Anomalous Laterally Stressed Kinetically Trapped DNA Surface Conformations.

HIGHLIGHTS: DNA kinking is inevitable for the highly anisotropic 1D-1D electrostatic interaction with the one-dimensionally periodically charged surface. The double helical structure of the DNA kinetically trapped on positively charged monomolecular films comprising the lamellar templates is strongly laterally stressed and extremely perturbed at the nanometer scale. The DNA kinetic trapping is not a smooth 3D-> 2D conformational flattening but is a complex nonlinear in-plane mechanical response (bending, tensile and unzipping) driven by the physics beyond the scope of the applicability of the linear worm-like chain approximation. Up to now, the DNA molecule adsorbed on a surface was believed to always preserve its native structure. This belief implies a negligible contribution of lateral surface forces during and after DNA adsorption although their impact has never been elucidated. High-resolution atomic force microscopy was used to observe that stiff DNA molecules kinetically trapped on monomolecular films comprising one-dimensional periodically charged lamellar templates as a single layer or as a sublayer are oversaturated by sharp discontinuous kinks and can also be locally melted and supercoiled. We argue that kink/anti-kink pairs are induced by an overcritical lateral bending stress (> 30 pNnm) inevitable for the highly anisotropic 1D-1D electrostatic interaction of DNA and underlying rows of positive surface charges. In addition, the unexpected kink-inducing mechanical instability in the shape of the template-directed DNA confined between the positively charged lamellar sides is observed indicating the strong impact of helicity. The previously reported anomalously low values of the persistence length of the surface-adsorbed DNA are explained by the impact of the surface-induced low-scale bending. The sites of the local melting and supercoiling are convincingly introduced as other lateral stress-induced structural DNA anomalies by establishing a link with DNA high-force mechanics. The results open up the study in the completely unexplored area of the principally anomalous kinetically trapped DNA surface conformations in which the DNA local mechanical response to the surface-induced spatially modulated lateral electrostatic stress is essentially nonlinear. The underlying rich and complex in-plane nonlinear physics acts at the nanoscale beyond the scope of applicability of the worm-like chain approximation.

Electrical Excitation of Long-Range Surface Plasmons in PC/OLED Structure with Two Metal Nanolayers.

A current-driven source of long-range surface plasmons (LRSPs) on a duplex metal nanolayer is reported. Electrical excitation of LRSPs was experimentally observed in a planar structure, where an organic light-emitting film was sandwiched between two metal nanolayers that served as electrodes. To achieve the LRSP propagation in these metal nanolayers at the interface with air, the light-emitting structure was bordered by a one-dimensional photonic crystal (PC) on the other side. The dispersion of the light emitted by such a hybrid PC/organic-light-emitting-diode structure (PC/OLED) comprising two thin metal electrodes was obtained, with a clearly identified LRSP resonance peak.

Screening for Plant Volatile Emissions with Allelopathic Activity and the Identification of L-Fenchone and 1,8-Cineole from Star Anise (Illicium verum) Leaves.

One hundred and thirty-nine medicinal plant species were screened for their allelopathic activity through volatile emissions using Lactuca sativa as a test plant. Volatile emissions from the leaves of star anise (Illicium verum) showed the highest inhibition (100%) on the radicle and hypocotyl growth. Using headspace gas collection and gas chromatography-mass spectrometry (GC-MS), seven major volatile compounds from the leaves of star anise, including α-pinene, ß-pinene, camphene, 1,8-cineole, D-limonene, camphor, and L-fenchone were detected. To determine volatile compounds that may contribute to the inhibitory activity of star anise, the allelopathic potential of individual volatiles from star anise was evaluated using the cotton swab bioassay. The EC50 was calculated for each of the seven identified compounds. L-fenchone showed the strongest growth inhibitory activity (EC50 is 1.0 ng/cm3 for radicle and hypocotyl growth of lettuce), followed by 1,8-cineole, and camphene. This is the first report that L-fenchone could be an important volatile allelochemical from the leaves of star anise. From the actual concentration of each volatile compound in headspace and EC50 value, we concluded that the four volatile compounds, including L-fenchone, 1,8-cineole, ß-pinene, and camphene are the most important contributors to the volatile allelopathy of star anise.

Crystallography and Molecular Arrangement of Polymorphic Monolayer J-Aggregates of a Cyanine Dye: Multiangle Polarized Light Fluorescence Optical Microscopy Study.

The molecular orientation in monolayer J-aggregates of 3,3-di(γ-sulfopropyl)-5,5-dichlorotiamonomethinecyanine dye has been precisely estimated using improved linear polarization measurements in the fluorescence microscope in which a multiangle set of polarization data is obtained using sample rotation. The estimated molecular orientation supplemented with the previously established crystallographic constraints based on the analysis of the well-developed two-dimensional J-aggregate shapes unambiguously indicate the staircase type of molecular arrangement for striplike J-aggregates with the staircases oriented along strips. The molecular transition dipoles are inclined at an angle of ∼25° to the strip direction, whereas the characteristic strip vertex angle ∼45° is formed by the [100] and [1-10] directions of the monoclinic unit cell. Measurements of the geometry of partially unwound tubes and their polarization properties support the model of tube formation by close-packed helical winding of flexible monolayer strips. In the tubes, the long molecular axes are oriented at a small angle in the range of 5-15° to the normal to the tube axis providing low bending energy. At a nanoscale, high-resolution atomic force microscopy imaging of J-aggregate monolayers reveals a complex quasi-one-dimensional organization.

