Surface-Enhanced Raman Scattering of Phenols and Catechols by a Molecular Analogue of Titanium Dioxide.

Surface-enhanced Raman spectroscopy (SERS) of semiconducting TiO2 was used for studying binding modes and surface reactions of molecules bound at the interface but is generally limited by low signal intensity and lack of authentic structural information. Here, we report a representative titanium-oxide cluster (TOC), i.e., Ti17O24(OiC3H7)20 (Ti17), combines the benefits from both precise structures and intense SERS signals by providing a titania surface. According to the single-crystal X-ray diffraction analysis, phenols and catechols are vertically attached via σ-bonds to the certain sites of Ti17. Ti17 brings about much more intense Raman signals than the reference TiO2 NPs, leading to 10-5-10-6 M analyte detection (enhancement factors are 103-105). The contributions of focusing effect, CHEM effect and resonance mechanism, all of which are found responsible for the higher SERS activity of Ti17 than the reference TiO2 NPs, in the SERS by Ti17 are quantitatively analyzed. This study suggests SERS by TOCs may be promising for detection purposes and structural studies of environmentally and catalytically relevant molecules with fewer assumptions regarding molecular structures or binding mechanisms.

Peptide-Based Polymer-Polyoxometalate Supramolecular Structure with a Differed Antimicrobial Mechanism.

Because of the increasing prevalence of multidrug resistance feature, several investigations have been so far reported regarding the antibiotic alternative supramolecular bioactive agents made of hybrid assemblies. In this regard, it is well-established that combinational therapy inherited by assembled supramolecular structures can improve the bioactivity to some extent, but their mode of action has not been studied in detail. We provide first direct evidence that the improved mechanism of action of antimicrobial supra-amphiphilic nanocomposites differs largely from their parent antimicrobial peptide-based polymers. For the construction of a hybrid combinational system, we have synthesized side-chain peptide-based antimicrobial polymers via RAFT polymerization and exploited their cationic nature to decorate supra-amphiphilic nanocomposites via interaction with anionic polyoxometalates. Because of cooperative antimicrobial properties of both the polymer and polyoxometalate, the nanocomposites show an enhanced antimicrobial activity with a different antimicrobial mechanism. The cationic stimuli-responsive peptide-based polymers attack bacteria via membrane disruption mechanism, whereas free radical-mediated cell damage is the likely mechanism of polymer-polyoxometalate-based supra-amphiphilic nanocomposites. Thus, our study highlights the different antimicrobial mechanism of combinational systems in detail, which improves our understanding of enhanced antimicrobial efficacy.

Supramolecular polyelectrolyte complex (SPEC): pH dependent phase transition and exploitation of its carrier properties.

A supramolecular poly-electrolyte complex (SPEC) comprising poly-electrolyte acrylic acid with supramolecularly complexed guanidium is reported. This complex shows pH responsive phase transitions, which are described and characterized using microscopy, spectroscopy, density functional theory studies and Monte Carlo simulations. The phase behaviour of the SPEC is exploited by loading a dye like perylene and a drug, viz., doxorubicin, and their pH dependent controlled release is demonstrated, owing to the pH dependent phase change of the SPEC.

Direct Observation of the Formation Pathway of [Mo132] Keplerates.

The formation pathway of a closed spherical cluster [Mo132], starting from a library of building blocks of molybdate anions, has been reported. Electrospray ionization mass spectrometry, Raman spectroscopy, and theoretical studies describe the formation of such a complex cluster from a reduced and acidified aqueous solution of molybdate. Understanding the emergence of such an enormous spherical model cluster may lead to the design of new clusters in the future. Formation of such a highly symmetric cluster is principally controlled by charge balance and the emergence of more symmetric structures at the expense of less symmetric ones.

Polyoxometalate-Polymer Directed Macromolecular Architectonics of Silver Nanoparticles as Effective Antimicrobials.

A novel inorganic-organic-inorganic ternary bioactive material formulated on antimicrobial peptide-based polymer has been reported. Supramolecular approach has been employed to incorporate molecularly crowded tyrosine-based polymer stabilized silver nanoparticles into membrane bound vesicles exploiting polyoxometalate-triggered surface templating strategy. Utilizing the covalent reversible addition fragmentation chain transfer (RAFT) polymerization and exploiting templated supramolecular architectonics at biopolymer interface, the bioactive ternary polymeric nanohybrids have been designed against Shigellosis leveraging the antibacterial activities of silver nanoparticle, cationic amphiphilic tyrosine polymer and inorganic polyoxometalate. The detail investigation against Shigella flexneri 2a cell line demonstrates that the collaborative mechanism of the ternary hybrid composite enhances the bactericidal activity in comparison to only polyoxometalate and polymer stabilized silver nanoparticle with an altered mechanism of action which is established via detailed biological analysis.

In Operando Spectroscopic Ellipsometry Investigation of MOF Thin Films for the Selective Capture of Acetic Acid.

The emission of polar volatile organic compounds (VOCs) is a major worldwide concern of air quality and equally impacts the preservation of cultural heritage (CH). The challenge is to design highly efficient adsorbents able to selectively capture traces of VOCs such as acetic acid (AA) in the presence of relative humidity (RH) normally found at storage in museums (40-80%). Although the selective capture of VOCs over water is still challenging, metal-organic frameworks (MOFs) possess highly tunable features (Lewis, Bronsted, or redox metal sites, functional groups, hydrophobicity, etc.) suitable to selectively capture a large variety of VOCs. In this context, we have explored the adsorption efficiency of a series of MOFs thin films (ZIF-8(Zn), MIL-101(Cr), and UiO-66(Zr)-2CF3) for the selective capture of AA based on a UV/vis and FT-IR spectroscopic ellipsometry in operando study (2-6% of relative pressure of AA under 40% of RH), namely conditions close to the realistic environmental storage conditions of cultural artifacts. For that purpose, optical quality thin films of MOFs were prepared by dip-coating, and their AA adsorption capacity and selectivity were evaluated under humid conditions by measuring the variation of the refractive index as a function of the vapor pressures while the chemical nature of the coadsorbed analytes (water and AA) was identified by FT-IR ellipsometry. While thin films of ZIF-8(Zn) strongly degraded upon exposure to AA/water vapors, films of MIL-101(Cr) and UiO-66(Zr)-2CF3 present a high chemical stability under those conditions. It was shown that MIL-101(Cr) presents a high AA adsorption capacity due to its high pore volume but exhibits a poor AA adsorption selectivity under humid conditions. In contrast, UiO-66(Zr)-2CF3 was shown to overpass MIL-101(Cr) in terms of AA/H2O adsorption selectivity and AA adsorption/desorption cycling stability because of its high hydrophobic character, suitable pore size for adequate confinement, and specific interactions.

MIL-101(Cr) MOF as an Effective Siloxane Sensor.

Volatile methylsiloxanes (VMSs) are common silicone degradation byproducts that cause serious concern for the contamination of sensitive electronics and optics, among others. With the goal of fast, online detection of VMS, we herein highlight the mesoporous MIL-101(Cr) MOF as a promising mass sensing layer for integration with a quartz crystal microbalance (QCM), using an in-house modified gravimetric adsorption system capable of achieving extremely low concentrations of siloxane D4 (down to 0.04 ppm), targeting applications for monitoring in indoor spaces and spacecraft. Our developed MIL-101(Cr)@QCM sensor achieves near-perfect reversibility with no hysteresis alongside excellent repeatability over cycling and fast response/recovery times under 1 min. We attribute this capability to optimum host/guest interactions as uncovered through molecular simulations.