Distinguishing authentic and counterfeit banknotes by surface chemical composition determined using electrospray laser desorption ionization mass spectrometry

Electrospray laser desorption ionization mass spectrometry (ELDI/MS) was used to rapidly distinguish authentic banknotes from counterfeits of the US dollar and the New Taiwan dollar. The banknotes' surfaces were irradiated with a pulsed ultraviolet laser, after which the desorbed ink compounds entered an electrospray plume and formed ions via interactions with charged solvent species. Authentic banknotes were found to differ from their counterfeit equivalents in their surface chemical compositions. The detected chemical compounds included various polymers, plasticizers and inks; these results were comparable with those obtained using solvent extraction followed by electrospray ionization mass spectrometry analysis. Because of the high spatial resolution of the laser beam, ELDI/MS analysis resulted in minimal damage to the banknotes. Copyright © 2013 John Wiley & Sons, Ltd.     

Enhanced biocompatibility in biostable poly(carbonate)urethane

In this work, we synthesized two MDI-based polyurethanes, including a poly(ether)urethane (PEU) and a poly(carbonate)urethane (PCU), by using different soft segments, poly(tetramethylene oxide) and poly(hexyl, ethyl)carbonate diol (M approximately 2,000). We demonstrated that, in addition to the enhanced biostability of PCU over PEU, the biological performances of PCU in vitro were also improved in general. These included, better cellular attachment and proliferation, less platelet activation, as well as reduced monocyte activation. The unusual wide-ranging enhancement in biocompatibility for PCU was believed to be related to the larger micro-phase separation in PCU (approximately 25 nm) that caused distinct protein adsorption on the surface. The total number of adherent monocytes (nonactivated and activated) on the bare sample surfaces, albumin pre-adsorbed sample surfaces, and fibrinogen pre-adsorbed sample surfaces.     

Esterase-assisted accumulation of 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxyl into lymphocytes

The intracellular detection of hydroxyl radical (HO*) through spin trapping/electron paramagnetic resonance (EPR) spectroscopy has been one of the great challenges in studying free radicals in biology. While 5-carboxy-5-methyl-1-pyrroline N-oxide, can specifically spin trap HO* in homogeneous solutions, the ionic nature of nitrone at physiologic pH prevents its entry into cells. We hypothesized that conversion of carboxyl-bearing spin probes such as nitrone into an esterase-hydrolyzable labile ester would permit intracellular localization and accumulation of the spin probes. To test the feasibility of such an approach, we prepared the model compound, 3-acetoxymethoxycarbonyl-2,2,5,5-tetramethyl-1-pyrrolidinyloxyl. This ester enabled ready accumulation of spin label to mM levels in lymphocytes. We suggest that its retention within these cells was the result of intracellular hydrolysis to 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxyl. Moreover, our studies show that aminoxyl was stable in the intracellular environment. These model studies suggest a viable strategy for detecting intracellular HO* by using the acetoxymethyl ester of 5-carboxy-5-methyl-1-pyrroline N-oxide.     

信号处理技术在重叠化学信号解析中的应用*

重叠峰解析是目前分析化学中亟须解决的一个重要问题,化学计量学用于重叠峰解析就是借助某些数学或统计学方法,把通过化学方法和仪器未能完全分离的复合量测信号分解成几个单儿组分的信号,从而从重叠谱中获取每个组分的相关信息。本文综述了几种常见信号处理技术在重叠化学信号分辨中的应用,引用文献146篇。     

Isolation and characterization of a newly identified type II restriction endonuclease from a local streptomyces sp. in Taiwan

Streptomyces chusanensis ZS-2, isolated from a soil sample in Chusan in Taiwan, was found to produce a new Type II restriction endonuclease. This restriction enzyme was designated as SchI. The purified enzyme was characterized as having a subunit mol wt of 28 kDa, and was apparently free from exonuclease activities. It cleaves the phosphodiester bond between the fourth C and the fifth G on the 5’-CCGCGG-3’ sequence of DNAs, leaving a 2-nucleotide protruding end at its 3’ site. This data suggests that SchI is an isoschizomer of SacII. In addition, based on the comparison between SchI and SacII regarding reaction parameters, it seems that SchI is a better choice of restriction enzyme for genetic analysis and mapping.     

Effects of solute-matrix interaction on monitoring the conformational changes of immobilized proteins by surface plasmon resonance sensor

A real-time and labeling-free surface plasmon resonance (SPR) sensor was used to monitor the conformational changes of immobilized globule proteins (RNase A and lysozyme) in chemical unfolding and refolding. The effects of chemical denaturants on the protein structures were investigated. The methodology in protein conformational study on the solid surface is refined through the theoretic calculations and the conformational information of native/denatured proteins in solution. Additionally, our observation illustrates that the ambient buffer solution is merit to influence the refractive index of immobilized protein films and directly be observed from the SPR resonance angle shifts.     

