Directed energy transfer due to orientational broadening of energy levels in photosynthetic pigment solutions

The directed non-radiative energy transfer through monomeric molecules of chlorophyll “a” and pheophytin “a” at high concentrations (c~10^-2 M) in a rigid matrix of polyvinylbutyral has been found by using the nanosecond laser spectrofluorimeter. The phenomenon is caused by orientational broadening of pigment molecular spectra owing to its interaction with a solvent. The observed temporal shift of the luminescence spectrum to the red region in a nanosecond time scale as well as the red shift of the time integrated spectrum at a high concentration of pigment molecules and the monotonic growth of the luminescence lifetime with a shift to the red region of the spectrum served as indications of the directed energy transfer in the sample. The non-radiative energy transfer from monomeric molecules towards aggregates is also directly demonstrated by the deformation of instantaneous luminescence spectra in the long-wavelength range (λ>700 nm). The role and the possibility of the directed energy transfer between molecules with orientationally broadened spectra in the biological systens are discussed.     

Laser-Raman spectroscopy of living cells

Investigations into the laser—Raman shift spectra of bacterial and mammalian cells have revealed that many Raman lines observed at 4–6 K, do not appear in the spectra of cells held at 300 K. At 300 K, Raman activity, at set frequencies, is observed only when the cells are metabolically active; however, the actual live cell spectrum, between 0 and 3400 cm^?1, has been found to alter in a specific way with time as the cells' progress through their life cycles. Lines above 300 cm^?1, from in vivo Raman active states, appear to shift to higher wave numbers whereas those below 300 cm^?1 seem to shift to lower ones. The transient nature of many shift lines observed and the intensity of them when present in the spectrum indicates that, in vivo, a metabolically induced condensation of closely related states occurs at a set time in the life of a living cell. In addition, the calculated ratio between the intensities of Stokes and anti-Stokes lines observed suggests that the metabolically induced “collective” Raman active states are produced, in vivo, by non thermal means. It appears, therefore, that the energetics of the well established cell “time clock” may be studied by laser—Raman spectroscopy; moreover, Raman spectroscopy may yield a new type of information regarding the physics of such biological phenomena as nutrition, virus infection and oncogenesis.     

Is there a shift to “active nanostructures”?

It has been suggested that an important transition in the long-run trajectory of nanotechnology development is a shift from passive to active nanostructures. Such a shift could present different or increased societal impacts and require new approaches for risk assessment. An active nanostructure “changes or evolves its state during its operation,” according to the National Science Foundation’s (2006) Active Nanostructures and Nanosystems grant solicitation. Active nanostructure examples include nanoelectromechanical systems (NEMS), nanomachines, self-healing materials, targeted drugs and chemicals, energy storage devices, and sensors. This article considers two questions: (a) Is there a “shift” to active nanostructures? (b) How can we characterize the prototypical areas into which active nanostructures may emerge? We build upon the NSF definition of active nanostructures to develop a research publication search strategy, with a particular intent to distinguish between passive and active nanotechnologies. We perform bibliometric analyses and describe the main publication trends from 1995 to 2008. We then describe the prototypes of research that emerge based on reading the abstracts and review papers encountered in our search. Preliminary results suggest that there is a sharp rise in active nanostructures publications in 2006, and this rise is maintained in 2007 and through to early 2008. We present a typology that can be used to describe the kind of active nanostructures that may be commercialized and regulated in the future.     

Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis

Historically the interest in the catalytic properties of transition metal carbides (TMC) has been inspired by their “Pt-like” properties in the transformation reactions of hydrocarbon molecules. Recent studies, however, have revealed that the reaction pathways of oxygen-containing molecules are significantly different between TMCs and Pt-group metals. Nonetheless, TMCs demonstrate intriguing catalytic properties toward oxygen-containing molecules, either as the catalyst or as the catalytically active substrate to support metal catalysts, in several important catalytic and electrocatalytic applications, including water electrolysis, alcohol electrooxidation, biomass conversion, and water gas shift reactions. In the current review we provide a summary of theoretical and experimental studies of the interaction of TMC surfaces with oxygen-containing molecules, including both inorganic (O₂, H₂O, CO and CO₂) and organic (alcohols, aldehydes, acids and esters) molecules. We will discuss the general trends in the reaction pathways, as well as future research opportunities in surface science studies that would facilitate the utilization of TMCs as catalysts and electrocatalysts.     

