Modeling of nanoparticle coatings for medical applications

Abstract Gold nanoparticles (AuNPs) have been shown to possess properties beneficial for the treatment of cancerous tumors by acting as radiosensitizers for both photon and ion radiation. Blood circulation time is usually increased by coating the AuNPs with poly(ethylene glycol) (PEG) ligands. The effectiveness of the PEG coating, however, depends on both the ligand surface density and length of the PEG molecules, making it important to understand the structure of the coating. In this paper the thickness, ligand surface density, and density of the PEG coating is studied with classical molecular dynamics using the software package MBN Explorer. AuNPs consisting of 135 atoms (approximately 1.4 nm diameter) in a water medium have been studied with the number of PEG ligands varying between 32 and 60. We find that the thickness of the coating is only weakly dependent on the surface ligand density and that the degree of water penetration is increased when there is a smaller number of attached ligands

Symmetry breaking by quantum coherence in single electron attachment

Quantum coherence-induced effects in atomic and molecular systems are the basis of several proposals for laser-based control of chemical reactions. So far, these rely on coherent photon beams inducing coherent reaction pathways that may interfere with one another, in order to achieve the desired outcome. This concept has been successfully exploited for removing the inversion symmetry in the dissociation of homonuclear diatomic molecules, but it remains to be seen if such quantum coherent effects can also be generated by interaction of incoherent electrons with such molecules. Here we show that resonant electron attachment to H2 and the subsequent dissociation into H (n=2) + H− is asymmetric about the inter-nuclear axis, while the asymmetry in D2 is far less pronounced. We explain this observation as due to attachment of a single electron resulting in a coherent superposition of two resonances of opposite parity. In addition to exemplifying a new quantum coherent process, our observation of coherent quantum dynamics involves the active participation of all three electrons and two nuclei, which could provide new tools for studying electron correlations as a means to control chemical processes and demonstrates the role of coherent effects in electron induced chemistry

Using the C-O stretch to unravel the nature of hydrogen bonding in low-temperature solid methanol-water condensates

Transmission infrared spectroscopy has been used in a systematic laboratory study to investigate hydrogen bonding in binary mixtures of CH3OH and H2O, vapour deposited at 30 K, as a function of CH3OH/H2O mixing ratio, R. Strong intermolecular interactions are evident between CH3OH and H2O with infrared band profiles of the binary ices differing from that of the pure components and changing significantly with R. Consistent evidence from the O–H and C–H band profiles and detailed analysis of the C–O stretch band reveal two different hydrogen bonding structural regimes below and above R=0.6–0.7. The vapour deposited solid mixtures were found to exhibit behaviour similar to that of liquids with evidence of inhomogeneity and higher coordination number of hydrogen bonds that are concentration dependent. The C–O stretch band was found to consist of three components around 1039 cm-1 (’blue’), 1027 cm-1(’middle’) and 1011 cm-1 (’red’). The ’blue’ and ’middle’ components corresponding to environments with CH3OH dominating as a proton donor (PD) and proton acceptor (PA) respectively reveal preferential bonding of CH3OH as a PA and H2O as a PD in the mixtures. The ’red’ component is only present in the presence of H2O and has been assigned to the involvement of both lone pairs of electrons on the oxygen atom of CH3OH as a PA to two PD H2O atoms. Cooperative effects are evident with concurrent blue-shifts in the C–H stretching modes of CH3OH below R=0.6 indicating CH3 group participation in hydrogen bonding

Electron attachment and quantum coherence in molecular hydrogen

Single electron attachment to a molecule may invoke quantum coherence in different angular momentum transfer channels. This has been observed in the 14 eV dissociative electron attachment resonance in molecular hydrogen where a coherent superposition of two negative ion resonant states of opposite parity is created, with the s and p partial waves of the electron contributing to the attachment process. Interference between the two partial wave contributions leads to a forward – backward asymmetry in the angular distribution of the product negative ions. Since these two resonant states dissociate to the same n = 2 state of H and H−, this asymmetry is further modified due to interference between the two paths of the dissociating molecular negative ion along different potential energy curves. This interference manifests as a function of the electron energy as well as isotopic composition. This case is akin to the quantum interference observed in photodissociation by one-photon vs two-photon absorption

