Thenoyltrifluoroacetone (TTA)-Carbon Dot/Aerogel Fluorescent Sensor for Lanthanide and Actinide Ions.

Contamination of groundwater with radioactive substances comprising actinides and lanthanides is a significant environmental hazard and thus the development of selective, sensitive, and easy-to-apply sensors for water-soluble actinide and lanthanide ions is highly sought. We constructed a new selective fluorescent sensor for UO2 2+, Sm3+, and Eu3+ based on a carbon dot (C-dot)-aerogel hybrid prepared through in situ carbonization of 2-thenoyltrifluoroacetone (TTA), a high-affinity heavy metal chelator. The TTA-C-dot-aerogel enabled the detection of UO2 2+ ions, which induced a significant red fluorescence shift, whereas Eu3+ and particularly Sm3+ ions gave rise to pronounced fluorescence quenching. Importantly, the lanthanide/actinide ion-selective TTA-C-dots could be synthesized only in situ inside the aerogel pores, indicating the crucial role of the aerogel host matrix both in enabling the formation of the C-dots and in promoting the adsorption and interactions of the lanthanide and actinide metal ions with the embedded C-dots.

Bifunctional Carbon-Dot-WS2 Nanorods for Photothermal Therapy and Cell Imaging.

Multifunctional nanoparticles have attracted significant interest as biomedical vehicles, combining diagnostic, imaging, and therapeutic properties. We describe herein the construction of new nanoparticle conjugates comprising WS2 nanorods (NRs) coupled to fluorescent carbon dots (C-dots). We show that the WS2 -C-dot hybrids integrate the unique physical properties of the two species, specifically the photothermal activity of the WS2 NRs upon irradiation with near-infrared (NIR) light and the excitation-dependent luminescence emission of the C-dots. The WS2 -C-dot NRs have been shown to be non-cytotoxic and have been successfully employed for multicolour cell imaging and targeted cell killing under NIR irradiation, pointing to their potential utilization as effective therapeutic vehicles.

Colorimetric Polydiacetylene-Aerogel Detector for Volatile Organic Compounds (VOCs).

A new hybrid system comprising polydiacetylene (PDA), a chromatic conjugated polymer, embedded within aerogel pores has been constructed. The PDA-aerogel powder underwent dramatic color changes in the presence of volatile organic compounds (VOCs), facilitated through infiltration of the gas molecules into the highly porous aerogel matrix and their interactions with the aerogel-embedded PDA units. The PDA-aerogel composite exhibited rapid color/fluorescence response and enhanced signals upon exposure to low VOC concentrations. Encapsulation of PDA derivatives displaying different headgroups within the aerogel produced distinct VOC-dependent color transformations, forming a PDA-aerogel "artificial nose".

Carbon-Dot/Silver-Nanoparticle Flexible SERS-Active Films.

Development of effective platforms for surface enhanced Raman scattering (SERS) sensing has mostly focused on fabrication of colloidal metal surfaces and tuning of their surface morphologies, designed to create "hot spots" in which plasmonic fields yield enhanced SERS signals. We fabricated distinctive SERS-active flexible films comprising polydimethylsiloxane (PDMS) embedding carbon dots (C-dots) and coated with silver nano-particles (Ag NPs). We show that the polymer-associated Ag NPs and C-dots intimately affected the physical properties of each other. In particular, the C-dot-Ag-NP-polymer films exhibited SERS properties upon deposition of versatile targets, both conventional SERS-active dyes as well as bacterial samples. We show that the SERS response was correlated to the formation C-dots within the polymer film and the physical proximity between the C-dots and Ag NPs, indicating that coupling between the plasmonic fields of the Ag NPs and C-dots' excitons constituted a prominent factor in the SERS properties.

Detection of Vero Cells Infected with Herpes Simplex Types 1 and 2 and Varicella Zoster Viruses Using Raman Spectroscopy and Advanced Statistical Methods.

Of the eight members of the herpes family of viruses, HSV1, HSV2, and varicella zoster are the most common and are mainly involved in cutaneous disorders. These viruses usually are not life-threatening, but in some cases they might cause serious infections to the eyes and the brain that can lead to blindness and possibly death. An effective drug (acyclovir and its derivatives) is available against these viruses. Therefore, early detection and identification of these viral infections is highly important for an effective treatment. Raman spectroscopy, which has been widely used in the past years in medicine and biology, was used as a powerful spectroscopic tool for the detection and identification of these viral infections in cell culture, due to its sensitivity, rapidity and reliability. Our results showed that it was possible to differentiate, with a 97% identification success rate, the uninfected Vero cells that served as a control, from the Vero cells that were infected with HSV-1, HSV-2, and VZV. For that, linear discriminant analysis (LDA) was performed on the Raman spectra after principal component analysis (PCA) with a leave one out (LOO) approach. Raman spectroscopy in tandem with PCA and LDA enable to differentiate among the different herpes viral infections of Vero cells in time span of few minutes with high accuracy rate. Understanding cell molecular changes due to herpes viral infections using Raman spectroscopy may help in early detection and effective treatment.

