based on host-guest chemistry, have not yet been established. Here, supramolecular hydrogel networks assembled from highly branched cucurbit[8]uril-threaded polyrotaxanes (HBP-CB[8] ) and naphthyl-functionalized hydroxyethyl cellulose (HECNp) are reported, exploiting the CB[8] host-guest complexation. Mechanically locking CB[8] host molecules onto a highly branched hydrophilic polymer backbone, through selective binary complexation with viologen derivatives, dramatically increases the solubility of CB[8]. Additionally, the branched architecture enables tuning of material dynamics of the supramolecular hydrogel networks via both topological (spatial hierarchy) and kinetic (temporal hierarchy) control. Relationship between macroscopic properties (time- and temperature-dependent rheological properties, thermal stability, and reversibility), spatiotemporal hierarchy, and chain dynamics of the highly branched polyrotaxane hydrogel networks is investigated in detail. Such kind of tuning of material mechanics through spatiotemporal hierarchy improves our understanding of the challenging relationship between design of supramolecular polymeric materials and their complex viscoelasticity, and also highlights a facile strategy to engineer dynamic supramolecular materials.Ministry of Education of Malaysia and Universiti Teknologi MARA, Marie Curie Fellowship. Grant Number: 65836

A novel thiazolidine compound induces caspase-9 dependent apoptosis in cancer cells

Cataloged from PDF version of article.The forward chemogenomics strategy allowed us to identify a potent cytotoxic thiazolidine compound as an apoptosis-inducing agent. Chemical structures were designed around a thiazolidine ring, a structure already noted for its anticancer properties. Initially, we evaluated these novel compounds on liver, breast, colon and endometrial cancer cell lines. The compound 3 (ALC67) showed the strongest cytotoxic activity (IC50 ∼5 μM). Cell cycle analysis with ALC67 on liver cells revealed SubG1/G1 arrest bearing apoptosis. Furthermore we demonstrated that cytotoxicity of this compound was due to the activation of caspase-9 involved apoptotic pathway, which is death receptor independent. © 2012 Elsevier Ltd. All rights reserve

Quantitative multiplexing with nano-self-assemblies in SERS.

Multiplexed or simultaneous detection of multiple analytes is a valuable tool in many analytical applications. However, complications caused by the presence of interfering compounds in a sample form a major drawback in existing molecular sensor technologies, particularly in multi-analyte systems. Although separating analytes through extraction or chromatography can partially address the problem of interferents, there remains a need for developing direct observational tools capable of multiplexing that can be applied in situ. Surface-enhanced Raman Spectroscopy (SERS) is an optical molecular finger-printing technique that has the ability to resolve analytes from within mixtures. SERS has attracted much attention for its potential in multiplexed sensing but it has been limited in its quantitative abilities. Here, we report a facile supramolecular SERS-based method for quantitative multiplex analysis of small organic molecules in aqueous environments such as human urine.The authors thank Ms. Anna Andreou for the 1H-NMR measurements and acknowledge funding from Walters-Kundert Trust, EPSRC (EP/K028510/1, EP/G060649/1, EP/H007024/1, ERC LINASS 320503), an ERC starting investigator grant (ASPiRe 240629), EU CUBiHOLE grant. S.K. thanks Krebs Memorial Scholarship (The Biochemical Society) and Cambridge Commonwealth Trust for funding.This is the final version of the article. It first appeared from NPG via http://dx.doi.org/10.1038/srep0678