Highly Sensitive Switchable Sensors for Hydroxide on Glass Surfaces Based on Isoquinolinium-Quinolinium-substituted Acetylenes.

Bi-substituted acetylenes with a quinolinium and an isoquinolinium substituent are described, which reversibly form intensely colored adducts with O-nucleophiles and thus enable the detection of >0,5 ppm hydroxide on the surfaces of various glasses. Acids reconstitute the colorless bi-substituted acetylenes. The quinolinium and isoquinolinium rings are bound via their 2-, 3-, 4- and 1-, 3-, 4-positions to the triple bond, respectively. The choice of substitution sites of the hetarenium rings enables the design of mixed conjugated/cross-conjugated π-electron systems. Depending on the combination of binding sites, the frontier orbital profile, the triple bond polarization, the fluorescence behaviour, and the sensitivity to hydroxide differs.

Super-resolution Reflection Microscopy via Absorbance Modulation.

In recent years, fluorescence microscopy has been revolutionized. Reversible switching of fluorophores has enabled circumventing the limits imposed by diffraction. Thus, resolution down to the molecular scale became possible. However, to the best of our knowledge, the application of the principles underlying super-resolution fluorescence microscopy to reflection microscopy has not been experimentally demonstrated. Here, we present the first evidence that this is indeed possible. A layer of photochromic molecules referred to as the absorbance modulation layer (AML) is applied to a sample under investigation. The AML-coated sample is then sequentially illuminated with a one-dimensional (1D) focal intensity distribution (similar to the transverse laser mode TEM01) at wavelength λ1 = 325 nm to create a subwavelength aperture within the AML, followed by illumination with a Gaussian focal spot at λ2 = 633 nm for high-resolution imaging. Using this method, called absorbance modulation imaging (AMI) in reflection, we demonstrate a 2.4-fold resolution enhancement over the diffraction limit for a numerical aperture (NA) of 0.65 and wavelength (λ) of 633 nm.

Bis(thienyl)ethenes with α-methoxymethyl groups. Syntheses, spectroscopic Hammett plots, and stabilities in PMMA films.

A series of bis(thienyl)ethenes (BTEs) possessing perfluorocyclopentene backbones and methoxymethyl groups (MOM) in the 2/2'-positions of the thiophenes was prepared and examined. The substitution pattern of the 5/5'-positions was varied, covering the range from electron-donating to electron-withdrawing. The substituent effects of the absorption wavelengths of the ring-opened and the ring-closed isomers, which are interconverted by reversible 6π-electrocyclizations and cycloreversions, are studied by means of the spectroscopic Hammett equation and the Hammett-Brown equation. Excellent correlations of these linear free energy relationships were found, when the σp values of the Hammett equation, which summarize inductive, mesomeric and field effects, were replaced to the Hammett-Brown σp+ and σp- values which also take direct conjugation into account. We studied solvent effects on the spectroscopic properties and embedded the BTEs into polymethylmethacrylate (PMMA) coatings to examine their fatigue resistance. By our studies, the spectroscopic properties of BTEs can be adjusted by variation of the substitution pattern to a desired excitation wavelength for switching processes.

Buchwald-Hartwig Amination of Aryl Halides with Heterocyclic Amines in the Synthesis of Highly Fluorescent Benzodifuran-Based Star-Shaped Organic Semiconductors.

The study of palladium-catalyzed amination of bromobenzene with aromatic and heterocyclic amines, widely used in the synthesis of organic semiconductors, was performed. The best conditions for the coupling of aryl bromides with carbazole, diphenylamine, phenoxazine, phenothiazine, 9,9-dimethyl-9,10-dihydroacridine, and their derivatives have been developed. Based on the results, nine new star-shaped organic semiconductors, exhibiting up to 100% fluorescent quantum yield in the 400-550 nm range, have been synthesized in good yields. The TDDFT calculations of the absorption spectra revealed a good correlation with experimental results and slight solvatochromic effects with a change in the polarity of the solvent.

Zn2+ detection of a benzimidazole 8-aminoquinoline fluorescent sensor by inhibited tautomerization.

A new fluorescent chemosensor based on 8-aminoquinoline L1 bearing a benzimidazole moiety was synthesized, which exists as two predominant tautomers L1A and L1B in diluted DMSO-d6 solution. Among various metal ions, L1 showed a highly selective and sensitive turn-on fluorescence response to the presence of Zn2+ ions in methanol. The detection limit for Zn2+ by L1 was calculated to be 1.76 × 10-7 M. The 1 : 1 complexation ratio of the L1-Zn complex was confirmed through Job plot measurements. Complexation studies were performed by FT-IR, NMR and HR-ESI MS measurements and DFT calculations. With the gained insight, it was possible to successfully apply L1 in water sample analysis.

Studies of Langmuir and Langmuir-Schaefer Films of Poly(3-Hexylthiophene) and Poly(Vinylidene Fluoride).

