Laser-induced formation of "craters" and "hills" in azobenzene-containing polymethacrylate films.

Functional organic polymer materials with an ability to change their surface topography in response to external contactless stimuli, like light irradiation, have attracted considerable attention. This work is devoted to the study of contactless control of the surface topography and the formation of the surface features in the amorphousized and liquid crystalline films of two azobenzene-containing polymers. The investigated polymers are side-chain polymethacrylates containing azobenzene chromophores with two lateral methyl substituents in ortho-positions and differing in the length of flexible spacer with six and ten methylene units. Two lateral methyl substituents at the azobenzene chromophore ensure high photoresponses of these polymeric samples in the whole visible spectral range. Irradiation of the polymethacrylate films by focused polarized light of green (532 nm) and red (633 nm) lasers induces a specific photodeformation of the film surface. In the case of the green light formation of circular "craters" with anisotropic borders was found, whereas for the red light highly asymmetric "hills" were observed. The possible mechanisms of the surface topography formation and their features are discussed.

Polariton-assisted splitting of broadband emission spectra of strongly coupled organic dye excitons in tunable optical microcavity.

Resonance interaction between a localized electromagnetic field and excited states in molecules paves the way to control fundamental properties of a matter. In this study, we encapsulated organic molecules with relatively low unoriented dipole moments in the polymer matrix, placed them in tunable optical microcavity and realized, for the first time, controllable modification of the broad photoluminescence (PL) emission of these molecules in strong coupling regime at room temperature. Notably, while in most previous studies it was reported that the single mode dominates in the PL signal (radiation of the so-called branch of the lower polariton), here we report on the observation of two distinct PL peaks, evolution of which has been followed as the microcavity mode is detuned from the excitonic resonance. A significant Rabi splitting estimated from the modified PL spectra was as large as 225 meV. The developed approach can be used both in fundamental research of resonant light-mater coupling and its practical applications in sensing and development of coherent spontaneous emission sources using a combination of carefully designed microcavity with a wide variety of organic molecules.

Polariton-assisted manipulation of energy relaxation pathways: donor-acceptor role reversal in a tuneable microcavity.

Resonant interaction between excitonic transitions of molecules and localized electromagnetic field allows the formation of hybrid light-matter polaritonic states. This hybridization of the light and the matter states has been shown to significantly alter the intrinsic properties of molecular ensembles placed inside the optical cavity. Here, we have observed strong coupling of excitonic transition in a pair of closely located organic dye molecules demonstrating an efficient donor-to-acceptor resonance energy transfer with the mode of a tuneable open-access cavity. Analysing the dependence of the relaxation pathways between energy states in this system on the cavity detuning, we have demonstrated that predominant strong coupling of the cavity photon to the exciton transition in the donor dye molecule can lead not only to an increase in the donor-acceptor energy transfer, but also to an energy shift large enough to cause inversion between the energy states of the acceptor and the mainly donor lower polariton energy state. Furthermore, we have shown that the polariton-assisted donor-acceptor chromophores' role reversal or "carnival effect" not only changes the relative energy levels of the donor-acceptor pair, but also makes it possible to manipulate the energy flow in the systems with resonant dipole-dipole interaction and direct energy transfer from the acceptor to the mainly donor lower polariton state. Our experimental data are the first confirmation of the theoretically predicted possibility of polariton-assisted energy transfer reversal in FRET systems, thus paving the way to new avenues in FRET-imaging, remote-controlled chemistry, and all-optical switching.

Structure of Supramers Formed by the Amphiphile Biotin-CMG-DOPE.

Invited for this month's cover is the group of Prof. Nicolai Bovin from the Russian Academy of Sciences. The cover picture shows how a biotin residue initially hidden in a monolayer formed on the surface of a material by biot-CMG-DOPE (see top left) is pulled out of the layer by the streptavidin molecule (Str) that has come close to it (see below). This can be considered as a model of certain events (in particular, cis protein-ligand interactions) occurring on the surface of a living cell when it is necessary to hide the ligand from undesirable interactions, but leave the possibility of its recognition by a high-affinity protein. The picture is inspired by the legendary Yellow Submarine cartoon. Read the full text of their Full Paper at https://doi.org/10.1002/open.201900276.

Structure of Supramers Formed by the Amphiphile Biotin-CMG-DOPE.