溶液中β胡萝卜素的共振拉曼光谱性质的研究

β胡萝卜素是一种重要的共轭多烯生物分子, 其在光电器件与功能材料等研制方面有重要应用。本文利用金刚石对顶砧技术, 在0～0.60 GPa的压强范围下, 分别对β胡萝卜素溶于水和二硫化碳溶液进行了原位拉曼光谱测量, 比较了二者的拉曼频移和半高宽等光谱特性。实验结果表明, 两种样品的拉曼频移均随着压强的增加而向高波数方向移动, 半高宽也随之增加。引用线性链状多烯分子的两种理论模型, 即 “相干弱阻尼电子-晶格振动模型”和 “有效共轭长度模型”等理论给予了解释。其机理是由于压力的增加, β胡萝卜素分子被压缩, 结构有序性下降, 有效共轭长度减小, 拉曼活性降低, 碳碳键的相干弱阻尼电子-晶格振动减弱。CC键的键长变短, 因此拉曼蓝移; CC键的键长差增加, 从而使半高宽增加。此外, 由于β胡萝卜素溶于非极性溶剂CS₂溶液中, 受到周围溶剂分子的作用, 使溶质与溶剂之间的色散力作用对压力更敏感一些, 从而使得其拉曼频移和半高宽随压强变化的斜率要比溶于水中的大。为研究共轭多烯分子在外场下的分子结构变化以及溶剂中分子的存在形式等具有一定的应用价值。     

Excited state intramolecular proton transfer of 1,2-dihydroxyanthraquinone by femtosecond transient absorption spectroscopy

1,2-Dihydroxyanthraquinone (alizarin) shows dual emission bands with a large Stokes shift from a “locally-excited (LE)” and “proton-transferred (PT)” tautomers in the excited state. Excited state intramolecular proton transfer (ESIPT) reaction of alizarin is tunable by changing concentration, solvent polarity, excitation wavelength, and etc. ESIPT reaction of alizarin in the excited state was investigated by steady-state absorption/emission spectroscopy and femtosecond transient absorption spectroscopy. In ethanol solution, the lifetime of PT tautomer of alizarin was measured as 87 ps, in addition to 0.35 and 8.3 ps vibrational cooling dynamics for the LE and PT tautomers of alizarin, respectively. In binary mixtures of ethanol and water, the excited state dynamics became more complicated; the LE and PT tautomers appeared to decay with 8.9 and 30.8 ps lifetimes, which is much shorter compared to the lifetime of the PT tautomer in ethanol. A long-lived nonradiative state in the excited states of alizarin was found as well, which was proposed as a “trapped” state with tightly hydrogen-bonded water molecules. The ESIPT reaction of alizarin was blocked in a 1:1 mixture of ethanol-water due to strong hydrogen bonding between water molecules and alizarin, which was further confirmed by the efficient coupling of alizarin to TiO₂ nanoparticles in the 1:1 binary mixture of ethanol-water.     

