What controls the melting properties of DNA-linked gold nanoparticle assemblies?

We report a series of experiments and a theoretical model designed to systematically define and evaluate the relative importance of nanoparticle, oligonucleotide, and environmental variables that contribute to the observed sharp melting transitions associated with DNA-linked nanoparticle structures. These variables include the size of the nanoparticles, the surface density of the oligonucleotides on the nanoparticles, the dielectric constant of the surrounding medium, target concentration, and the position of the nanoparticles with respect to one another within the aggregate. The experimental data may be understood in terms of a thermodynamic model that attributes the sharp melting to a cooperative mechanism that results from two key factors: the presence of multiple DNA linkers between each pair of nanoparticles and a decrease in the melting temperature as DNA strands melt due to a concomitant reduction in local salt concentration. The cooperative melting effect, originating from short-range duplex-to-duplex interactions, is independent of DNA base sequences studied and should be universal for any type of nanostructured probe that is heavily functionalized with oligonucleotides. Understanding the fundamental origins of the melting properties of DNA-linked nanoparticle aggregates (or monolayers) is of paramount importance because these properties directly impact one's ability to formulate high sensitivity and selectivity DNA detection systems and construct materials from these novel nanoparticle materials.     

Preparation and characterization of p-tert-butylcalix[8]arene bonded capillaries for open-tubular capillary electrochromatography

p-tert-Butylcalix[8]arene bonded capillaries for open-tubular capillary electrochromatography were prepared with γ-glycidoxypropyltrimethoxysilane as a bridge. The bonded capillary displayed low and steady electroosmotic flow (EOF) values over the pH range from 4 to 9. Detection limits for direct spectrophotometric detection at 277 nm for benzenediols (at a signal to noise ratio of 2) were 0.96 mg l⁻¹ for the unbonded capillary and 1.48 mg l⁻¹ for the bonded capillary, showing that the bonded layer did not show significant absorbance and hence decreased sensitivity. The bonded capillaries showed good separation selectivity for o-, m- and p-benzenediols, α- and β-naphthols, and α- and β-naphthylamines. This selectivity was attributed to significant interactions between the analytes and the bonded p-tert-butylcalix[8]arene, which contributed to the electrochromatographic separation mechanism. The bonded capillaries gave high stability and reproducibility.     

Studies on the Binding Mode of Pinacyanol Chloride to Nucleic Acids

The interaction of pinacyanol chloride(PC) with nucleic acids has been investigated by a series of experiments.Extensive hypochromism,appreciable peak shifts,isosbestic points and new peaks of the product of binding to nucleic acids in the spectra were observed.They showed that the interaction between PC and nucleic acids occurred.The results from absorption spectra of DNA,DNA melting,electrophoresis and fluorescence polarization studies have indicated that PC binds to DNA in nonintercalative way.Consistent with the nonintercalation,the studies of fluorescence titration and absorption titration specified that the binding of PC to nucleic acids occurred by an outside stacking binding,in which nucleic acids served for acting templates,The fact that the new absorption peaks of bound PC at ca,485nm are just close to the absorption bands of Haggregate of PC at high concentrations without DNA further supports the outside stacking binding mode,In addition,other evidence indicated that the interaction between PC and nucleic acids is not purely electrostatic.     

Functional characterization of two-dimensional gel-separated proteins using sequential staining