Hydrogen‐Bonding Induced Cooperative Effect on the Energy Transfer in Helical Polynorbornenes Appended with Porphyrin‐Containing Amidic Alanine Linkers

Polynorbornenes appended with porphyrins containing a range of different linkers are synthesized. The use of bisamidic chiral alanine linkers between the pending porphyrins and the polymeric backbone has been shown to bring the adjacent porphyrin chromophores to more suitable orientation for exciton coupling owing to hydrogen bonding between the adjacent linkers. The hydrogen bonding between the adjacent pendants in these polymers may induce a cooperative effect and therefore render single‐handed helical structures for these polymers. Such a cooperative effect is reflected in the enhancement of FRET efficiencies between zinc–porphyrin and free base porphyrin in random copolymers.     

New Epoxy‐Substituted Nitrogenous Bisabolene‐Type Sesquiterpenes from a Hainan Sponge Axinyssa sp.

Two new uncommon epoxy‐substituted nitrogenous bisabolene‐type sesquiterpenes, 3‐formamido‐7,8‐epoxy‐α‐bisabolane ( 4 ), 3‐isocyano‐7,8‐epoxy‐α‐bisabolane ( 5 ), together with three known related sesquiterpenes, 1 – 3 , were isolated from the Hainan sponge Axinyssa sp. Their structures were determined on the basis of extensive spectroscopic analyses and by comparison of their NMR data with those of structurally related compounds.     

Determination of 77Se-77Se and 77Se-13C J-coupling parameters for the clusters [Re5OsSe8(CN)6]3- and [Re4Os2Se8(CN)6]2-

We have investigated rarely observed 77Se J-couplings (spin-spin couplings) in the mixed-metal face-capped octahedral clusters [Re5OsSe8(CN)6]3- and [Re4Os2Se8(CN)6]2- at natural abundance. To the best of our knowledge, these are the first observations of Se-Se spin-spin interactions between mu3-Se sites, important for stereochemical assignments in hexarhenium analogues, Chevrel phase materials, and similar cluster materials. NMR techniques such as COSY, INADEQUATE, and 2D J-resolved spectroscopy have been used in conjunction to study these interactions. The two isomers (cis and trans) of [Re4Os2Se8(CN)6]2- were distinguishable, and selective isotopic labeling of [Re5OsSe8(CN)6]3- with 13CN ligands enabled resonances to be assigned by observing the 2J (Se-M-C) couplings. For [Re5OsSe8(CN)6]3-, two different 2J (Se-M-Se) couplings were measurable on a single cluster, and these are related to one another through spin-spin interactions across a face diagonal or along an edge of the cube of inner selenium ligands. A rigorous analysis based on combinatorial math has been invoked to assign the couplings on the basis of the probability of multiple-spin interactions. The face diagonal association is found to result in a J-coupling interaction larger in magnitude than that from coupling along an edge of the cube-information critical for making stereochemical assignments of selenium sites.     

Hydration dynamics and time scales of coupled water-protein fluctuations

We report experimental and theoretical studies on water and protein dynamics following photoexcitation of apomyoglobin. Using site-directed mutation and with femtosecond resolution, we experimentally observed relaxation dynamics with a biphasic distribution of time scales, 5 and 87 ps, around the site Trp7. Theoretical studies using both linear response and direct nonequilibrium molecular dynamics (MD) calculations reproduced the biphasic behavior. Further constrained MD simulations with either frozen protein or frozen water revealed the molecular mechanism of slow hydration processes and elucidated the role of protein fluctuations. Observation of slow water dynamics in MD simulations requires protein flexibility, regardless of whether the slow Stokes shift component results from the water or protein contribution. The initial dynamics in a few picoseconds represents fast local motions such as reorientations and translations of hydrating water molecules, followed by slow relaxation involving strongly coupled water-protein motions. We observed a transition from one isomeric protein configuration to another after 10 ns during our 30 ns ground-state simulation. For one isomer, the surface hydration energy dominates the slow component of the total relaxation energy. For the other isomer, the slow component is dominated by protein interactions with the chromophore. In both cases, coupled water-protein motion is shown to be necessary for observation of the slow dynamics. Such biologically important water-protein motions occur on tens of picoseconds. One significant discrepancy exists between theory and experiment, the large inertial relaxation predicted by simulations but clearly absent in experiment. Further improvements required in the theoretical model are discussed.