Extremophilic Polysaccharide for Biosynthesis and Passivation of Gold Nanoparticles and Photothermal Ablation of Cancer Cells

Extremophiles are the group of organisms that are far overlooked for exploring novel biomaterials in the field of material science and bionanotechnology. Extremophilic bacterial‐sulfated exopolysaccharide, mauran (MR), is employed for the bioreduction and passivation of gold nanoparticles (AuNps) to enhance the biocompatibility of AuNps and used for photothermal ablation of cancer cells. Here, various concentrations of MR solution are tested for the reduction of HAuCl₄ solution in the presence as well as in the absence of an external reducing agent, to produce mauran‐gold nanoparticles (MRAu Nps). These biocompatible nanocomposites are treated with cancer cell lines under in vitro conditions and NIR irradiated for complete ablation. MRAu Nps‐treated cancer cells on immediate exposure to infrared radiation from a femtosecond pulse laser of operating wavelength 800 nm are subjected to hyperthermia causing cell death. Biocompatible MR stabilization could fairly reduce the cytotoxicity caused by bare AuNps during biomedical applications. Application of a biocompatible polysaccharide from extremophilic bacterial origin for reduction and passivation of AuNps and used for a biomedical purpose is known to be first of its kind in bionanofusion studies.     

A minimal implementation of the AMBER-GAUSSIAN interface for ab initio QM/MM-MD simulation

For applying to a number of theoretical methodologies based on an ab initio quantum mechanical/molecular mechanical (QM/MM) molecular dynamics method connecting AMBER9 with GAUSSIAN03, we have developed an AMBER-GAUSSIAN interface (AG-IF), which can be one of the simplest architectures. In the AG-IF, only a few subroutines addition is necessary to retrieve the QM/MM energy and forces, obtained by GAUSSIAN, for solving a set of Newtonian equations of motion in AMBER. It is, therefore, easy to be modified for individual applications since AG-IF utilizes most of those functions originally equipped not only in AMBER but also in GAUSSIAN. In the present minimal implementation, only AMBER is modified, whereas GAUSSIAN is left unchanged. Moreover, a different method of calculating electrostatic forces of MM atoms interacting with QM region is proposed. Using the AG-IF, we also demonstrate three examples of application: (i) the QM versus MM comparison in the radial distribution function, (ii) the free energy gradient method, and (iii) the charge from interaction energy and forces.     

Soft- and reactive-landing of Cr(aniline)2 sandwich complexes onto self-assembled monolayers: separation between functional and binding sites

Soft- and reactive-landing of gas-phase synthesized cationic Cr(aniline)(2) complexes onto self-assembled monolayers of methyl-terminated (CH(3)-SAM) and carboxyl-terminated (COOH-SAM) organothiolates coated on gold were performed at hyperthermal collision energy (5-20 eV). The properties of the Cr(aniline)(2) complexes on the SAM surfaces were characterized using infrared reflection absorption spectroscopy (IRAS) and temperature-programmed desorption (TPD), together with theoretical calculations based on density functional theory (DFT). For the CH(3)-SAM, the Cr(aniline)(2) complexes were embedded inside the SAM matrix in a neutral charge state, keeping a sandwich structure. For the COOH-SAM, the IRAS and TPD study revealed that the amine-containing Cr(aniline)(2) complexes were bound to the SAM surface in two forms of physisorption and chemical linking through an amide bond. In the desorption, the latter form appeared as the reaction product between organothiolates and Cr(aniline)(2) above 400 K, where the organothiolate molecules, forming the SAM, were desorbed from the gold surface. The results show that the hyperthermal depositions onto a COOH-SAM bring about reactive-landing followed by covalent linking of an amide bond between the amine-containing Cr(aniline)(2) complexes to the carboxyl-terminated SAM surface, in which the binding sites can be separated from the functional sites of the d-π interaction.     