Probing the interaction between solid benzene and water using vacuum ultraviolet and infrared spectroscopy

We present results of a combined vacuum ultravioloet (VUV) and infrared (IR) photoabsorption study of amorphous benzene:water mixtures and layers to investigate the benzene-water interaction in the solid phase. UV spectra of 1:1, 1:10 and 1:100 benzene:water mixtures at 24 K reveal a concentration dependent shift in the energies of the 1B2u, 1B1u and 1E1u electronic states of benzene. All the electronic bands blueshift from pure amorphous benzene towards gas phase energies with increasing water concentration. IR results reveal a strong dOH-π benzene-water interaction via the dangling OH stretch of water with the delocalised π system of the benzene molecule. Although this interaction influences the electronic states of benzene with the benzenewater interaction causing a redshift in the electronic states from that of the free benzene molecule, the benzene-benzene interaction has a more significant effect on the electronic states of benzene. VUV spectra of benzene and water layers show evidence of non-wetting between benzene and water, characterised by Rayleigh scattering tails at wavelengths greater than 220 nm. Our results also show evidence of benzene-water interaction at the benzene-water interface affecting both the benzene and the water electronic states. Annealing the mixtures and layers of benzene and water show that benzene remains trapped within in/under water ice until water desorption near 160 K. These first systematic studies of binary amorphous mixtures in the VUV, supported with complementary IR studies, provide a deeper insight into the influence of intermolecular interactions on intramolecular electronic states with significant implications for our understanding of photochemical processes in more realistic astrochemical environments

Vacuum ultraviolet photoabsorption of prime ice analogues of Pluto and Charon

Here we present the first Vacuum UltraViolet (VUV) photoabsorption spectra of ice analogues of Pluto and Charon ice mixtures. For Pluto the ice analogue is an icy mixture containing nitrogen (N2), carbon monoxide (CO), methane (CH4) and water (H2O) prepared with a 100:1:1:3 ratio, respectively. Photoabsorption of icy mixtures with and without H2O were recorded and no significant changes in the spectra due to presence of H2O were observed. For Charon a VUV photoabsorption spectra of an ice analogue containing ammonia (NH3) and H2O prepared with a 1:1 ratio was recorded, a spectrum of ammonium hydroxide (NH4OH) was also recorded. These spectra may help to interpret the P-Alice data from New Horizons

A multidisciplinary investigation of Martian atmospheric chemistry

For many years the Mars exploration program has focused on the mantra 'follow the water' as a means of unraveling key questions about the red planet such as whether the surface has ever supported life and what the ancient climate could have been like. However, with discoveries such as the seasonal plume of methane and sulfate-bearing soil, many have now turned to 'follow the chemistry' as being the true way to make progress. It is clear that the interaction of the atmosphere and the lithosphere and any potential biosphere will mark the atmosphere in ways we can only speculate about at present. Currently, there are many proposals for possible missions to monitor trace gases in the Martian atmosphere with a view to studying these possible interactions. The aim of these missions will be to constrain the possible reactions taking place in the Martian system and to finally allow us to begin answering some of these questions. The current project will investigate the chemistry of the Martian atmosphere through laboratory-based simulation and with computational experiments using a Mars General Circulation Model. Plasma discharge experiments have been used with Mars-like gas mixtures to gain insight into the possible reactions occurring in the atmosphere and their rates under different conditions. Eventually these experiments will be scaled up to use in the Open University Mars Simulation Chamber complete with Mars analogue soil and a Solar UV simulator. The data collected will be used in the Mars GCM to investigate how the trace species are transported around the planet from potential surface source regions and calculate their lifetimes and distributions in the atmosphere. It is hoped that these simulations will constrain some of the reactions occurring between trace species in the atmosphere and identify their sources and sinks be they geological or biological in origin. An understanding of the reactions involved is necessary to gain knowledge not just of Mars but other planets in our own solar system and beyond. To identify biosignatures such as ozone and methane on other worlds we must first understand their presence in the Martian system, a system for which detailed, high-resolution observation is possible