The synthetic function-spacer-lipid (FSL) amphiphile biotin-CMG-DOPE is widely used for delicate ligation of living cells with biotin residues under physiological conditions. Since this molecule has an "apolar-polar-hydrophobic" gemini structure, the supramolecular organization is expected to differ significantly from the classical micelle. Its organization is investigated with experimental methods and molecular dynamics simulations (MDS). Although the linear length of a single biotin-CMG-DOPE molecule is 9.5 nm, the size of the dominant supramer globule is only 14.6 nm. Investigations found that while the DOPE tails form a hydrophobic core, the polar CMG spacer folds back upon itself and predominantly places the biotin reside inside the globule or planar layer. MDS demonstrates that <10 % of biotin residues on the highly water dispersible globules and only 1 % of biotin residues in layer coatings are in an linear conformation and exposing biotin into the aqueous medium. This explains why in biotin-CMG-DOPE apolar biotin residues both in water dispersible globules and coatings on solid surfaces are still capable of interacting with streptavidin.

A versatile tunable microcavity for investigation of light-matter interaction.

Light-matter interaction between a molecular ensemble and a confined electromagnetic field is a promising area of research, as it allows light-control of the properties of coupled matter. The common way to achieve coupling is to place an ensemble of molecules or quantum emitters into a cavity. In this approach, light-matter coupling is evidenced by modification of the spectral response of the emitter, which depends on the strength of interaction between emitter and cavity modes. However, there is not yet a user-friendly approach that allows the study of a large number of different and replaceable samples in a wide optical range using the same resonator. Here, we present the design of such a device that can speed up and facilitate investigation of light-matter interaction ranging from weak to strong coupling regimes in ultraviolet-visible and infrared (IR) spectral regions. The device is based on a tunable unstable λ/2 Fabry-Pérot microcavity consisting of plane and convex mirrors that satisfy the plane-parallelism condition at least at one point of the curved mirror and minimize the mode volume. Fine tuning of the microcavity length is provided by a Z-piezopositioner in a range up to 10 µm with a step of several nm. This design makes a device a versatile instrument that ensures easy finding of optimal conditions for light-matter interaction for almost any sample in both visible and IR areas, enabling observation of both electronic and vibrational couplings with microcavity modes thus paving the way to investigation of various coupling effects including Raman scattering enhancement, modification of chemical reactivity rate, lasing, and long-distance nonradiative energy transfer.

A novel design of a scanning probe microscope integrated with an ultramicrotome for serial block-face nanotomography.

We present a new concept of a combined scanning probe microscope (SPM)/ultramicrotome apparatus. It enables "slice-and-view" scanning probe nanotomography measurements and 3D reconstruction of the bulk sample nanostructure from series of SPM images after consecutive ultrathin sections. The sample is fixed on a flat XYZ scanning piezostage mounted on the ultramicrotome arm. The SPM measuring head with a cantilever tip and a laser-photodiode tip detection system approaches the sample for SPM measurements of the block-face surface immediately after the ultramicrotome sectioning is performed. The SPM head is moved along guides that are also fixed on the ultramicrotome arm. Thereby, relative dysfunctional displacements of the tip, the sample, and the ultramicrotome knife are minimized. The design of the SPM head enables open frontal optical access to the sample block-face adapted for high-resolution optical lenses for correlative SPM/optical microscopy applications. The new system can be used in a wide range of applications for the study of 3D nanostructures of biological objects, biomaterials, polymer nanocomposites, and nanohybrid materials in various SPM and optical microscopy measuring modes.

An instrumental approach to combining confocal microspectroscopy and 3D scanning probe nanotomography.

In the past decade correlative microscopy, which combines the potentials of different types of high-resolution microscopies with a variety of optical microspectroscopy techniques, has been attracting increasing attention in material science and biological research. One of outstanding solutions in this area is the combination of scanning probe microscopy (SPM), which provides data on not only the topography, but also the spatial distribution of a wide range of physical properties (elasticity, conductivity, etc.), with ultramicrotomy, allowing 3D multiparametric examination of materials. The combination of SPM and ultramicrotomy (scanning probe nanotomography) is very appropriate for characterization of soft multicompound nanostructurized materials, such as polymer matrices and microstructures doped with different types of nanoparticles (magnetic nanoparticles, quantum dots, nanotubes, etc.), and biological materials. A serious problem of this technique is a lack of chemical and optical characterization tools, which may be solved by using optical microspectroscopy. Here, we report the development of an instrumental approach to combining confocal microspectroscopy and 3D scanning probe nanotomography in a single apparatus. This approach retains all the advantages of SPM and upright optical microspectroscopy and allows 3D multiparametric characterization using both techniques. As the first test of the system developed, we have performed correlative characterization of the morphology and the magnetic and fluorescent properties of fluorescent magnetic microspheres doped with a fluorescent dye and magnetic nanoparticles. The results of this study can be used to obtain 3D volume images of a specimen for most high-resolution near-field scanning probe microscopies: SNOM, TERS, AFM-IR, etc. This approach will result in development of unique techniques combining the advantages of SPM (nanoscale morphology and a wide range of physical parameters) and high-resolution optical microspectroscopy (nanoscale chemical mapping and optical properties) and allowing simultaneous 3D measurements.