分子空位缺陷对环三亚甲基三硝胺含能材料几何结构、电子结构及振动特性的影响

含能材料中的微观缺陷是导致“热点”形成并相继引发爆轰的重要因素. 然而, 由于目前人们对材料内部微观缺陷的认识不足, 限制了对含能材料中“热点”形成微观机理的理解, 进而阻碍了含能材料的发展和应用. 为了洞悉含能材料内部微观缺陷特性及探索缺陷引发“热点”的形成机理, 利用第一性原理方法研究了分子空位缺陷对环三亚甲基三硝胺(RDX) 含能材料的几何结构、电子结构及振动特性的影响, 探讨了微观缺陷对初始“热点”形成的基本机理. 采用周期性模型分析了分子空位缺陷对RDX几何结构、电子能带结构、电子态密度及前线分子轨道的影响. 采用团簇模型分析了分子空位缺陷对RDX振动特性的影响. 结果发现, 分子空位缺陷的存在使其附近的N–N键变长, 分子结构变得松弛; 使导带中很多简并的能级发生分离, 电子态密度减小, 并使由N-2p和O-2p轨道形成的导带底和价带顶均向费米面方向移动, 降低了能带隙值, 增加了体系活性. 前线分子轨道及红外振动光谱的计算分析表明, 分子缺陷使最高已占分子轨道电荷主要集中在缺陷附近的分子上, 且分子中C–H键和N–N键能减弱. 这些特性表明, 分子空位缺陷的存在使体系能带隙变小, 并使缺陷附近的分子结构松弛, 电荷分布增多, 反应活性增强; 在外界能量激发下, 缺陷附近分子将变得不稳定, 分子中的C–H键或N–N键较易先发生断裂, 发生化学反应释放能量, 进而成为形成“热点”的根源.     

Living fluids

One of the major emerging fields of research of the beginning of this century concerns living fluids. By “living fluids”, we mean two major categories of complex fluids: (i) fluids which are essential to life, like blood, and (ii) active fluids made of particles that are able to propel themselves in the suspending fluid by converting a form of their energy into mechanical motion. Studies on active fluids have known a considerable interest since the last decade. Blood might be viewed as an old topic, but the progresses in experimental techniques, analytical concepts and numerics, have contributed nowadays to a dramatic renewal of the interest in this field, with a great potential towards understanding physical and mechanical factors in cardiovascular diseases. These fields have considerably strengthened interdisciplinary research. The series of reviews of this dossier focus on the tremendous recent progress achieved in research on living fluids both from the experimental and theoretical points of views. These reviews present also the major open issues, making of this dossier a unique guide for future research in these fields. This project grew up thanks to the international summer school that we organized on the topic “living fluids” at the IES (Institut dʼétudes scientifiques) of Cargèse (Corsica) in 2012.     

Scattering of Polarized and Natural Light by a Monolayer of Spherical Homogeneous Spatially Ordered Particles under Normal Illumination

We consider distortions of the shapes of absorption bands of strongly scattering samples in the spectra of molecules adsorbed on the surface of dispersed solids. We show that the influence of the scattering on IR spectra of dispersed samples is not reduced merely to a weakening of the intensity of the transmitted light, but, rather, the scattering affects the contour of a spectral band due to changes in the refractive index of the substance in the range of the absorption band. Using carbon dioxide adsorbed on a NaX zeolite as an example, we demonstrate two methods for taking into account the contribution of the scattering to the spectra of surface compounds: the registration of the “diffuse-transmission” spectrum and placing a sample into an immersion liquid, for which liquid oxygen is used. The obtained spectra indicate that, if the zeolite is saturated with the adsorbate, the band of the antisymmetric stretching vibration of CO₂ molecules broadens and reveals a complex structure as a result of the resonant dipole–dipole interaction between adsorbed molecules.     

Interaction of water molecules with defective carbonaceous clusters: An ab initio study

First-principle calculations are used to study the interaction of water molecules with carbonaceous clusters containing single carbon atom vacancy, similar to those which may be found in soot nanoparticles. It is shown that the dissociative adsorption of one water molecule at the vacancy site may lead to the formation of a “ketone-like” structure which can then act as a nucleation center for additional water molecules. Such a mechanism can thus participate in the hydrophilic behavior of soot primary particles although it appears less favorable than water nucleation around more hydrophilic sites such as carboxyl or hydroxyl groups.     

