Study of the cyanoacrylate fuming mechanism by matrix‐assisted laser desorption/ionization mass spectrometry

Despite cyanoacrylate fuming being widely used in the forensic science field, its mechanism is not well understood. In this study, matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry is used to study latent fingerprints that have been cyanoacrylate fumed in an attempt to gain insight into the fuming mechanism. In the negative mode mass spectrometry data, four compounds related to the polymerization of cyanoacrylate are identified and their structures are determined from accurate mass and MS/MS. A mechanism is proposed for the formation of these compounds that are regarded as intermediates in the polymerization reaction. In addition, based on the fuming of standard endogenous compounds, we suggest that fatty acids and amino acids are the major catalytic nucleophiles that initiate the polymerization reactions.     

A Review of Instrumental Approaches for Studying Historical Inks

In the last 10 years researchers have adapted a number of instrumental techniques for studying various aspects of historical inks that have been used in historical documents. In this paper, the applications of atomic spectroscopy such as GFAAS, ICP-MS, XRF, PIXE, and XANES are described for identifying and quantifying metals that are found in historical inks. Applications of vibrational spectroscopy, primarily Raman and near/mid-IR spectroscopy, are described for detecting organic and inorganic compounds in ink and paper.     

How to handle nanomaterials? The re-entry of individuals into the philosophy of chemistry

In this paper we will argue that the categories of physical individuals and chemical stuff are not sufficient to face the chemical ontology if nanomaterials are taken into account. From a perspective that considers ontological questions and wonders which the items involved in science are, we will argue that the domain of nanoscience must be considered as populated by entities that are neither individuals, as those of physics, nor stuff, as those items of macro-chemistry. This discussion, in virtue of the analysis of the nature of nanomaterials, leads to propose a proper ontological category for nanoparticles: nanoindividuals. Nanomaterials are sorts of individuals, but they are different from physical individuals and from chemical stuff. We will also claim to contribute to the growing field of the philosophy of chemistry, especially regarding discussions that manifest not only epistemological but also ontological issues. In this scenario, the field on nanoscience is particularly challenging.     

Structural chemistry of polycyclic heteroaromatic compounds. Part XI. Photoelectron spectra and electronic structures of tetracyclic hetarenes of the triphenylene type

The UV photoelectron spectra of several tetracyclic heteroaromatic compounds (2-9) which are pi-isoelectronic with triphenylene (1) have been recorded and analysed making use of semiempirical AM1 and PM3 as well as ab initio/DFT B3LYP calculations. In one series of compounds (2-7), the peripheral benzene rings of 1 are successively substituted by thiophene rings that are either [b]- or [c]-annellated with the central benzene unit. In 2-7 only marginal shifts are found for most of the IPs of electrons. In the benzotrithiophenes 5-7, a systematic variation is displayed by IP(pi7). Compared to 1, the pi electron system of benzo[c]trithiophene (7) is approximately two times as much destabilized as in the isomers 5 and 6 with [b]annellated thiophene rings. The IP[n(S)] values of the thiophene derivatives 2-7 indicate that these orbitals are clearly destabilized relative to thiophene. The same holds for the n(O) orbital of the furane derivative 9 in comparison with that of furane. In 9, only the higher pi MOs (pi7-pi9) are destabilized whereas the lower levels (pi1-pi4) are stabilized, and those in between (pi5-pi6) remain essentially unshifted. In the pyrrole derivative 8, all pi MOs are substantially destabilized by about 0.5-1.6 eV relative to 1.     

Application of flow field-flow fractionation for the characterization of macromolecules of biological interest: a review

An overview is given of the recent literature on (bio) analytical applications of flow field-flow fractionation (FlFFF). FlFFF is a liquid-phase separation technique that can separate macromolecules and particles according to size. The technique is increasingly used on a routine basis in a variety of application fields. In food analysis, FlFFF is applied to determine the molecular size distribution of starches and modified celluloses, or to study protein aggregation during food processing. In industrial analysis, it is applied for the characterization of polysaccharides that are used as thickeners and dispersing agents. In pharmaceutical and biomedical laboratories, FlFFF is used to monitor the refolding of recombinant proteins, to detect aggregates of antibodies, or to determine the size distribution of drug carrier particles. In environmental studies, FlFFF is used to characterize natural colloids in water streams, and especially to study trace metal distributions over colloidal particles. In this review, first a short discussion of the state of the art in instrumentation is given. Developments in the coupling of FlFFF to various detection modes are then highlighted. Finally, application studies are discussed and ordered according to the type of (bio) macromolecules or bioparticles that are fractionated.     