The synergistic use of blends of regioregular poly(3-hexylthiophene) (P3HT) and poly(vinylidene fluoride) (PVDF) or poly((vinylidene fluoride)-block-(methyl methacrylate)) (PVDF-PMMA) to form Langmuir and Langmuir-Schaefer (LS) films is reported. P3HT has wide applications in sensor devices because of its properties such as conductivity, luminescence, and chromism; however, the stiffness of the films and the difficulty in organizing the molecules may pose a problem in these applications. In this context, polymers based on PVDF can be used in the formation of thin P3HT films and present an alternative to improve the organization of P3HT molecules. In addition, PVDF acts as a plasticizer, making the film less rigid. The films were obtained from the blends of P3HT/PVDF and P3HT/PVDF-PMMA in a solution containing chloroform and DMAc (N,N-dimethylacetamide). Surface pressure isotherms, in situ ultraviolet-visible (UV-vis) spectroscopy, polarization-modulation infrared reflection-absorption spectroscopy, and Brewster angle microscopy techniques were used to analyze Langmuir films. The surface morphology of LS films was characterized by atomic force microscopy and UV-vis spectroscopy, and their degradation was analyzed by UV-vis spectroscopy after exposure to natural light under atmospheric conditions. The Langmuir films containing PVDF indicate a direct formation of the ferroelectric ß phase, with dipoles parallel to the water surface. The Langmuir films formed by P3HT presented dipoles of side chains parallel and aromatic groups perpendicular to the water surface. P3HT and PVDF or PVDF-PMMA films show high molecular organization compared with pure P3HT films. The results suggest that these films could be used to improve the properties of P3HT in several device applications, such as in optical and electrical sensors.

Inducing ß Phase Crystallinity in Block Copolymers of Vinylidene Fluoride with Methyl Methacrylate or Styrene.

Block copolymers of poly(vinylidene fluoride) (PVDF) with either styrene or methyl methacrylate (MMA) were synthesized and analyzed with respect to the type of the crystalline phase occurring. PVDF with iodine end groups (PVDF-I) was prepared by iodine transfer polymerization either in solution with supercritical CO2 or in emulsion. To activate all iodine end groups Mn2(CO)10 is employed. Upon UV irradiation Mn(CO)5 radicals are obtained, which abstract iodine from PVDF-I generating PVDF radicals. Subsequent polymerization with styrene or methyl methacrylate (MMA) yields block copolymers. Size exclusion chromatography and NMR results prove that the entire PVDF-I is converted. XRD, FT-IR, and differential scanning calorimetry (DSC) analyses allow for the identification of crystal phase transformation. It is clearly shown that the original α crystalline phase of PVDF-I is changed to the ß crystalline phase in case of the block copolymers. For ratios of the VDF block length to the MMA block length ranging from 1.4 to 5 only ß phase material was detected.

Correlation between particle deformation kinetics and polymer interdiffusion kinetics in drying latex films.

Using an experimental setup which determines the turbidity of the sample and the efficiency of Förster resonance energy transfer (FRET) at the same time, we have correlated the particle deformation kinetics in a drying latex film, quantified by light scattering with the kinetics of polymer interdiffusion. Interdiffusion was quantified making use of energy transfer (FRET) between donor molecules and acceptor molecules, bound to polymer chains on different particles. When the chains cross the interparticle boundaries, the rate of energy transfer increases. The latex was prepared by miniemulsion polymerization. The amount of emulsifier employed during polymerization had a pronounced effect on the relative timing of interdiffusion and particle deformation. Increasing the amount of emulsifier delayed the onset of interdiffusion relative to the time when the film became transparent. This is mostly the consequence of a size effect, as opposed to surfactant acting as a barrier for transport.

Addition of halloysite nanotubes prevents cracking in drying latex films.

Investigating the process of film drying from aqueous dispersions containing a polymer latex as well as halloysite nanotubes (HNTs), we found that composite films could be formed without cracking under conditions where films of the pure polymer would always crack. Scanning electron micrographs showed that the HNTs were well dispersed and, further, that the distribution of fiber orientations was close to isotropic. The pendulum hardness of films formed from acrylate dispersions strongly increased upon addition of the inorganic phase. The pencil hardness, on the other hand, was poor, which presumably goes back to insufficient coupling between the organic and the inorganic phase. All films were white in appearance. For fiber concentrations higher than 10 vol %, the final films were porous.

Self-stratification during film formation from latex blends driven by differences in collective diffusivity.

Coatings with vertical gradients in composition were produced by drying an aqueous polymer dispersion containing both charged and neutral particles. After drying, the neutral component was enriched at the film/air interface. The spontaneous vertical segregation between the two types of particles goes back to a difference in collective diffusivity. As the film dries, a layer enriched in polymer develops at the top. Due to their mutual repulsion, charged spheres escape from this layer more quickly than their neutral counterparts. Provided that the total time of drying is between the times of diffusion for the two types of particles (approximately H(0)(2)/D(c) with H(0) the initial film thickness and D(c) the collective diffusivity of the respective species), a concentration gradient persists after the film has turned dry. This effect can be used to create a functionally graded material (FGM) in a single coating step.