Proteins separated by two-dimensional (2-D) gel electrophoresis can be visualized using various protein staining methods. This is followed by downstream procedures, such as image analysis, gel spot cutting, protein digestion, and mass spectrometry (MS), to characterize protein expression profiles within cells, tissues, organisms, or body fluids. Characterizing specific post-translational modifications on proteins using MS of peptide fragments is difficult and labor-intensive. Recently, specific staining methods have been developed and merged into the 2-D gel platform so that not only general protein patterns but also patterns of phosphorylated and glycosylated proteins can be obtained. We used the new Pro-Q Diamond phosphoprotein dye technology for the fluorescent detection of phosphoproteins directly in 2-D gels of mouse leukocyte proteins, and Pro-Q Emerald 488 glycoprotein dye to detect glycoproteins. These two fluorescent stains are compatible with general protein stains, such as SYPRO Ruby stain. We devised a sequential procedure using Pro-Q Diamond (phosphoprotein), followed by Pro-Q Emerald 488 (glycoprotein), followed by SYPRO Ruby stain (general protein stain), and finally silver stain for total protein profile. This multiple staining of the proteins in a single gel provided parallel determination of protein expression and preliminary characterization of post-translational modifications of proteins in individual spots on 2-D gels. Although this method does not provide the same degree of certainty as traditional MS methods of characterizing post-translational modifications, it is much simpler, faster, and does not require sophisticated equipment and expertise in MS.     

Synergism in the spreading of hydrocarbon-chain surfactants on polyethylene film-anionic and cationic mixtures by a two-step procedure

A study has been made of the adsorption, interaction, and spreading of mixtures of anionic and cationic surfactants at the aqueous solution/polyethylene (PE) interface. When a drop of an aqueous solution of an anionic or cationic hydrocarbon-chain surfactant is placed on a highly hydrophobic PE film (contact angle of water > 90 degrees ), it spreads to an area very little larger than that of a drop of water of the same volume. If the anionic and cationic hydrocarbon-chain surfactant solutions are mixed prior to being applied to PE film, synergism is small, if any, and the reproducibility of the experimental results is poor. However, when the cationic and anionic aqueous solutions are applied on the PE film in a sequential manner, a remarkable synergism in spreading is observed and the results are very reproducible. The area spread by an aqueous solution of the anionic-cationic mixture may be more than 400 times that of aqueous solutions of the same volume and surfactant concentration of the individual surfactant components. Previous work in this laboratory on surfactant systems showing synergism in spreading on PE film, but only weak interaction at the aqueous solution/air interface, showed that the synergy was due to changes at the aqueous solution/PE interface and not to the changes at the aqueous solution/air or PE/air interface. Investigation of the adsorption behavior at the aqueous solution/solid interface of two of the anionic-cationic mixtures studied here indicates the reason for differences in spreading behavior observed with different anionic-cationic mixtures. The more similar the adsorption tendencies at the solid/aqueous solution interface of the anionic and cationic surfactants, and the closer their adsorption to an equimolar monolayer there, the stronger their interaction there and the greater their enhancement of the spreading. A mechanism is proposed for the synergy in spreading observed, based upon the difference between the surface tension in the precursor film at the spreading interface and that at the top of the spreading drop.     

Nanotubes fabricated from Ni-naphthalocyanine by a template method

Novel naphthalocyanine (Nc) nanotubes with special wall structures were fabricated by a template method using Nc molecules as building blocks. Thermal stabilization of the ordered columnar structures of the tetrakis(tert-butyl)naphthalocyanine (Ni-BNc) molecules, induced from the pi-pi interactions in the nanoscale channels of an alumina template, resulted in Nc nanotubes with walls consisting of well-ordered Nc molecular disks. Further thermal treatment of Ni-BNc at 600 degrees C produced carbonized Nc nanotubes containing ordered columnar, graphitic wall structures with the graphene disks arranged perpendicular to the tube axis. These nanotubes may be useful for extending the application of Nc molecules for nanodevice fabrication.     