Accurate quantification of polycyclic aromatic hydrocarbons in dust samples using microwave-assisted solvent extraction combined with isotope-dilution mass spectrometry

For accurate quantification of polycyclic aromatic hydrocarbons (PAHs) in dust samples, we investigated the use of microwave-assisted solvent extraction (MAE) combined with isotope-dilution mass spectrometry (IDMS) using deuterium-labelled PAHs (D-PAHs). Although MAE with a methanol/toluene mixture (1:3 by volume) at 160 °C for 40 min was best for extracting PAHs from tunnel dust among examined, the recovery yields of D-PAHs decreased with increasing molecular weight (<40% for MW ≥ 264; that of deuterium-labelled indeno[123-cd]pyrene (D-IcdP) was only 7.1%). Although the residues were extracted a second time, the observed concentrations did not change dramatically (<5%), and the recovery yields of heavier D-PAHs (i.e., MW ≥ 264) were approximately half of those of the first extract, including D-IcdP (3.4%). These results suggest that both partitioning and isotopic equilibria of PAHs and D-PAHs between sample and solvent were achieved for extractable heavier PAHs under the condition. Thus, the observed concentrations of PAHs obtained by MAE–IDMS were reasonable, even though recovery yields of D-PAHs were <50%. From the results of carbon analyses and extractable contents, lower recovery yields of D-PAHs from the tunnel dust were due to a large content of char with low extractable contents.     

Radial transport characteristics of fast ions due to energetic-particle modes inside the last closed-flux surface in the compact helical system

The internal behavior of fast ions interacting with magnetohydrodynamic bursts excited by energetic ions has been experimentally investigated in the compact helical system. The resonant convective oscillation of fast ions was identified inside the last closed-flux surface during an energetic-particle mode (EPM) burst. The phase difference between the fast-ion oscillation and the EPM, indicating the coupling strength between them, remains a certain value during the EPM burst and drives an anomalous transport of fast ions.     

Direct observation of optically induced transient structures in graphite using ultrafast electron crystallography

We use ultrafast electron crystallography to study structural changes induced in graphite by a femtosecond laser pulse. At moderate fluences of < or =21 mJ/cm2, lattice vibrations are observed to thermalize on a time scale of approximately 8 ps. At higher fluences approaching the damage threshold, lattice vibration amplitudes saturate. Following a marked initial contraction, graphite is driven nonthermally into a transient state with sp3-like character, forming interlayer bonds. Using ab initio density functional calculations, we trace the governing mechanism back to electronic structure changes following the photoexcitation.     

RbCl和CsCl水溶液结构的X射线散射及经验势结构精修模拟

采用X射线散射法研究了RbCl和CsCl水溶液的结构,利用基于经验势的结构精修(EPSR)方法获得了溶液中的水合Cl^-、Rb⁺、Cs⁺、离子缔合及本体水的对径向分布函数、配位数分布及空间密度分布(3D结构)等结构信息。在水溶液中,Cl^-具有相对稳定的6水合结构,其水合距离为0.321 nm,外加阳离子对其水合作用的影响不明显。7.3 ± 1.4个水分子与Rb⁺水合,其特征水合距离为0.297 nm,8.4 ± 1.6个水分子与Cs⁺水合其水合距离为0.312 nm。Cs⁺不具有第二水合层,而Rb⁺表现出了更强的水合能力,具有较明显的第二水合层。Cl^-、Rb⁺及Cs⁺常被认为是“结构破坏”型离子。从微观角度来看这种所谓的“结构破坏”主要体现在破坏了本体水分子的第二水合层保持四面体构型的趋势。RbCl和CsCl水溶液中部分存在着Rb-Cl和Cs-Cl直接接触离子对,在1.0 mol·dm^-3的溶液中Rb-Cl及Cs-Cl的特征距离分别为0.324和0.336 nm,溶剂分割离子对的距离则都在0.6 nm左右。相对于Cs⁺,Rb⁺与Cl^-离子之间表现出了更强的缔合能力。