Photoinduced Changes of Surface Topography in Amorphous, Liquid-Crystalline, and Crystalline Films of Bent-Core Azobenzene-Containing Substance.

Recently, photofluidization and mass-transfer effects have gained substantial interest because of their unique abilities of photocontrolled manipulation with material structure and physicochemical properties. In this work, the surface topographies of amorphous, nematic, and crystalline films of an azobenzene-containing bent-core (banana-shaped) compound were studied using a special experimental setup combining polarizing optical microscopy and atomic force microscopy. Spin-coating or rapid cooling of the samples enabled the formation of glassy amorphous or nematic films of the substance. The effects of UV and visible-light irradiation on the surface roughness of the films were investigated. It was found that UV irradiation leads to the fast isothermal transition of nematic and crystalline phases into the isotropic phase. This effect is associated with E-Z photoisomerization of the compound accompanied by a decrease of the anisometry of the bent-core molecules. Focused polarized visible-light irradiation (457.9 nm) results in mass-transfer phenomena and induces the formation of so-called "craters" in amorphous and crystalline films of the substance. The observed photofluidization and mass-transfer processes allow glass-forming bent-core azobenzene-containing substances to be considered for the creation of promising materials with photocontrollable surface topographies. Such compounds are of principal importance for the solution of a broad range of problems related to the investigation of surface phenomena in colloid and physical chemistry, such as surface modification for chemical and catalytic reactions, predetermined morphology of surfaces and interfaces in soft matter, and chemical and biochemical sensing.

DNA structural alterations induced by bis-netropsins modulate human DNA topoisomerase I cleavage activity and poisoning by camptothecin.

Bis-netropsins (bis-Nts) are efficient catalytic inhibitors of human DNA topoisomerase I (top I). These DNA minor groove binders are considered to serve as suppressors of top I-linked DNA breaks, which is generally believed to be related to their affinity to DNA. In this study, it was found that bis-Nts exhibit sequence-specificity of suppression of the strong top I-specific DNA cleavage sites and that this sequence-specificity is determined by differential ligand-induced structural alterations of DNA. Raman scattering analysis of bis-Nts interactions with double-stranded oligonucleotides, each containing the site of specific affinity to one of bis-Nts and a distinctly located top I degenerate consensus, demonstrated that bis-Nts induce not only structural changes in duplex DNA at their loading position, but also conformational changes in a distant top I-specific DNA cleavage site. The ability to alter the DNA structure correlates with the anti-top I inhibitory activities of the ligands. In addition, DNA structural alterations induced by bis-Nts were shown to be responsible for modulation of the camptothecin (CPT)-mediated DNA cleavage by top I. This effect is expressed in the bis-Nts-induced enhancement of some of the CPT-dependent DNA cleavage sites as well as in the CPT-induced enhancement of some of the top I-specific DNA cleavage sites suppressed by bis-Nts in the absence of CPT.

Engineering a Robust Photovoltaic Device with Quantum Dots and Bacteriorhodopsin.

We present a route toward a radical improvement in solar cell efficiency using resonant energy transfer and sensitization of semiconductor metal oxides with a light-harvesting quantum dot (QD)/bacteriorhodopsin (bR) layer designed by protein engineering. The specific aims of our approach are (1) controlled engineering of highly ordered bR/QD complexes; (2) replacement of the liquid electrolyte by a thin layer of gold; (3) highly oriented deposition of bR/QD complexes on a gold layer; and (4) use of the Forster resonance energy transfer coupling between bR and QDs to achieve an efficient absorbing layer for dye-sensitized solar cells. This proposed approach is based on the unique optical characteristics of QDs, on the photovoltaic properties of bR, and on state-of-the-art nanobioengineering technologies. It permits spatial and optical coupling together with control of hybrid material components on the bionanoscale. This method paves the way to the development of the solid-state photovoltaic device with the efficiency increased to practical levels.