Current sol-gel activities in Japan

In Japan, sol-gel research activities are very prosperous and there are many successful commercial products. It appears that this trend will continue into the future. In this article, basic sol-gel research carried out in Japanese universities and applications of the sol-gel method to industrial production will be described. It should be noted that many unique studies, including photocatalysts and products involving coatings applied to automobiles and display panels, are found in Japan.     

Raft domain reorganization driven by short- and long-chain ceramide: a combined AFM and FCS study

Naturally occurring long-chain ceramides (Cer) are known to alter the lateral organization of biological membranes. In particular, they produce alterations of microdomains that are involved in several cellular processes, ranging from apoptosis to immune response. In order to induce similar biological effects, short-chain Cer are extensively used in in vivo experiments to replace their long-chain analogues. In this work, we used the combined approach of atomic force microscopy (AFM) and fluorescence correlation spectroscopy (FCS) to investigate the effect of Cer chain length in lipid bilayers composed of sphingomyelin, dioleoyl-phosphatidylcholine, and cholesterol. Our results show that only long-chain Cer, like C18 and C16, are able to segregate from the liquid-ordered phase, forming separate Cer-enriched domains. Conversely, short-chain Cer do not form a separate phase but alter the physical properties of the liquid-ordered domains, decreasing their stability and viscosity and perturbing the lipid packing. These differences may contribute to the explanation of the different physiological effects that are often observed for the long- and short-chain Cer.     

Theoretical study of structure and photoelectron spectroscopy of In(x)P(y)- and In(x)P(y) (x + y < or = 6) clusters

The geometries and vibrational frequencies of In(x)P(y)- and In(x)P(y) are investigated by hybrid B3LYP functional for x + y < or = 6 and CCSD(T) method for x + y < or = 3. As for the small clusters having two to three atoms, the geometrical and electronic structures and vibrational frequencies at the B3LYP level are in good agreement with those at the CCSD(T) level. Among the most stable structures of In(x)P(y)- and In(x)P(y) (x + y < or = 6) clusters the P-rich clusters are more stable than In-rich clusters. Moreover, we found that those P atoms in In(x)P(y)- and In(x)P(y) (x + y < or = 6) clusters prefer to form a P-P bond, triangle, quadrangle, and pentagon for y = 2, 3, 4, and 5, respectively. Also, the vertical detachment energies of In(x)P(y)- (x + y < or = 6) and electron affinities of In(x)P(y) (x + y < or = 6) clusters obtained by B3LYP are in good agreement with the experimental values available. Theoretically, we show that the electron affinity of In3P3 is very low because, as observed in the experiment, there is a formation of a new P-P bond after an electron is lost from In(3)P(3)-, and we find that the similar phenomena exhibit in In2P4(-) cluster as well.     

On the interactions of ions with the air/water interface

In the vicinity of a charged interface, the Poisson-Boltzmann approach considers that the ions obey Boltzmann distributions in a mean electrical field that satisfies the Poisson equation. However, the boundary between two dielectrics generates additional interactions between ions and the interface. The traditional models of ion hydration interactions, that assume that water is a homogeneous dielectric, predict that these interactions are repulsive for all kinds of ions, since all ions should prefer the medium with a larger dielectric constant, where they are better hydrated. In reality, the interactions between the ions and the neighboring water molecules can generate additional short-range ion-hydration interactions, which are either repulsive (for structure-making ions) or attractive (for structure-breaking ions). In the present paper, various models for the ion-hydration forces are examined and compared with the results of molecular dynamics simulations. At large ionic strengths, the latter results could be reproduced qualitatively only when short-ranged attractions between the structure-breaking ions and the interface were taken into account.     

Polymerization of styrene oxide by nitronium tetrafluoroborate

The polymerization of styrene oxide by nitronium tetrafluoroborate in nitromethane and methylene chloride at 5, 20, and 50°C is investigated. GPC analyses of the products combined with isocyanate method show that both cyclic and linear oligomers are formed. In CH₃NO₂ the cyclic dimer and trimer are 2-benzyl-4-phenyl-1,3-dioxolane and 1,3,5-tribenzyl-trioxane, respectively. In CH₂Cl₂ 2,5-diphenyldioxane is isolated. In nitromethane, mainly isomerized structures with acetal linkage are produced, while in methylene chloride isomerization does not proceed. By NMR and IR spectra the presence of C?O and OH end groups in the linear oligomers is shown. There are indications that oligomers are formed both directly from the monomer and by degradation of the polymer.     