Metabolite Pools and Metabolic Branching as Factors of in-vivo Isotope Discriminations by Kinetic Isotope Effects

Abstract

Inter- and intra-molecular non-statistical isotope distributions do not only require the existence of a kinetic isotope effect on a defined enzyme catalyzed reaction, but also the prerequisite that this reaction is located at a metabolic branching point. Furthermore a metabolic and isotopic balance demand that the extent of the isotopic shift is reciprocal to the products' yields. On this base the ¹³C-enrichment of L-ascorbic acid in position C-1 and the depletion of glycerol in C-1 are interpreted. The ¹³C-pattern of natural malic acid is discussed as a consequence of isotope effects on the carboxylation of pyruvate and PEP and on the pyruvate dehydrogenase reaction. The patterns of natural products synthezised by transfer of “active acetaldehyde” is proposed to be due to an isotope effect on the thiamine pyrophosphate containing lyase reaction. An isotope effect on the reduction of “active formaldehyde” to “active methyl” and the existence of corresponding pools is responsible for ¹³C-enrichments and depletions of natural products in positions bearing these intermediates. Finally a model for the main nitrogen pools and for isotope discriminations between α-amino, ω-amino-N and amide pools in plants is proposed.     

Mössbauer spectroscopy of <Superscript>57</Superscript>Fe in <Emphasis Type="Italic">α</Emphasis>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> following implantation of <Superscript>57</Superscript>Mn<Superscript>*</Superscript>

Two Fe/MCM-41 systems, one of them sylilated, were obtained to be used as catalysts in Fischer–Tropsch reaction. They have more than 90% of the iron species located inside the support channels, leading to a narrow crystal size distribution accessible to reactive gases. The samples were characterized by X-ray diffraction, atomic absorption spectroscopy, N₂ adsorption, Mössbauer spectroscopy and Fourier transformer infrared spectroscopy. Mössbauer spectroscopy allowed us to demonstrate that the catalytic active species were the same in both catalysts. The only difference between them was the surface hydrophobicity, which decreases the “water gas shift reaction” in the sylilated catalyst. Besides, this solid is more active for hydrocarbon production, with a lower methane yield.     

Scanning photoluminescent spectroscopy of bioconjugated quantum dots

We report on the application of the bio-conjugated quantum dots (QDs) for a “sandwich” enzyme-linked immunosorbent assay (ELISA) cancer testing technique. Quantum dot ELISA detection of the cancer PSA antigen at concentrations as low as 0.01 ng/ml which is ～50 times lower than the classic “sandwich” ELISA was demonstrated. Scanning photoluminescence (PL) spectroscopy was performed on dried ELISA wells and the results compared with the same QD samples dried on a solid substrate. We confirmed a “blue” up to 37 nm PL spectral shift in a case of QDs conjugated to PSA antibodies. Increasing of the “blue” spectral shift was observed at lower PSA antigen concentrations. The results can be used to improve sensitivity of “sandwich” ELISA cancer antigen detection.     

New injector boosts light intensity at the LNLS

The active participation by more than 70 attendees in a one-day workshop on in situ XAFS studies of nanocatalysts demonstrated that even though in situ XAFS studies of catalysts have been performed for over 30 years, the field is as vibrant and stimulating as ever. The workshop, held May 16, part of the 2006 Joint NSLS/CFN Users' Meeting, was co-organized by Simon Bare (UOP LLC) and Anatoly Frenkel (Yeshiva University). The format of the workshop was two overview presentations on the Synchrotron Catalysis Consortium, followed by nine technical presentations, and a poster session in conjunction with the main Users' Meeting. It is a pleasure to announce that the first place cash award for best student/postdoc poster was given to Minhua Shao (Stony Brook University) for his work on “novel electrocatalysts for oxygen reduction reaction,” and the second place award was presented to Wen Wen (BNL – Chemistry) for his work on “in situ time-resolved characterization of novel Cu-MoO₂ catalysts during the water gas shift reaction.”     