Two Suns in The Sky: Stellar Multiplicity in Exoplanet Systems

We present results of a reconnaissance for stellar companions to all 131 radial-velocity-detected candidate extrasolar planetary systems known as of July 1, 2005. CPM companions were investigated using the multi-epoch DSS images, and confirmed by matching the trigonometric parallax distances of the primaries to companion distances estimated photometrically. We also attempt to confirm or refute companions listed in the Washington Double Star Catalog, the Catalogs of Nearby Stars, in Hipparcos results, and in Duquennoy & Mayor (1991). Our findings indicate that a lower limit of 30 (23%) of the 131 exoplanet systems have stellar companions. We report new stellar companions to HD 38529 and HD 188015, and a new candidate companion to HD 169830. We confirm many previously reported stellar companions, including six stars in five systems that are recognized for the first time as companions to exoplanet hosts. We have found evidence that 20 entries in the Washington Double Star Catalog are not gravitationally bound companions. At least three, and possibly five, of the exoplanet systems reside in triple star systems. Three exoplanet systems have potentially close-in stellar companions ~ 20 AU away from the primary. Finally, two of the exoplanet systems contain white dwarf companions. This comprehensive assessment of exoplanet systems indicates that solar systems are found in a variety of stellar multiplicity environments - singles, binaries, and triples; and that planets survive the post-main-sequence evolution of companion stars.Comment: 52 pages, 7 figures, Accepted for publication in Ap

Topical Issue "Dynamics of Systems on the Nanoscale (2021)". Editorial

Exploration of the structure formation and dynamics of animate and inanimate matter on the nanometer scale is a highly interdisciplinary field of rapidly emerging research. It is relevant for various molecular and nanoscale systems of different origins and compositions and concerns numerous phenomena originating from physics, chemistry, biology, and materials science. This topical issue presents a collection of research papers devoted to different aspects of the Dynamics of Systems on the Nanoscale. Some of the contributions discuss specific applications of the research results in several modern and emerging technologies, such as controlled nanofabrication with charged particle beams or the design and practical realization of novel gamma-ray crystal-based light sources. Most works presented in this topical issue were reported at the joint Sixth International Conference "Dynamics of Systems on the Nanoscale" and the tenth International Symposium "Atomic Cluster Collisions" (DySoN-ISACC 2021), which were held in Santa Margherita Ligure, Italy, in October 2021.Comment: Editorial for the topical issue "Dynamics of Systems on the Nanoscale (2021)" of the European Physical Journal D; see https://epjd.epj.org/component/toc/?task=topic&id=161

UV degradation of deoxyribonucleic acid

The effects of UV synchrotron radiation on deoxyribonucleic acid (DNA) cast films have been systematically investigated by vacuum ultraviolet and infrared spectrophotometry as a function of irradiation time. Cast DNA films exposed at 140 nm (8.85 eV) for different irradiations times, revealed consistent changes in their VUV spectra which indicate a decrease of thymine groups and an increase of ? ? ?* transition spectral signature associated with the C=O group of the open sugar chain. This result was corroborated by a decrease in C-O stretching vibration at 1061 cm?1 observed in the infrared spectra. Both these results are consistent with the creation of single strand breaks in the deoxyribose component of DNA molecule and a decrease in the phosphate groups. It was also shown that UV radiation is effective in damaging the thymine groups involved in Hoogsteen base pairing with adenine. The analysis of the infrared data suggests that the usual spectroscopic fingerprints of DNA denaturation are not necessarily a reliable measure of DNA damage