Impact of multiple re-use of anion-exchange chromatography media on virus removal

We evaluated viral clearance in multiply-cycled anion-exchange media run in flow-through mode. We found that anion-exchange columns do not lose viral clearance capacity after extensive re-use, if they are cleaned with recommended buffers that do not chemically degrade the media. In contrast, anion-exchange (AEX) columns that are not cleaned or are cleaned with buffers that chemically degrade the media lost viral clearance capacity after extended use. In these cases, other performance attributes that changed at the same time were increased band spreading, decreased DNA clearance and accumulating backpressure that prevented re-use past 80-120 cycles. Thus, our data suggests that flow through mode anion-exchange columns that are cleaned with recommended cleaning buffers, and periodically monitored for band spreading, DNA clearance and/or backpressure need not be re-evaluated for viral clearance at the end of the validated media lifetime.     

Synthesis, characterization, and X-ray crystal structure of In(DOTA-AA) (AA = p-aminoanilide): a model for 111In-labeled DOTA-biomolecule conjugates

This report describes the synthesis and structural characterization of the indium complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid mono(p-aminoanilide) (DOTA-AA), a model compound for (111)In-labeled DOTA-biomolecule conjugates. In(DOTA-AA) was prepared by reacting DOTA-AA with 1 equiv of InCl(3) in 0.5 M ammonium acetate buffer (pH approximately 6). It was characterized by spectroscopic methods (IR, ES-MS, and (1)H NMR), elemental analysis, and X-ray crystallography. For comparison purposes, we also prepared the complex Y(DOTA-AA). ES-MS and (1)H NMR data are consistent with the proposed structure. HPLC analysis using a reversed phase method shows that the retention time of In(DOTA-AA) is approximately 2.0 min shorter than that of Y(DOTA-AA), demonstrating that In(DOTA-monoamide) is more hydrophilic than Y(DOTA-monoamide). In the solid state, In(DOTA-AA) has a twisted square antiprismatic coordination geometry with all eight donor atoms (N(4)O(4)) bonded to the In center. The average In-N and In-O distances are almost identical to those of Y-N and Y-O bonds found in Y(DOTA-d-Phe-NH(2)) even though the ionic radius of Y(3+) is much longer than that of In(3+). It seems that In(3+) does not fit the coordination cavity of DOTA-AA perfectly. The (1)H NMR data clearly demonstrated that In(DOTA-AA) becomes fluxional at room temperature, most likely due to dissociation of the acetamide-oxygen, rotation of acetate chelating arms, and inversion of ethylenic groups of the macrocyclic ring. Results from this study and our previous studies (Liu, S.; Pietryka, J.; Ellars C. E.; Edwards D. S. Bioconjugate Chem. 2002, 13, 902-913) suggest that the In(3+) complex of DOTA-monoamide in the solid state might be different from that in solution due to dissociation of the carbonyl-oxygen donor. Although Y(3+) and In(3+) complexes of DOTA-monoamide are both eight-coordinate in the solid state, the difference in their solution structures is most likely responsible for their difference in lipophilicity.     

Liquid crystals and life

The molecules of living systems invariably exhibit both thermotropic and/or lyotropic liquid crystalline properties. In some cases the mesophases formed by bio-materials have lamellar structures, whereas in other situations they form columnar phases. Many liquid crystal biomaterials are found in cell membranes, indicating that such structures have properties that are dependent on liquid crystallinity for their behaviour of a variety of bio-materials is discussed. function. In this article the mesomorphic     

Existence of nonlinear resonances in polyethylene

In this paper, we demonstrate that the internal dynamics and vibrational spectra of polyethylene are influenced by Fermi and other nonlinear resonances. In previous work, the first semiclassical theory and quantum numbers (in parabolic coordinates) appropriate for this type of resonance were developed. We find from detailed molecular dynamics simulations that the same types of quantum numbers are applicable for polyethylene stretch-bend mode interactions. In addition, a one-to-one resonance is found to exist from one local C H stretch to another C H stretch along the polymer chain.     

Microemulsion polymerization for producing fluorinated structured materials

When perfluoropolyether microemulsions are used during polymerization of fluoropolymers, the structure of the reaction environment can be strictly controlled. In particular, the number and size of polymer particles in latexes can be set freely, yielding a number of advantages. First, as a result of radical segregation, terminations can be decreased without reducing polymerization rate: in this way high molecular weights are easily obtained also with poorly reactive monomers. Moreover, in combination with a reversible chain transfer mechanism based on iodine, particle segregation allows establishing pseudo-living polymerization conditions. In this situation formation of long branches in the polymer can be controlled by using bifunctional molecules that are able to link two different polymer chains to each other during polymerization. This is the so-called “branching and pseudo-living” technology. Finally, by co-coagulating latexes of different polymers prepared by microemulsion polymerization, very small particles and, thus, high interface areas are generated. In this way properties of different polymers, such as fluoroelastomers and fluorinated semicrystalline polymers, are matched effectively, generating new nanocomposite materials that exhibit outstanding properties. In this paper these results are reported and an overview of some novel sophisticated fluoropolymers obtained in microemulsion is given.     