Confinement of atoms with Robin’s condition: Spontaneous symmetry breaking

The properties of the ground state of the hydrogen atom in a spherical vacuum cavity with general boundary “not going out” conditions (i.e., when the probability current through the boundary vanishes) are studied. It is shown that in contrast to the confinement of an atom by a potential barrier, in this case depending on the parameters of the cavity, the atom could be in stable equilibrium at the center of the cavity or shift towards its periphery: spontaneous breaking of spherical symmetry occurs. The phase diagram of the shift and the dependence of the shift value and the binding energy of the ground state of the atom on the cavity parameters are presented. At the same time, the deformation properties of the electron wave function (WF) for an asymmetric distortion are so nontrivial that a non-zero shift occurs even when an electron is repulsed from the cavity boundary.     

Corrugated single layer templates for molecules: From h-BN nanomesh to graphene based quantum dot arrays

Functional nano-templates enable self-assembly of otherwise impossible arrangements of molecules. A particular class of such templates is that of sp² hybridized single layers of hexagonal boron nitride or carbon (graphene) on metal supports. If the substrate and the single layer have a lattice mismatch, superstructures are formed. On substrates like rhodium or ruthenium these superstructures have unit cells with ~3-nm lattice constant. They are corrugated and contain sub-units, which behave like traps for molecules or quantum dots, which are small enough to become operational at room temperature. For graphene on Rh(111) we emphasize a new structural element of small extra hills within the corrugation landscape. For the case of molecules like water it is shown that new phases assemble on such templates, and that they can be used as “nano-laboratories” where many individual processes are studied in parallel. Furthermore, it is shown that the h-BN/Rh(111) nanomesh displays a strong scanning tunneling microscopy-induced luminescence contrast within the 3 nm unit cell which is a way to address trapped molecules and/or quantum dots.     

The study of microwave pressure lineshifts

The results of experimental investigations of pressure shifts and broadening of spectral lines of polar molecules performed in the submillimeter region by a microwave spectrometer RAD are reported. About 30 measurements were made of self-shift and foreign gas shift parameters of the lines of NH₃, PH₃, AsH₃, and H₂O molecules including lineshifts in excited vibrational states, lineshifts of transitions connected by common levels, lines with various values of J and K quantum numbers, and the “forbidden” |ΔK| = 3 lines. On the basis of the data obtained in this work and data available in the literature, new experimental dependences of lineshifts on molecular parameters are found. The results are well described by a simple “Stark effect” model of lineshifts. Some new directions of investigations are outlined.     

Attosecond physics with neutrons and electrons: Ultrafast entanglement and decoherence phenomena involving protons in condensed matter and molecules

Nuclei and electrons in condensed matter and/or molecules are usually entangled, due to the prevailing electromagnetic interactions. Usually, the “environment” of a microscopic scattering system (e.g., a proton) causes an ultrafast decoherence, thus making atomic and/or nuclear entanglement effects not directly accessible to experiments. However, neutron Compton scattering (NCS) and electron Compton scattering represent ultrafast techniques operating in the sub-femtosecond timescale, thus opening a way for investigation of such dehoherence and short-lived entanglement phenomena of atoms in molecules and condensed matter. The experimental context of NCS and a new striking scattering effect from protons (H-atoms) in several condensed systems and molecules are described. In short, one observes an “anomalous” decrease of scattering intensity from protons, which seem to become partially “invisible” to the neutrons. The experiments apply large energy (several electronvolts) and momentum (10–200 Å^?1 transfers, and the collisional (or scattering) time between the neutron and a struck proton is only 100–1000 attoseconds long. Similar results are also obtained with electron-atom Compton scattering at large momentum transfers. As an example, we present new NCS experimental results from a single crystal, which also provide new physical insights into the attosecond quantum dynamics of protons in molecules and condensed matter. Theoretical discussions and models are presented which show that the effect under consideration is caused by the non-unitary time evolution (due to decoherence) of open quantum systems during the ultrashort, but finite, time-window of the neutron-proton scattering process. The conceptual connection with the well known Quantum Zeno Effect is pointed out. The experimental results, together with their qualitative interpretation “from first principles,” show that epithermal neutrons being available at spallation sources, and electron spectrometers providing large momentum transfers, may represent novel tools for investigation of thus far unknown physical and chemical attosecond phenomena.