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We show that DNA carrying 5-methylcytosine modifications or methylated DNA (m-DNA) can be distinguished from DNA with unmodified cytosine by Raman spectroscopy enhanced by both a bowtie nanoantenna and excitation resonance. In particular, m-DNA can be identified by a peak near 1000 cm−1and changes in the Raman peaks in the 1200–1700 cm−1band that are enhanced by the ring-absorption resonance. The identification is robust to the use of resonance Raman and nanoantenna excitation used to obtain significant signal improvement. The primary differences are three additional Raman peaks with methylation at 1014, 1239, and 1639 cm−1and spectral intensity inversion at 1324 (C5=C6) and 1473 cm−1(C4=N3) in m-DNA compared to that of DNA with unmodified cytosine. We attribute this to the proximity of the methyl group to the antenna, which brings the (C5=C6) mode closer to experiencing a stronger near-field enhancement. We also show distinct Raman spectral features attributed to the transition of DNA from a hydrated state, when dissolved, to a dried/denatured state. We observe a general broadening of the larger lines and a transfer of spectral weight from the ∼1470 cm−1vibration to the two higher-energy lines of the dried m-DNA solution. We attribute the new spectral characteristics to DNA softening under high salt conditions and find that the m-DNA is still distinguishable via the ∼1000 cm−1peak and distribution of the signal in the 1200–1700 cm−1band. The nanoantenna gain exceeds 20,000, whereas the real signal ratio is much less because of a low average enhanced region occupancy even with these relatively high DNA concentrations. It is improved when fixed DNA in a salt crystal lies near the nanoantenna. The Raman resonance gain profile is consistent with A-term expectations, and the resonance is found at ∼259 nm excitation wavelength.

Telomeres, complexes of DNA and proteins, protect ends of linear chromosomes. In humans, the two shelterin proteins TRF1 and TIN2, along with cohesin subunit SA1, were proposed to mediate telomere cohesion. While the ability of the TRF1-TIN2 and TRF1-SA1 systems to compact telomeric DNA by DNA-DNA bridging has been reported, the function of the full ternary TRF1-TIN2-SA1 system has not been explored in detail. Here, we quantify the compaction of nanochannel-stretched DNA by the ternary system, as well as its constituents, and obtain estimates of the relative impact of its constituents and their interactions. We find that TRF1, TIN2, and SA1 work synergistically to cause a compaction of the DNA substrate, and that maximal compaction occurs if all three proteins are present. By altering the sequence with which DNA substrates are exposed to proteins, we establish that compaction by TRF1 and TIN2 can proceed through binding of TRF1 to DNA, followed by compaction as TIN2 recognizes the previously bound TRF1. We further establish that SA1 alone can also lead to a compaction, and that compaction in a combined system of all three proteins can be understood as an additive effect of TRF1-TIN2 and SA1-based compaction. Atomic force microscopy (AFM) of intermolecular aggregation confirms that a conbination of TRF1, TIN2, and SA1 together drive strong intermolecular aggregation as it would be required during chromosome cohesion.

We report the fabrication of a two-dimensional periodic structure made from the conjugated, fluorescent polymer poly(p-phenylene vinylene), PPV, by direct-write near-field lithography of a photosensitive precursor of the conjugated polymer. The precursor film is illuminated with ultraviolet radiation using the apertured fibre of a home-built scanning near-field optical microscope (SNOM), and unexposed areas are subsequently dissolved in methanol. The fully conjugated polymer is obtained by thermal conversion under vacuum. The structure is approximately 10 µm × 10 µm, and consists of 30 nm tall pillars on a 330 nm periodicity lattice. We present a calculation of the photonic properties and propose that structures made with the method investigated here are promising candidates for photonic crystal lasers. We also report the results of preliminary investigations aimed at increasing the pillar height.

We report the fabrication of a two-dimensional periodic structure made from the conjugated, fluorescent polymer poly(p-phenylene vinylene), PPV, by direct-write near-field lithography of a photosensitive precursor of the conjugated polymer. The precursor film is illuminated with ultraviolet radiation using the apertured fibre of a home-built scanning near-field optical microscope (SNOM), and unexposed areas are subsequently dissolved in methanol. The fully conjugated polymer is obtained by thermal conversion under vacuum. The structure is approximately 10 µm × 10 µm, and consists of 30 nm tall pillars on a 330 nm periodicity lattice. We present a calculation of the photonic properties and propose that structures made with the method investigated here are promising candidates for photonic crystal lasers. We also report the results of preliminary investigations aimed at increasing the pillar height.

In recent years, variously substituted derivatives of poly(1,4-phenylene vinylene)s have emerged as efficient candidates for the emissive layer in polymer light emitting diodes. The synthetic routes for these polymers divide between precursor routes and those leading to fully conjugated solvent-processible polymers. The Gilch dehydrohalogenation polycondensation has largely been used for the latter class. In this presentation, we describe a novel family of 2,3-disubstituted aromatic precursors, derived from catechol, and we report their efficient polymerisation as homo- and copolymers with, for example, silyl-substituted derivatives to give materials which are highly fluorescent and serve as interesting materials in polymer LEDs.

2,3-Dialkoxy-substituted poly(1,4-phenylene vinylene) (PPV) homo- and co-polymers have been prepared by the Gilch dehydrohalogenation polycondensation of the corresponding bishalomethyl-substituted benzene monomers, and double layer light emitting devices fabricated with these materials exhibited high electroluminescence efficiencies with low turn-on voltages.