全金属负离子团簇Ga42-、In42-芳香性的磁特征与多重芳香性

The optimized geometries, frequencies, and total electronic energies of two all-metal dianionic clusters Ga42- , In42- are calculated at the B3LYP, B3PW91, and MP2 levels of theory. There are two stable structures for each Ga42- , In42- species. For Ga42- , In42- species the square isomers are the most stable. On the basis of these computed stable structures we focus on two magnetic properties: magnetic susceptibility anisotropy and nucleus-independent chemical shift (NICS) for the square planar Ga42- , In42- isomers, which are calculated with B3LYP and HF methods. The computed results of NICS show that the square planar Ga42- , In42- isomers possess strong aromaticity. The detailed molecular orbital analysis for the two isomers further reveals that the two square planar Ga42- , In42- isomers have multiple-fold aromaticity: one delocalized π MOs and two delocalized σ MOs, which play important role in explaining the special stability of these all-metal square clusters.     

磺酸基修饰复合功能树脂对水中对氨基苯酚的吸附行为研究

利用新型磺酸基修饰复合功能树脂NG-6对水中对氨基苯酚进行吸附,深入探讨了吸附中的动力学及热力学行为.实验结果表明,对氨基苯酚在NG-6上的吸附能够在较短的时间内达到平衡,动力学特性符合准二级动力学方程.此吸附是一个放热的自发过程,Freundlich等温吸附方程能够较好地拟合吸附等温线.     

The role of configurational entropy in biochemical cooperativity

Cooperativity is a common biochemical phenomenon in which two or more otherwise independent processes are thermodynamically coupled. Because cooperative processes are usually attended by changes in molecular conformation, thermodynamic coupling is usually attributed to an enthalpy-driven mechanism. In the family of glycopeptide antibiotics that includes vancomycin, however, cooperative phenomena occur that cannot be explained by conformational change. In this communication, we demonstrate that cooperativity in these systems can arise solely from changes in vibrational activity.     

Gas-phase separations of complex tryptic peptide mixtures

High-resolution ion mobility and time-of-flight mass spectrometry techniques have been used to analyze complex mixtures of peptides generated from tryptic digestion of fourteen common proteins (albumin, bovine, dog, horse, pig, and sheep; aldolase, rabbit; beta-casein, bovine; cytochrome c, horse; beta-lactoglobulin, bovine; myoglobin, horse; hemoglobin, human, pig, rabbit, and sheep). In this approach, ions are separated based on differences in mobilities in helium in a drift tube and on differences in their mass-to-charge ratios in a mass spectrometer. From data recorded for fourteen individual proteins (over a m/z range of 405 to 1,000), we observe 428 peaks, of which 205 are assigned to fragments that are expected from tryptic digestion. In a separate analysis, the fourteen mixtures have been combined and analyzed as one system. In the single dataset, we resolve 260 features and are able to assign 168 peaks to unique peptide sequences. Many other unresolved features are observed. Methods for assigning peptides based on the use of m/z information and existing mobilities or mobilities that are predicted by use of intrinsic size parameters are described.     

The Identification of Cotton Fibers Dyed with Reactive Dyes for Forensic Purposes

Some of the most common microtraces that are currently collected at crime scenes are fragments of single fibers. The perpetrator leaves them at a crime scene or takes them away, for example, on their clothing or body. In turn, the microscopic dimensions of such traces mean that the perpetrator does not notice them and therefore usually does not take action to remove them. Cotton and polyester fibers dyed by reactive and dispersion dyes, respectively, are very popular within clothing products, and they are hidden among microtraces at the scene of a crime. In our recently published review paper, we summarized the possibilities for the identification of disperse dyes of polyester fibers for forensic purposes. In this review, we are concerned with cotton fibers dyed with reactive dyes. Cotton fibers are natural ones that cannot easily be distinguished on the basis of morphological features. Consequently, their color and consequently the dye composition are often their only characteristics. The presented methods for the identification of reactive dyes could be very interesting not only for forensic laboratories, but also for scientists working in food, cosmetics or pharmaceutical/medical sciences.