Stereochemical Effects on Platinum Acetylide Two-Photon Chromophores.

A series of cis-platinum(II) acetylide complexes containing two-photon-absorbing chromophores have been synthesized and characterized to explore the effects of stereochemistry on the nonlinear absorption properties. The molecules feature 4-(phenylethynyl)phenylethynylene (PE2), diphenylaminofluorene (DPAF), and benzothiazolylfluorene (BTF) ligands. The photophysical properties were investigated under one- and two-photon conditions and compared to the known trans analogues via UV-visible absorption, photoluminescence, femtosecond and nanosecond transient absorption (TA), nanosecond z-scan, and femtosecond two-photon absorption (2PA). The bent cis complexes exhibit blue shifts in the absorption, emission, femtosecond, and nanosecond TA spectra along with lower molar extinction coefficients and lower phosphorescence yields relative to the trans complexes suggesting less efficient Pt-induced spin-orbit coupling and intersystem crossing in the cis configuration. The cis chromophores are noncentrosymmetric and therefore show dipolar behavior with a pronounced 2PA in the 0-0 transition of the S0 → S1 band, while the trans complexes show quadrupolar behavior with a forbidden 0-0 transition. In the S0 → Sn region, both cis and trans complexes show intense two-photon-absorption bands (up to 3700 GM by the peak cross section for cis-BTF) which contain a significant contribution from the excited state absorption (S1 → Sn). All six complexes exhibit comparable nonlinear absorption response with a significant contribution from triplet-triplet absorption that slightly favors trans complexes but is more strongly dependent upon the structure of the π-conjugated chromophore.

Polymer Monoliths Containing Two-Photon Absorbing Phenylenevinylene Platinum(II) Acetylide Chromophores for Optical Power Limiting.

A series of platinum(II) acetylide complexes containing p-phenylenevinylene and moieties end-capped with triphenylamine groups have been incorporated into poly(methyl methacrylate) (PMMA) monoliths for optical power limiting applications. The one- and two-photon photophysical properties were investigated and compared to the photophysical properties in THF. The absolute two-photon absorption cross-section values for the monolith samples were measured and are comparable to the values obtained in solution. In the PMMA monoliths, the complexes retained the important two-photon absorption and reverse saturable absorption properties necessary for optical power limiting via dual mode mechanism, and their strong nonlinear absorption property was demonstrated by the open-aperture Z-scan method. Photostability studies of the p-phenylenevinylene platinum(II) acetylide complexes showed two photodegradation processes: a trans-to-cis isomerization and a singlet-oxygen sensitized self-oxidative cleavage. The photostability of the least photostable complex TPV0 was increased upon incorporation into a PMMA matrix.

Discovery of MLL1 binding units, their localization to CpG Islands, and their potential function in mitotic chromatin.

BACKGROUND: Mixed Lineage Leukemia 1 (MLL1) is a mammalian ortholog of the Drosophila Trithorax. In Drosophila, Trithorax complexes transmit the memory of active genes to daughter cells through interactions with Trithorax Response Elements (TREs). However, despite their functional importance, nothing is known about sequence features that may act as TREs in mammalian genomic DNA. RESULTS: By analyzing results of reported DNA binding assays, we identified several CpG rich motifs as potential MLL1 binding units (defined as morphemes). We find that these morphemes are dispersed within a relatively large collection of human promoter sequences and appear densely packed near transcription start sites of protein-coding genes. Genome wide analyses localized frequent morpheme occurrences to CpG islands. In the human HOX loci, the morphemes are spread across CpG islands and in some cases tail into the surrounding shores and shelves of the islands. By analyzing results of chromatin immunoprecipitation assays, we found a connection between morpheme occurrences, CpG islands, and chromatin segments reported to be associated with MLL1. Furthermore, we found a correspondence of reported MLL1-driven "bookmarked" regions in chromatin to frequent occurrences of MLL1 morphemes in CpG islands. CONCLUSION: Our results implicate the MLL1 morphemes in sequence-features that define the mammalian TREs and provide a novel function for CpG islands. Apparently, our findings offer the first evidence for existence of potential TREs in mammalian genomic DNA and the first evidence for a connection between CpG islands and gene-bookmarking by MLL1 to transmit the memory of highly active genes during mitosis. Our results further suggest a role for overlapping morphemes in producing closely packed and multiple MLL1 binding events in genomic DNA so that MLL1 molecules could interact and reside simultaneously on extended potential transcriptional maintenance elements in human chromosomes to transmit the memory of highly active genes during mitosis.

High efficiency platinum acetylide nonlinear absorption chromophores covalently linked to poly(methyl methacrylate).

We report three platinum acetylide acrylate monomers containing known two-photon absorption (TPA) chromophores and their covalent incorporation into polymers via free radical polymerization with methyl methacrylate. The photophysical properties of the platinum acetylide monomers and resulting poly(methyl methacrylate) (PMMA) copolymers were investigated to determine if the one- and two-photon photophysical properties of the chromophores were maintained in the copolymers. The photophysical properties of the series of copolymers were studied in solution and solid state with minimum shifts exhibited in the ground state absorption, photoluminescence, and triplet-triplet transient absorption spectra. The polymer films displayed markedly stronger phosphorescence and longer triplet excited state lifetimes than the polymers in solution or the monomers. The incorporation of the platinum acetylide chromophores into the PMMA copolymers allows the materials to be cast as thin films or into free-standing monoliths. Films with ~3.6 µm in thickness and monoliths with 1 mm path length were fabricated and examined. The nonlinear absorption responses of the polymers in solution were measured via the nanosecond z-scan method, and the solid state polymer monoliths were measured via nonlinear transmittance. Both measurements indicate that the polymers exhibited strong transmittance attenuation at input pulse energies exceeding 100 µJ.

Phenylene vinylene platinum(II) acetylides with prodigious two-photon absorption.

The linear and nonlinear optical properties of a series of linear and cross-conjugated platinum(II) acetylide complexes that contain extended p-(phenylene vinylene) chromophores are reported. The complexes exhibit very high femtosecond two-photon absorption (2PA) cross section values (σ(2) up to 10,000 GM), as measured by nonlinear transmission (NLT) and two-photon excited fluorescence (2PEF) methods. The large 2PA cross sections span a broad range of wavelengths, 570-810 nm, and they overlap with the triplet excited state absorption. Spectral coincidence of high cross section 2PA and triplet absorption is a key feature giving rise to efficient dual-mode optical power limiting (OPL).

Determination of quaternary ammonium compounds by potentiometric titration with an ionic surfactant electrode: single-laboratory validation.

A potentiometric titration for determining the quaternary ammonium compounds (QAC) commonly found in antimicrobial products was validated by a single laboratory. Traditionally, QACs were determined by using a biphasic (chloroform and water) manual titration procedure. Because of safety considerations regarding chloroform, as well as the subjectivity of color indicator-based manual titration determinations, an automatic potentiometric titration procedure was tested with quaternary nitrogen product formulations. By using the Metrohm Titrando system coupled with an ionic surfactant electrode and an Ag/AgCl reference electrode, titrations were performed with various QAC-containing formulation products/matrixes; a standard sodium lauryl sulfate solution was used as the titrant. Results for the products tested are sufficiently reproducible and accurate for the purpose of regulatory product enforcement. The robustness of the method was measured by varying pH levels, as well as by comparing buffered versus unbuffered titration systems. A quantitation range of 1-1000 ppm quaternary nitrogen was established. Eight commercially available antimicrobial products covering a variety of matrixes were assayed; the results obtained were comparable to those obtained by the manual titration method. Recoveries of 94 to 104% were obtained for spiked samples.