Identifying Cytosine-Specific Isomers via High-Accuracy Single Photon Ionization.

Biological entities, such as DNA bases or proteins, possess numerous tautomers and isomers that lie close in energy, making the experimental characterization of a unique tautomer challenging. We apply VUV synchrotron-based experiments combined with state-of-the-art ab initio methodology to determine the adiabatic ionization energies (AIEs) of specific gas-phase cytosine tautomers produced in a molecular beam. The structures and energetics of neutral and cationic cytosine tautomers were determined using explicitly correlated methods. The experimental spectra correspond to well-resolved bands that are attributable to the specific contributions of five neutral tautomers of cytosine prior to ionization. Their AIEs are experimentally determined for the first time with an accuracy of 0.003 eV. This study also serves as an important showcase for other biological entities presenting a dense pattern of isomeric and tautomeric forms in their spectra that can be investigated to understand the charge redistribution in these species upon ionization.

Hybrid nanostructures of nitrogen-doped carbon dots and aromatic amino acids: Synthesis, interactions at interfaces and optical properties.

Nitrogen-doped carbon dots (NCD) were synthesized using a simple and fast hydrothermal route, employing citric acid and urea as precursors. The resulting NCDs were non-covalently functionalized (conjugated) with aromatic amino acids, namely phenylalanine (Phe) and tryptophan (Trp). Atomic force microscopy revealed that the NCDs exhibit a disk-like morphology with an average diameter of approximately 60 nm and an average height of about 0.5 nm. Following conjugation, the particle height increased to around 3 nm. UV-vis spectroscopy analysis indicated successful conjugation of the amino acids to the NCD nanostructures. Additionally, DFT numerical calculations based on three differently N-doped clusters were performed to elucidate the nature of the non-covalent interactions between NCDs and the corresponding amino acids. Photoluminescent spectra demonstrated a stable and strong fluorescence signal for both hybrids in the UV region. The most significant changes were observed in the case of Trp-conjugation. In contrast to phenylalanine, the non-covalent bonding of tryptophan to NCDs strongly influenced the visible emission (around 500 nm) originating from surface states of the dots.

Enhanced resonance energy transfer in gold nanoparticles bifunctionalized by tryptophan and riboflavin and its application in fluorescence bioimaging.

Gold nanoparticles were functionalized by amino acid tryptophan and vitamin riboflavin - a resonance energy transfer (RET) pair of biomolecules. The presence of the gold nanoparticles resulted in 65% increase in RET efficiency. Because of enhanced RET efficiency, the photobleaching dynamics of the fluorescent molecules at the surface of the nanoparticles is different from that of molecules in solution. The observed effect was used for detection of the functionalized nanoparticles within biological material rich with autofluorescent species. Synchrotron radiation deep-ultraviolet fluorescence microscopy is used to study the photobleaching dynamics of the fluorescence centers within human hepatocellular carcinoma Huh7.5.1 cells incubated with the nanoparticles. The fluorescent centers were classified according to their photobleaching dynamics, which enabled the discrimination of the cell areas where the accumulation of the nanoparticles takes place, even though the particles were smaller than the spatial resolution of the images.

Condensation Effects on Electron Chiral Asymmetries in the Photoionization of Serine: From Free Molecules to Nanoparticles.

Structural changes at the molecular level, occurring at the onset of condensation, can be probed by angle-resolved valence photoelectron spectroscopy, which is inherently sensitive to the electronic structure. For larger condensed systems like aerosol particles, the observation of intrinsic angular anisotropies in photoemission (ß parameters) is challenging due to the strong reduction of their magnitude by electron transport effects. Here, we use a less common, more sensitive observable in the form of the chiral asymmetry parameter to perform a comparative study of the VUV photoelectron spectroscopy and photoelectron circular dichroism (PECD) between pure gas phase enantiomers of the amino acid serine and their corresponding homochiral nanoparticles. We observe a relatively large (1%) and strongly kinetic energy-dependent asymmetry, discussed in terms of the emergence of local order and conformational changes potentially counterbalancing the loss of angular information due to electron transport scattering. This demonstrates the potential of PECD as a sensitive probe of the condensation effects from the gas phase to bulk-like chiral aerosol particles surpassing the potential of conventional photoemission observables such as ß parameters.

Conformer-dependent vacuum ultraviolet photodynamics and chiral asymmetries in pure enantiomers of gas phase proline.

Proline is a unique amino-acid, with a secondary amine fixed within a pyrrolidine ring providing specific structural properties to proline-rich biopolymers. Gas-phase proline possesses four main H-bond stabilized conformers differing by the ring puckering and carboxylic acid orientation. The latter defines two classes of conformation, whose large ionization energy difference allows a unique conformer-class tagging via electron spectroscopy. Photoelectron circular dichroism (PECD) is an intense chiroptical effect sensitive to molecular structures, hence theorized to be highly conformation-dependent. Here, we present experimental evidence of an intense and striking conformer-specific PECD, measured in the vacuum ultraviolet (VUV) photoionization of proline, as well as a conformer-dependent cation fragmentation behavior. This finding, combined with theoretical modeling, allows a refinement of the conformational landscape and energetic ordering, that proves inaccessible to current molecular electronic structure calculations. Additionally, astrochemical implications regarding a possible link of PECD to the origin of life's homochirality are considered in terms of plausible temperature constraints.

Electronic Properties of Free-Standing Surfactant-Capped Lead Halide Perovskite Nanocrystals Isolated in Vacuo.