Combined scanning probe nanotomography and optical microspectroscopy: a correlative technique for 3D characterization of nanomaterials.

Combination of 3D structural analysis with optical characterization of the same sample area on the nanoscale is a highly demanded approach in nanophotonics, materials science, and quality control of nanomaterial. We have developed a correlative microscopy technique where the 3D structure of the sample is reconstructed on the nanoscale by means of a "slice-and-view" combination of ultramicrotomy and scanning probe microscopy (scanning probe nanotomography, SPNT), and its optical characteristics are analyzed using microspectroscopy. This approach has been used to determine the direct quantitative relationship of the 3D structural characteristics of nanovolumes of materials with their microscopic optical properties. This technique has been applied to 3D structural and optical characterization of a hybrid material consisting of cholesteric liquid crystals doped with fluorescent quantum dots (QDs) that can be used for photochemical patterning and image recording through the changes in the dissymmetry factor of the circular polarization of QD emission. The differences in the polarization images and fluorescent spectra of this hybrid material have proved to be correlated with the arrangement of the areas of homogeneous distribution and heterogeneous clustering of QDs. The reconstruction of the 3D nanostructure of the liquid crystal matrix in the areas of homogeneous QDs distribution has shown that QDs do not perturb the periodic planar texture of the cholesteric liquid crystal matrix, whereas QD clusters do perturb it. The combined microspectroscopy-nanotomography technique will be important for evaluating the effects of nanoparticles on the structural organization of organic and liquid crystal matrices and biomedical materials, as well as quality control of nanotechnology fabrication processes and products.

Optically and electrically controlled circularly polarized emission from cholesteric liquid crystal materials doped with semiconductor quantum dots.

Novel types of electro- and photoactive quantum dot-doped cholesteric materials have been engineered. UV-irradiation or electric field application allows one to control the degree of circular polarization and intensity of fluorescence emission by prepared quantum dot-doped liquid crystal films.

DNA binding induces conformational transition within human DNA topoisomerase I in solution.

We employed Raman and circular dichroism (CD) spectroscopy to probe the molecular structure of 68-kDa recombinant human DNA topoisomerase I (TopoI) in solution, in a complex with a 16-bp DNA fragment containing a camptothecin-enhanced TopoI cleavage site, and in a ternary complex with this oligonucleotide and topotecan. Raman spectroscopy reveals a TopoI secondary structure transition and significant changes in the hydrogen bonding of the tyrosine residues induced by the DNA binding. CD spectroscopy confirms the Raman data and identifies a DNA-induced (>7%) decrease of the TopoI alpha helix accompanied by at least a 6% increase of the beta structure. The Raman DNA molecular signatures demonstrated a bandshift that is expected for a net change in the environment of guanine C6 [double bond] O groups from pairing to solvent exposure. The formation of a ternary cleavage complex with TopoI, DNA, and topotecan as probed by CD spectroscopy reveals neither additional modifications of the TopoI secondary structure nor of the oligonucleotide structure, compared to the TopoI-oligonucleotide complex.

Interaction of clinically important human DNA topoisomerase I poison, topotecan, with double-stranded DNA.

Topotecan (TPT), a water-soluble derivative of camptothecin, is a potent antitumor poison of human DNA topoisomerase I (top1) that stabilizes the cleavage complex between the enzyme and DNA. The role of the recently discovered TPT affinity to DNA remains to be defined. The aim of this work is to clarify the molecular mechanisms of the TPT-DNA interaction and to propose the models of TPT-DNA complexes in solution in the absence of top1. It is shown that TPT molecules form dimers with a dimerization constant of (4.0 +/- 0.7) x 10(3) M(-1) and the presence of DNA provokes more than a 400-fold increase of the effective dimerization constant. Flow linear dichroism spectroscopy accompanied by circular dichroism, fluorescence, and surface-enhanced Raman scattering experiments provide evidence that TPT dimers are able to bind DNA by bridging different DNA molecules or distant DNA structural domains. This effect may provoke modification of the intrinsic geometry of the cruciform DNA structures, leading to the appearance of new crossover points that serve as the sites of the top1 loading position. The data presume the hypothesis of TPT-mediated modulation of top1-DNA recognition before ternary complex formation.