How mobile NMR can help with the conservation of paintings

The conservation of paintings is fundamental to ensure that future generations will have access to the ideas of the grand masters who created these art pieces. Many factors, such as humidity, temperature, light, and pollutants, pose a risk to the conservation of paintings. To help with painting conservation, it is essential to be able to noninvasively study how these factors affect paintings and to develop methods to investigate their effects on painting degradation. Hence, the use of mobile nuclear magnetic resonance (NMR) as a method of investigation of paintings is gaining increased attention in the world of Heritage Science. In this mini-review, we discuss how this method was used to better understand the stratigraphy of paintings and the effect different factors have on the painting integrity, to analyze the different cleaning techniques suitable for painting conservation, and to show how mobile NMR can be used to identify forgeries. It is also important to keep in mind its limitations and build upon this information to optimize it to extend its applicability to the study of paintings and other precious objects of cultural heritage.     

TG and DSC analyses of eucalyptus black liquor as alternative methods to estimate solids content

As a consequence of the continuous increase in the production rate of pulp and paper mills around the world, a great quantity of black liquor, a by-product of the wood digestion process, is produced. This by-product has a great potential as biomass, but needs to be concentrated to higher solids content to be burned as fuel in a recovery boiler. This is necessary to make the pulping process economically feasible, incinerating black liquor to produce high pressure steam, recycling inorganic chemicals to the process. The greater the solids content in black liquor, the better the combustion process in the boiler. Nevertheless, concentration of solids in black liquor above 75 mass/%, causes scaling formation on the heat transfer surfaces of evaporators and concentrators, due to the precipitation of sodium salts, reducing the overall efficiency of this equipment. The aim of this work is to evaluate the use of thermal analyses techniques, TG and DSC, as alternative methods to estimate solids content in eucalyptus black liquor samples since this information is essential to understand scaling formation process, allowing actions to reduce this industrial problem. Traditional techniques applied to determine solids content use gravimetric methods, which are simple, fine, but take a lot of time to be executed. Thermal analyses have proved to be very accurate and have the advantage to be faster than the traditional techniques. On the other hand, the cost-benefit relationship of the traditional technique is much greater and the final decision which one should be used depends on the conditions available.     

Developing front‐end devices for improved sample preparation in MS‐based proteome analysis

Chemical analysis has long relied on instrumentation, from the simplest (eg, burets) to the more sophisticated (eg, mass spectrometers) to facilitate precision measurements. Regardless of their complexity, the development of a new instrumental device can be a valued approach to address problems in science. In this perspective, we outline the process of novel device design, from early phase conception to the manufacturing and testing of the tool or gadget. Focus is placed on the development of improved front‐end devices to facilitate protein sample manipulations ahead of mass spectrometry, which therefore augment the proteomics workflow. Highlighted are some of the many training secrets, choices, and challenges that are inherent to the often iterative process of device design. In hopes of inspiring others to pursue instrument design to address relevant research questions, we present a summary list of points to consider prior to innovating their own devices.     

Density functional theory for strongly-interacting electrons: perspectives for physics and chemistry

Improving the accuracy and thus broadening the applicability of electronic density functional theory (DFT) is crucial to many research areas, from material science, to theoretical chemistry, biophysics and biochemistry. In the last three years, the mathematical structure of the strong-interaction limit of density functional theory has been uncovered, and exact information on this limit has started to become available. The aim of this paper is to give a perspective on how this new piece of exact information can be used to treat situations that are problematic for standard Kohn-Sham DFT. One way to use the strong-interaction limit, more relevant for solid-state physical devices, is to define a new framework to do practical, non-conventional, DFT calculations in which a strong-interacting reference system is used instead of the traditional non-interacting one of Kohn and Sham. Another way to proceed, more related to chemical applications, is to include the exact treatment of the strong-interaction limit into approximate exchange-correlation energy density functionals in order to describe difficult situations such as the breaking of the chemical bond.     