Nanostructure synthesis at the solid-water interface: spontaneous assembly and chemical transformations of tellurium nanorods.

Bottom-up synthesis offers novel routes to obtain nanostructures for nanotechnology applications. Most self-assembly processes are carried out in three dimensions (i.e. solutions); however, the large majority of nanostructure-based devices function in two dimensions (i.e. on surfaces). Accordingly, an essential and often cumbersome step in bottom-up applications involves harvesting and transferring the synthesized nanostructures from the solution onto target surfaces. We demonstrate a simple strategy for the synthesis and chemical transformation of tellurium nanorods, which is carried out directly at the solid-solution interface. The technique involves binding the nanorod precursors onto amine-functionalized surfaces, followed by in situ crystallization/oxidation. We show that the surface-anchored tellurium nanorods can be further transformed in situ into Ag2Te, Cu2Te, and SERS-active Au-Te nanorods. This new approach offers a way to construct functional nanostructures directly on surfaces.

Poly(methyl methacrylate)-supported polydiacetylene films: unique chromatic transitions and molecular sensing.

Polydiacetylenes (PDAs) constitute a family of conjugated polymers exhibiting unique colorimetric and fluorescence transitions, and have attracted significant interest as chemo- and biosensing materials. We spin-coated PDA films upon poly(methyl methacrylate) (PMMA), and investigated the photophysical properties and sensing applications of the new PDA configuration. Specifically, the as-polymerized blue PDA layer underwent distinct transformations to purple, red, and yellow phases, which could be quantified through conventional color scanning combined with application of image analysis algorithms. Furthermore, we recorded a reversible red-purple PDA transition that was induced by ultraviolet irradiation, a phenomenon that had not been reported previously in PDA film systems. We show that distinct color and fluorescence transitions were induced in the PMMA-supported PDA films by amphiphilic substances-surfactants and ionic liquids-and that the chromatic transformations were correlated to the analyte structures and properties. Overall, this study presents a new chromatic PDA film system in which noncovalent interactions between the PMMA substrate and spin-coated PDA give rise to distinct chromatic properties and molecular sensing capabilities.

Transparent, conductive, and SERS-active Au nanofiber films assembled on an amphiphilic peptide template.

The use of biological materials as templates for functional molecular assemblies is an active research field at the interface between chemistry, biology, and materials science. We demonstrate the formation of gold nanofiber films on ß-sheet peptide domains assembled at the air/water interface. The gold deposition scheme employed a recently discovered chemical process involving spontaneous crystallization and reduction of water-soluble Au(SCN)4(1-) upon anchoring to surface-displayed amine moieties. Here we show that an interlinked network of crystalline Au nanofibers is readily formed upon incubation of the Au(iii) thiocyanate complex with the peptide monolayers. Intriguingly, the resultant films were optically transparent, enabled electrical conductivity, and displayed pronounced surface enhanced Raman spectroscopy (SERS) activity, making the approach a promising avenue for construction of nano-structured films exhibiting practical applications.

Silver nanoparticles deposited on porous silicon as a surface-enhanced Raman scattering (SERS) active substrate.

Silver nanoparticles were deposited spontaneously from their aqueous solution on a porous silicon (PS) layer. The PS acts both as a reducing agent and as the substrate on which the nanoparticles nucleate. At higher silver ion concentrations, layers of nanoparticle aggregates were formed on the PS surface. The morphology of the metallic layers and their SERS activity were influenced by the concentrations of the silver ion solutions used for deposition. Raman measurements of rhodamine 6G (R6G) and crystal violet (CV) adsorbed on these surfaces showed remarkable enhancement of up to about 10 orders of magnitude.

Effect of metal cations on polydiacetylene Langmuir films.

Polydiacetylene (PDA) Langmuir films (LFs) are a unique class of materials that couple a highly aligned conjugated backbone with tailorable pendant side groups and terminal functionalities. The films exhibit chromatic transitions from monomer to blue polymer and finally to a red phase that can be activated optically, thermally, chemically, and mechanically. The properties of PDA LFs are strongly affected by the presence of metal cations in the aqueous subphase of the film due to their interaction with the carboxylic head groups of the polymer. In the present study the influence of divalent cadmium, barium, copper, and lead cations on the structural, morphological, and optical properties of PDA LFs was investigated by means of surface pressure-molecular area (π-A) isotherms, atomic force microscopy, optical absorbance, and Raman spectroscopy. The threshold concentrations for the influence of metal cations on the film structure, stability, and phase transformation were determined by π-A analyses. It was found that each of the investigated cations has a unique influence on the properties of PDA LFs. Cadmium cations induce moderate phase transition kinetics with reduced domain size and fragmented morphology. Barium cations contribute to stabilization of the PDA blue phase and enhanced linear strand morphology. On the other hand, copper cations enhance rapid formation of the PDA red phase and cause fragmented morphology of the film, while the presence of lead cations results in severe perturbation of the film with only a small area of the film able to be effectively polymerized. The influence of the metal cations is correlated with the solubility product (K(sp)), association strength, and ionic-covalent bond nature between the metal cations and the PDA carboxylic head groups.