AFM visualization at a single-molecule level of denaturated states of proteins on graphite.

Different graphitic materials are either already used or believed to be advantageous in biomedical and biotechnological applications, e.g., as biomaterials or substrates for sensors. Most of these applications or associated important issues, such as biocompatibility, address the problem of adsorption of protein molecules and, in particular the conformational state of the adsorbed protein molecule on graphite. High-resolution AFM demonstrates highly oriented pyrolytic graphite (HOPG) induced denaturation of four proteins of blood plasma, such as ferritin, fibrinogen, human serum albumin (HSA) and immunoglobulin G (IgG), at a single molecule level. Protein denaturation is accompanied by the decrease of the heights of protein globules and spreading of the denatured protein fraction on the surface. In contrast, the modification of HOPG with the amphiphilic oligoglycine-hydrocarbon derivative monolayer preserves the native-like conformation and provides even more mild conditions for the protein adsorption than typically used mica. Protein unfolding on HOPG may have universal character for "soft" globular proteins.

Polymorphism of Two-Dimensional Cyanine Dye J-Aggregates and Its Genesis: Fluorescence Microscopy and Atomic Force Microscopy Study.

Polymorphic J-aggregates of monomethine cyanine dye 3,3'-di(γ-sulfopropyl)-5,5'-dichlorotiamonomethinecyanine (TC) have been studied by fluorescence optical microscopy (FOM) and by atomic force microscopy (AFM). The in situ FOM observations in a solution drop distinguish two J-aggregate morphology classes: flexible strips and rigid rods. The AFM imaging of dried samples reveals a strong J-aggregate structural rearrangement under adsorption on a mica surface with the strips self-folding and the rods squashing into rectangular bilayers and much deeper destruction. In the present work, the following structural conclusions have been drawn on the basis of careful consideration of strip crystal habits and various structural features of squashed/destructed rods: (1) the tubular morphology of TC rods is directly proved by FOM measurements in the solution bulk; (2) the staircase model of molecular arrangement in strips is proposed explaining the characteristic ∼44° skew angle in strip vertices; (3) a model of tube formation by a close-packed helical winding of flexible monolayer strips is proposed and justified which explains the observed J-aggregate polymorphism and strip-to-rod polymorphic transformations in a wide spatiotemporal scale; (4) at a nanoscale, an unexpectedly complex quasi-one-dimensional organization in J-aggregate two-dimensional monolayers is observed by high-resolution AFM imaging of constituent nanostrips separated by a characteristic distance in the range of 6-10 nm. The obtained results indicate that the underlying monolayer structure is the same for all J-aggregate polymorphs.

Angelicin as the principal allelochemical in Heracleum sosnowskyi fruit.

Distribution patterns of furocoumarins in fruits of the invasive species Heracleum sosnowskyi Manden. (Sosnowskyi's hogweed) during a cold stratification period were investigated. Angelicin, bergapten, methoxalen and imperatorin were mainly localized in the fruit coats and their content varied depending on the fruit source. Cold stratification treatment (90 days, 2-3 degrees C) reduced the content of furocoumarins in the fruit coats by more than two times, compared with those before stratification. The specific activity of the detected furocoumarins and total activity of crude extracts were evaluated using Lactuca sativa, as acceptor plant. Crude extracts obtained from fruit coats and seeds of H. sosnowskyi suppressed 50% of radicle and hypocotyl growth of lettuce seedlings at the concentration range of 1.0-1.7 mg/mL. The inhibitory activity of angelicin was proved to be the highest compared with the other tested furocoumarins, and the inhibitory activity of crude extracts could be explained mainly by the presence of angelicin. Both, monocots (Lolium multiflorum, Phleum pratensis, Festuca pratesis, Lolium perenne) and dicots (Tripholium repens, Trifolium pretense) were found to be sensitive to the exudates of whole H. sosnowskyi fruits. Thus, we assume, that high inhibitory potential of furocoumarins, especially angelicin, at high seed productivity of H. sosnowskyi might have an ecological significance in plant-plant interaction.

Identification of octanal as plant growth inhibitory volatile compound released from Heracleum sosnowskyi fruit.

Heracleum sosnowskyi Manden of the Apiaceae family is a malignant invasive plant in Eastern Europe, Belarus and Russia. The species is known for its prolific seed production, which has been linked to the plant's invasive success. The fruit also has a strong aroma, but the contribution of the fruit's volatile constituent to out-compete neighboring plants has not been fully established. In this study, fruit volatiles of H. sosnowskyi and conspecifics (i.e. H. asperum, H. lescovii, H. dissectum, H. hirtum) were identified by headspace gas chromatography-mass spectrometry (HS-GC-MS). Octyl acetate, octanol, octanal, hexyl isobutyrate, and hexyl-2-methyl butyrate were found to be the principal volatiles. Using authentic standards, the growth-inhibitory property of the individual compounds was assayed by the novel Cotton swab method. Assay results with lettuce (Lactuca sativa) showed that octanal strongly inhibited seed germination and radicle elongation of seedlings. The results suggest that octanal may be the main contributor to the allelopathic activity of H. sosnowksyi fruits. Furthermore, the mixture of fruit volatiles from the invasive H. sosnowskyi more strongly delayed lettuce seedling elongation than the volatiles from fruits of the non-invasive H. asperum, H. lescovii, H. dissectum and H. hirtum. Thus, the present study is the first to demonstrate the possible involvement of fruit volatiles of Heracleum species in plant-plant interaction.