Measurement of trace explosive residues in a surrogate operational environment: implications for tactical use of chemical sensing in C-IED operations

A campaign to measure the amount of trace explosive residues in an operational military environment was conducted on May 27–31, 2007, at the National Training Center at Fort Irwin, CA, USA. The objectives of this campaign were to develop the methods needed to collect and analyze samples from tactical military settings, to use the data obtained to determine what the trace explosive signatures suggest about the potential capabilities of chemical-based means to detect IEDs, and, finally, to present a framework whereby a sound understanding of the signature science can be used to guide development of new sensing technologies and sensor concepts of operation. Through our use of combined background and threat signature data, we have performed statistical analyses to estimate upper limits of notional sensor performance that is limited only by the spatial correlation of the signature chemicals to the threats of interest.     

Sensitivity of metal nanoparticle surface plasmon resonance to the dielectric environment

Electrodynamic simulations of gold nanoparticle spectra were used to investigate the sensitivity of localized surface plasmon band position to the refractive index, n, of the medium for nanoparticles of various shapes and nanoshells of various structures. Among single-component nanoparticles less than 130 nm in size, sensitivities of dipole resonance positions to bulk refractive index are found to depend only upon the wavelength of the resonance and the dielectric properties of the metal and the medium. Among particle plasmons that peak in the frequency range where the real part of the metal dielectric function varies linearly with wavelength and the imaginary part is small and slowly varying, the sensitivity of the peak wavelength, lambda, to refractive index, n, is found to be a linearly increasing function of lambda, regardless of the structural features of the particle that determine lambda. Quasistatic theory is used to derive an analytical expression for the refractive index sensitivity of small particle plasmon peaks. Through this analysis, the dependence of sensitivity on band position is found to be determined by the wavelength dependence of the real part, epsilon', of the particle dielectric function, and the sensitivity results are found to extend to all particles with resonance conditions of the form, epsilon' = -2chin(2), where chi is a function of geometric parameters and other constants. The sensitivity results observed using accurate computational methods for dipolar plasmon bands of gold nanodisks, nanorods, and hollow nanoshells extend, therefore, to particles of other shapes (such as hexagonal and chopped tetrahedral), composed of other metals, and to higher-order modes. The bulk refractive index sensitivity yielded by the theory serves as an upper bound to sensitivities of nanoparticles on dielectric substrates and sensitivities of nanoparticles to local refractive index changes, such as those associated with biomolecule sensing.     

Size-Exclusion Chromatography: A Twenty-First Century Perspective

Now in its sixth decade, size-exclusion chromatography (SEC) remains the premier method by which to determine the molar mass averages and distributions of natural and synthetic macromolecules. Aided by its coupling to a variety and multiplicity of detectors, it has also shown its ability to characterize a host of other physicochemical properties, such as branching, chemical, and sequence length heterogeneity size distribution; chain rigidity; fractal dimension and its change as a function of molar mass; etc. SEC is also an integral part of most macromolecular two-dimensional separations, providing a second-dimension size-based technique for determining the molar mass of the components separated in the first dimension according to chemical composition, thus yielding the combined chemical composition and molar mass distributions of a sample. While the potential of SEC remains strong, our awareness of the pitfalls and challenges inherent to it and to its practice must also be ever-present. This Perspective aims to highlight some of the advantages and applications of SEC, to bring to the fore these caveats with regard to its practice, and to provide an outlook as to potential areas for expansion and growth.

     

Voronoi deformation density (VDD) charges: Assessment of the Mulliken, Bader, Hirshfeld, Weinhold, and VDD methods for charge analysis

We present the Voronoi Deformation Density (VDD) method for computing atomic charges. The VDD method does not explicitly use the basis functions but calculates the amount of electronic density that flows to or from a certain atom due to bond formation by spatial integration of the deformation density over the atomic Voronoi cell. We compare our method to the well-known Mulliken, Hirshfeld, Bader, and Weinhold [Natural Population Analysis (NPA)] charges for a variety of biological, organic, and inorganic molecules. The Mulliken charges are (again) shown to be useless due to heavy basis set dependency, and the Bader charges (and often also the NPA charges) are not realistic, yielding too extreme values that suggest much ionic character even in the case of covalent bonds. The Hirshfeld and VDD charges, which prove to be numerically very similar, are to be recommended because they yield chemically meaningful charges. We stress the need to use spatial integration over an atomic domain to get rid of basis set dependency, and the need to integrate the deformation density in order to obtain a realistic picture of the charge rearrangement upon bonding. An asset of the VDD charges is the transparency of the approach owing to the simple geometric partitioning of space. The deformation density based charges prove to conform to chemical experience.     