Flexible pores of a metal oxide-based capsule permit entry of comparatively larger organic guests.

In zeolites and other rigid solid-state oxides, substrates whose sizes exceed the pore dimensions of the material are rigorously excluded. Now, using a porous 3 nm diameter capsule-like oxomolybdate complex [{Mo(VI)(6)O(21)(H(2)O)(6)}(12){(Mo(V)(2)O(4))(30)(OAc)(21)(H(2)O)(18)}](33-) as a water-soluble analogue of solid-state oxides (e.g., as a soluble analogue of 3 A molecular sieves), we show that carboxylates (RCO(2)(-)) can negotiate passage through flexible Mo(9)O(9) pores in the surface of the capsule and that the rates follow the general trend R = 1 degree >> 2 degrees > 3 degrees >> phenyl (no reaction). Surprisingly, the branched alkanes (R = iso-Pr and tert-Bu) enter the capsule even though they are larger than the crystallographic dimensions of the Mo(9)O(9) pores. Four independent lines of spectroscopic and kinetic evidence demonstrate that these organic guests enter the interior of the capsule through its Mo(9)O(9) apertures and that no irreversible changes in the metal oxide framework are involved. This unexpected phenomenon likely reflects the greater flexibility of molecular versus solid-state structures and represents a sharp departure from traditional models for diffusion through porous solid-state (rigid) oxides.

Two-photon polymerization of polydiacetylene.

We show that visible light can polymerize diacetylene monomers into polydiacetylene (PDA) in a two-photon process. We monitor the process by measuring Raman intensities of PDA using a Raman laser at 633 nm with variable intensity I and show that the Raman cross section at short times increases as I3, corresponding to a two-photon process. The process generates a relatively stable blue phase PDA, in contrast with UV polymerization that leads to a fast blue to red phase transformation.

Lipid/polydiacetylene films for colorimetric protein surface-charge analysis.

The distribution and organization of charges on a protein surface are fundamental properties which affect protein functions and interactions. We demonstrate a new approach for protein surface-charge analysis through modulating protein interactions with chromatic lipid/polydiacetylene (PDA) films. We show that visible and easily quantifiable blue-red transitions, induced on the film surface through electrostatic interactions between the negatively charged PDA and positive soluble species, constitute an effective means for characterizing protein surface charge. Specifically, protein-film interactions can be significantly modulated by complexation between the tested macromolecules and lipid-embedded multivalent calixarene ligands displaying charged residues, making possible protein discrimination based upon the abundance and organization of surface charge. The lipid/PDA film system, in conjunction with the calixarene-derived ligands, facilitates characterization of protein surface charges and identification of anomalous protein electrostatic properties.

Raman and infrared fingerprint spectroscopy of peroxide-based explosives.

A comparative study of the vibrational spectroscopy of peroxide-based explosives is presented. Triacetone triperoxide (TATP) and hexamethyl-enetriperoxide-diamine (HMTD), now commonly used by terrorists, are examined as well as other peroxide-ring structures: DADP (diacetone diperoxide); TPTP [3,3,6,6,9,9-Hexaethyl-1,2,4,5,7,8-hexaoxo-nonane (tripentanone triperoxide)]; DCypDp {6,7,13,14-Tetraoxadispiro [4.2.4.2]tetradecane (dicyclopentanone diperoxide)}; TCypDp {6,7,15,16,22,23-Hexaoxatrispiro[4.2.4.2.4.2] henicosane (tricyclopentanone triperoxide)}; DCyhDp {7,8,15,16-tetraoxadispiro [5.2.5.2] hexadecane (dicyclohexanone diperoxide)}; and TCyhTp {7,8,14,15,21,22-hexaoxatrispiro [5.2.5.2.5.2] tetracosane (tricyclohexanone triperoxide)}. Both Raman and infrared (IR) spectra were measured and compared to theoretical calculations. The calculated spectra were obtained by calculation of the harmonic frequencies of the studied compounds, at the density functional theory (DFT) B3LYP/cc-pVDZ level of theory, and by the use of scaling factors. It is found that the vibrational features related to the peroxide bonds are strongly mixed. As a result, the spectrum is congested and highly sensitive to minor changes in the molecule.

Synthesis, two-dimensional assembly, and surface pressure-induced coalescence of ultranarrow PbS nanowires.

Ultranarrow (1.8 nm) PbS nanowires are synthesized in a single step, under benchtop conditions at relatively low temperature (90 degrees C). The nanowires exhibit a nearly perfect crystal lattice, high width uniformity, and tight side-by-side registry. Two-dimensional (2D) assembly over large areas (>15 microm2) is achieved using the Langmuir Blodgett method. The wire width can be readily controlled in the range 1.8-10 nm by a surface pressure-induced coalescence reaction, as monitored by transmission electron microscopy and Raman spectroscopy. The fluorescence of the 2D assembly shows strong polarization dependence along the long axis of the wires, making the system potentially suitable for orientation-sensitive devices.