We report an investigation of lead halide perovskite CH3NH3PbBr3 nanocrystals and associated ligand molecules by combining several different state-of-the-art experimental techniques, including synchrotron radiation-based XPS and VUV PES of free-standing nanocrystals isolated in vacuum. By using this novel approach for perovskite materials, we could directly obtain complete band alignment to vacuum of both CH3NH3PbBr3 nanocrystals and the ligands widely used in their preparation. We discuss the possible influence of the ligand molecules to apparent perovskite properties, and we compare the electronic properties of nanocrystals to those of bulk material. The experimental results were supported by DFT calculations.

Interaction of amino acid-functionalized silver nanoparticles and Candida albicans polymorphs: A deep-UV fluorescence imaging study.

The interaction of the tryptophan functionalized Ag nanoparticles and live Candida albicans cells was studied by synchrotron excitation deep-ultraviolet (DUV) fluorescence imaging at the DISCO beamline of Synchrotron SOLEIL. DUV imaging showed that incubation of the fungus with functionalized nanoparticles results in significant increase in the fluorescence signal. The analysis of the images revealed that the interaction of the nanoparticles with (pseudo)hyphae polymorphs of the diploid fungus was less pronounced than in the case of yeast cells or budding spores. The changes in the intensity of the fluorescence signals of the cells after incubation were followed in [327-353nm] and [370-410nm] spectral ranges that correspond to the fluorescence of tryptophan in non-polar and polar environment, respectively. As a consequence of the environmental sensitivity of the silver-tryptophan fluorescent nanoprobe, we were able to determine the possible accumulation sites of the nanoparticles. The analysis of the intensity decay kinetics showed that the photobleaching effects were more pronounced in the case of the functionalized nanoparticle treated cells. The results of time-integrated emission in the mentioned spectral ranges suggested that the nanoparticles penetrate the cells, but that the majority of the nanoparticles attach to the cells' surfaces.

Tryptophan-functionalized gold nanoparticles for deep UV imaging of microbial cells.

Biocompatible fluorescent nanostructures were prepared by a functionalization of gold nanoparticles with the amino acid tryptophan. The gold-tryptophan bioconjugates were investigated by TEM and HRTEM and various spectroscopy methods (XPS, FTIR, UV-vis and photoluminescence). It was found that the gold nanoparticles, initially 8 nm in diameter, aggregate in the presence of the amino acid. From the XPS and FTIR spectroscopy results, it was concluded that the tryptophan gold interactions mainly take place via indole and carboxyl groups. Although the indole group is involved in the interaction with the gold surfaces, the tryptophan-gold hybrids showed strong fluorescence due to the presence of multilayers of tryptophan. Deep ultra violet (DUV) imaging performed at the SOLEIL synchrotron showed that it is possible to detect these hybrid nanostructures within Escherichia coli cells.

Viscoelastic properties and antimicrobial activity of cellulose fiber sheets impregnated with Ag nanoparticles.

A silver nanoparticle colloid was prepared by a modified Tollens method using d-glucose as the reduction agent. The obtained nanoparticles were used for the modification of pine, linter and recycled cellulose fibers. Although the silver contents were relatively low (0.05-0.13 wt.%), the cellulose-sheets prepared from the modified fibers show improved mechanical and viscoelastic properties. The tensile index (strength) increased with up to 30% in comparison to the index of the sheets obtained from the untreated fibers. The influence of the nanoparticles on the viscoelastic properties of the cellulose sheets was investigated by dynamic mechanical analysis (DMA) in the temperature range from -120 to 20 °C and with a force frequency of 100 Hz. A broad relaxation transition positioned at -80 °C was observed in the loss modulus spectrum of all the cellulose sheets, while the Ag-modified sheets exhibited higher storage moduli values in the whole temperature range. The antimicrobial activity tests show that the pine, silver and recycled cellulose fiber sheets with silver nanoparticles can be successfully employed to prevent the viability and growth of the common pathogens Staphylococcus aureus, Escherichia coli and Candida albicans.

Inhibition of microbial growth by silver-starch nanocomposite thin films.

A sago starch biopolymer with embedded silver nanoparticles has been studied as a material for the prevention of microbial growth. Approximately 8 nm in size, silver nanoparticles have been synthesized by reduction of the silver salt in aqueous solution in the presence of sago starch using sodium borohydride as a reducing agent. The obtained solutions were cast on glass plates to obtain thin supported silver-starch nanocomposite films. The morphology of the nanocomposites was investigated by scanning and transmission electron microscopy. UV-Vis absorption spectroscopy showed that during the film formation a part of the silver nanoparticles has been trapped in the water present in the sample, which enabled their partial oxidation into active Ag(+) species. The oxidation of the silver nanoparticles was confirmed by X-ray photoelectron spectroscopy. The antimicrobial activity tests have shown that the nanocomposite material can be successfully employed to prevent the viability and growth of the common pathogens Staphylococcus aureus, Escherichia coli and Candida albicans.

Adsorption of sulfur onto a surface of silver nanoparticles stabilized with sago starch biopolymer.

Adsorption of sulfide ions onto a surface of starch capped silver nanoparticles upon addition of thioacetamide was investigated. UV-vis absorption spectroscopy revealed that the adsorption of the sulfide ion on the surface of the silver nanoparticles induced damping as well as blue shift of the silver surface plasmon resonance band. Further increase in thioacetamide concentration led to shift of the resonance band toward higher wavelengths indicating the formation of the continuous Ag2S layer on the silver surface. Thus fabricated nanoparticles were investigated using electron microscopy techniques (TEM, HRTEM, and HAADF-STEM) and X-ray photoelectron spectroscopy (XPS), which confirmed their core-shell structure.