Curvature Effects in the Analysis of Pendant Bubble Data: Comparison of Numerical Solutions, Asymptotic Arguments, and Data

The pendant bubble method is commonly used to measure the evolution of the surface tension of surfactant solutions. Initially, the bubble interface is free of adsorbed surfactant. As time progresses, surfactant diffuses to the interface, adsorbs, and reduces the surface tension. The surface tension is assumed to be in equilibrium with the instantaneous surface concentration. Therefore, surface tension data are analyzed in terms of interfacial thermodynamics and mass transfer models in order to infer the mechanisms which determine the surfactant transport. Diffusion from the bulk solution to the bubble can be approximated as diffusion to a spherical interface. Approximating this process as diffusion to a plane introduces significant errors into the data analysis. Mass transfer to a sphere differs from that to a plane; the equilibration of the spherical interface is more rapid simply because of geometry. The failure to account for this effect in the interpretation of pendant bubble data can lead to serious errors in the transport coefficients for the surfactants. In the diffusion-controlled limit, surfactant diffuses to the sublayer immediately adjacent to the interface and adsorbs in local equilibrium according to the adsorption isotherm. There is a closed-form solution for Fick's law describing adsorption to a sphere in an infinite solution which reduces to the Ward and Tordai solution when the bubble radius is large. This equation, along with the adsorption isotherm relating the surface concentration and the sublayer concentration, must be solved numerically in order to solve for the time evolution of the surface concentration. At early times, the adsorption isotherm can be expanded about the clean interface state. At long times, small departures from the equilibrium state can be assumed. In these limits, asymptotic expansions can be obtained. The short- and long-time expansions are found in this study for adsorption to a sphere and compared to those obtained previously for adsorption to a planar interface. In particular, the long-time asymptote for adsorption to a sphere is proportional to t(-3/2); this asymptote differs significantly from that for adsorption to a plane, which goes as t(-1/2). The full solution for adsorption to a sphere is compared to the Ward and Tordai solution for adsorption to a planar interface. From a comparison of the full solutions, it is established that curvature cannot be neglected unless the ratio of the adsorption depth to the bubble radius is negligible. This ratio can be calculated a priori from equilibrium isotherm parameters. Using constants which describe the surfactant C(12)E(8), for which curvature plays a strong role in the surfactant adsorption dynamics, the short- and long-time solutions for adsorption to the interface are compared to the full solutions and to dynamic surface tension data to infer the range of validity of the approximations. Copyright 2001 Academic Press.     

Efficient analyte oxidation in an electrospray ion source using a porous flow-through electrode emitter

This article describes the components, operation, and use of a porous flow-through electrode emitter in an electrospray ion source. This emitter electrode geometry provided enhanced mass transport to the electrode surface to exploit the inherent electrochemistry of the electrospray process for efficient analyte oxidation at flow rates up to 800 microL/min. An upstream current loop in the electrospray source circuit, formed by a grounded contact to solution upstream of the emitter electrode, was utilized to increase the magnitude of the total current at the emitter electrode to overcome current limits to efficient oxidation. The resistance in this upstream current loop was altered to control the current and "dial-in" the extent of analyte oxidation, and thus, the abundance and nature of the oxidized analyte ions observed in the mass spectrum. The oxidation of reserpine to form a variety of products by multiple electron transfer reactions and oxidation of the ferroceneboronate derivative of pinacol to form the ES active radical cation were used to study and to illustrate the performance of this new emitter electrode design. Flow injection, continuous infusion, and on-line HPLC experiments were performed.     

Molecular polarizability of organic compounds and their complexes: LVI. Molar volume and structure in a solution of the compounds with several axes of intramolecular rotation

Molar volumes in solutions of compounds like orthoformic esters, trialkyl phosphates, trialkylphosphites, substituted aziridines, cyclopropanes, cyclohexanes, boroxines, N-aryl-4-pyridones, decalines, and cyclooctane were determined and discussed. Conformations of alkyl substituents in the esters were found to be similar to the conformations of the corresponding alkanes. Molar volumes of aziridines and cyclopropanes were found to be additive with respect to the molar volumes of bond and group increments. The nature of solvation of the molecules of these compounds was found to be similar to that in the model systems which served for the calculations of the increments. Molar volumes of cyclohexane, decaline, and cyclooctane also were found to be additive with respect to the contributions of the molar volumes of increments of the corresponding bonds and groups. The solvation and the steric structure of substituted boroxines were found to be similar to those of the structurally analogous substituted benzenes. Conformations of N-aryl-4-pyridone and its substituted derivatives in solutions were found to be similar to the conformations of biphenyl and its derivatives. A possibility of simplification of the methods for determining the dipole moments and Kerr constants of compounds from their additive molar volumes was demonstrated.     

化学平衡有向图

根据化学平衡原理和图论中的基本概念，提出了一种适用于化学平衡计算的赋权有向图。这种有向图具有三个重要性质：其一，边的方向改变则该边的权随着取逆(取原权的倒数或负值)；其二，顺乘逆除(或顺加逆减)一条路上的各权得到自起点至终点的累积权；其三，回路的权等于1(或零)。本文主要叙述这种图的提出及其在化学平衡中的初步应用。     

Self-consistent field study of the alignment by an electric field of a cylindrical phase of block copolymer

Self-consistent field theory is applied to a film of cylindrical-forming block copolymer subject to a surface field which tends to align the cylinders parallel to electrical plates, and to an external electric field tending to align them perpendicular to the plates. The Maxwell equations and self-consistent field equations are solved exactly, numerically, in real space. By comparing the free energies of different configurations, we show that for weak surface fields, the phase of cylinders parallel to the plates makes a direct transition to a phase in which the cylinders are aligned with the field throughout the sample. For stronger surface fields, there is an intermediate phase in which cylinders in the interior of the film, aligned with the field, terminate near the plates. For surface fields which favor the minority block, there is a boundary layer of hexagonal symmetry at the plates in which the monomers favored by the surface field occupy a larger area than they would if the cylinders extended to the surface.     

Surfing silica surfaces superciliously

The present mini-review summarizes the experience gathered by our group in developing different classes of novel quaternarized heterocyclic compounds able to modulate and reverse the electroendoosmotic flow (EOF) in a most peculiar manner. The first class comprises mono-salt compounds, with the determinant omega-iodoalkyl chains of different lengths (typically C4-C8), able to be adsorbed by silicas, at alkaline pH, and spontaneously alkylate ionised silanols, thus becoming covalently affixed to it. The second class is constituted by di-salt compounds, attached at the termini of an alkyl chain of variable lengths (here too, typically, C4-C8). This second class is unable to bind covalently silica surfaces, although, in thin-layer chromatography, it exhibits an extraordinary affinity for silica beads, contrary to the first one. On the basis of the strikingly different behaviour, structural rules are derived for the minimum requirements for general classes of amines to bind to silica walls and modify EOF. For compounds unable to bind covalently to the wall, the most important structural motif is two quaternary nitrogens spaced apart by a C4 chain: this seems to be the average distance (i.e., 0.8 nm) between two adjacent, ionized silanols for a snug fit. The other structural binding motif is the "hydrophobic decoration", i.e., the ratio of charged groups to alkyl residue in the various amines; amines with high levels of such alkane groups (i.e., with higher hydrophobicity), seem to bind more tenaciously to the wall, probably due to hydrophobic interaction not to the wall but among the amine derivatives themselves, when carpeting the silica.     

杨石先对农药化学学科的重要贡献及其学术思想

杨石先先生一生献身于我国的教育事业与化学学科的发展,在62年中为我国培养了无数高质量的科教人才。他除了长期担任南开大学校长之外, 还创建了我国大学第一个专职研究所,即元素有机化学研究所。他率先开展了我国元素有机化学与农药化学的科学研究,领导了元素有机化学国家重点实验室的建立,是我国元素有机化学和农药化学的奠基人和开拓者。他倡导用有机化学的专业知识,科学和系统地开展农药化学研究,组建队伍获得20项科研成果,发表上百篇科学与论述性论文,为我国开展自主创新农药研究事业作出重要贡献。在农药化学学科的学术思想中,他强调要弄清该学科的交叉性、系统性和内在规律性,倡导要学习国际先进经验,要结合国情自主创新,要为国家经济服务,要对世界农药科技做出贡献。他毕生对人才培养给予了特别的重视,为我国科技事业持续发展作出了重大贡献。     

Orbital phase control of the preferential branching of chain molecules.

The orbital phase theory was applied to the stabilities of the branched isomers (1) of E(4)H(10) (E = C, Si, Ge, Sn) relative to the normal ones (2). The orbital phase prediction was confirmed by ab initio molecular orbital (MO) and density functional theory (DFT) calculations as well as by some experimental results. Further applications to the relative stabilities of other alkane and alkene isomers lead to the preference of the branched to the normal isomers, the neopentane-type to isobutane-type branching, the terminal to inner methyl branching, and the methyl to ethyl inner substitution in the longer alkanes, as well as the preference of isobutene to 2-butene moieties. The preferential stabilization of the branched isomers was shown to be general and controlled by the orbital phase.     

Multivalent ions and biomolecules: Attempting a comprehensive perspective

Ions are ubiquitous in nature. They play a key role for many biological processes on the molecular scale, from molecular interactions, to mechanical properties, to folding, to self-organisation and assembly, to reaction equilibria, to signalling, to energy and material transport, to recognition etc. Going beyond monovalent ions to multivalent ions, the effects of the ions are frequently not only stronger (due to the obviously higher charge), but qualitatively different. A typical example is the process of binding of multivalent ions, such as Ca²⁺, to a macromolecule and the consequences of this ion binding such as compaction, collapse, potential charge inversion and precipitation of the macromolecule. Here we review these effects and phenomena induced by multivalent ions for biological (macro)molecules, from the “atomistic/molecular” local picture of (potentially specific) interactions to the more global picture of phase behaviour including, e. g., crystallisation, phase separation, oligomerisation etc. Rather than attempting an encyclopedic list of systems, we rather aim for an embracing discussion using typical case studies. We try to cover predominantly three main classes: proteins, nucleic acids, and amphiphilic molecules including interface effects. We do not cover in detail, but make some comparisons to, ion channels, colloidal systems, and synthetic polymers. While there are obvious differences in the behaviour of, and the relevance of multivalent ions for, the three main classes of systems, we also point out analogies. Our attempt of a comprehensive discussion is guided by the idea that there are not only important differences and specific phenomena with regard to the effects of multivalent ions on the main systems, but also important similarities. We hope to bridge physico-chemical mechanisms, concepts of soft matter, and biological observations and connect the different communities further.     

Labile Metabolites

The importance of ascertaining the possible presence of unstable metabolites at an early stage in the drug development process cannot be underestimated. Failure to detect labile metabolites could lead to costly delays to development. Very often, erratic or difficult to explain analytical or kinetic data provide clues to metabolite degradation, the most commonly encountered reaction being the conversion of a metabolite to parent drug. Examples of unstable glucuronide conjugates, N-oxides, alcohols and phenols abound in the literature. They are not easy to find, however, and have to be ‘mined’ by extensive searching. This report, by no means exhaustive, brings together the major examples according to substance class. Remedial action to avoid metabolite degradation is discussed, as well as a number of specific examples which cannot be categorised under the main substance classes.     

Exploring supramolecular interactions and architectures by scanning force microscopies

The development of new methodologies based on scanning force microscopy (SFM) has made it possible to map topographies, chemical functionalities, and numerous other physicochemical properties of complex assemblies, to unravel dynamic processes, to measure forces generated along a reaction coordinate, to nanopattern surfaces and to nanomanipulate objects. This tutorial review highlights the most recent applications of these SFM-based capabilities, on and beyond imaging, to the exploration of supramolecular interactions and architectures, to the fabrication of smart materials and to the optimization of (nano)devices.