REAuAl4Ge2 and REAuAl4(AuxGe1−x)2 (RE=rare earth element): Quaternary intermetallics grown in liquid aluminum

The two families of intermetallic phases REAuAl₄Ge₂ (1) (RE=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb) and REAuAl₄(Au_xGe_1−x)₂ (2) (x=0.4) (RE=Ce and Eu) were obtained by the reactive combination of RE, Au and Ge in liquid aluminum. The structure of (1) adopts the space group R-3m (CeAuAl₄Ge₂, , ; NdAuAl₄Ge₂, , ; GdAuAl₄Ge₂, , ; ErAuAl₄Ge₂, , ). The structure of (2) adopts the tetragonal space group P4/mmm with lattice parameters: , for EuAuAl₄(Au_xGe_1−x)₂ (x=0.4). Both structure types present slabs of “AuAl₄Ge₂” or “AuAl₄(Au_xGe_1−x)₂” stacking along the c-axis with layers of RE atoms in between. Magnetic susceptibility measurements indicate that the RE atoms (except for Ce and Eu) possess magnetic moments consistent with +3 species. The Ce atoms in CeAuAl₄Ge₂ and CeAuAl₄(Au_xGe_1−x)₂ (x=0.4) appear to be in a mixed +3/+4 valence state; DyAuAl₄Ge₂ undergoes an antiferromagnetic transition at 11 K and below this temperature exhibits metamagnetic behavior. The Eu atoms in EuAuAl₄(Au_xGe_1−x)₂ (x=0.4) appear to be in a 2+ oxidation state.     

Long‐range π‐type hydrogen bond in dimers CH2?HF,CH2O?H2O,and CH2O?NH3

Using four basis bets, (6‐311G(d,p), 6‐31+G(d,p), 6‐31++G(2d,2p), and 6‐311++G(3df,3pd), the optimized structures with all real frequencies were obtained at the MP2 level for the dimers CH₂O? HF, CH₂O? H₂O, CH₂O? NH₃, and CH₂O? CH₄. The structures of CH₂O? HF, CH₂O? H₂O, and CH₂O? NH₃ are cycle‐shaped, which result from the larger bend of σ‐type hydrogen bonds. The bend of σ‐type H‐bond O…H? Y (Y?F, O, N) is illustrated and interpreted by an attractive interaction of a chemically intuitive π‐type hydrogen bond. The π‐type hydrogen bond is the interaction between one of the H atoms of CH₂O and lone pair(s) on the F atom in HF, the O atom in H₂O, or the N atom in NH₃. In contrast with the above three dimers, for CH₂O? CH₄, because there is not a π‐type hydrogen bond to bend its linear hydrogen bond, the structure of CH₂O? CH₄ is noncyclic shaped. The interaction energy of hydrogen bonds and the π‐type H‐bond are calculated and discussed at the CCSD (T)/6‐311++G(3df,3pd) level. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

分散聚合水基聚苯胺乳胶微球制备与表征

水溶性空间稳定剂聚乙烯吡咯烷酮（PVP）存在时，采用分散聚合制备水溶性单分散的聚苯胺(PAn)乳胶粒子，采用透射电子显微镜（TEM）观察粒子形态及尺寸；利用紫外-可见吸收光谱对胶体分散体系进行表征.实验结果表明，当PAn含量较少（w< 16.78％）时， PAn-PVP复合乳胶粒子呈米粒状；当PAn含量较大（w >23.22％）时， PAn-PVP复合乳胶粒子呈球形.     

Ultraviolet photochemistry of ethane: implications for the atmospheric chemistry of the gas giants

Chemical processing in the stratospheres of the gas giants is driven by incident vacuum ultraviolet (VUV) light. Ethane is an important constituent in the atmospheres of the gas giants in our solar system. The present work describes translational spectroscopy studies of the VUV photochemistry of ethane using tuneable radiation in the wavelength range 112 ≤ λ ≤ 126 nm from a free electron laser and event-triggered, fast-framing, multi-mass imaging detection methods. Contributions from at least five primary photofragmentation pathways yielding CH₂, CH₃ and/or H atom products are demonstrated and interpreted in terms of unimolecular decay following rapid non-adiabatic coupling to the ground state potential energy surface. These data serve to highlight parallels with methane photochemistry and limitations in contemporary models of the photoinduced stratospheric chemistry of the gas giants. The work identifies additional photochemical reactions that require incorporation into next generation extraterrestrial atmospheric chemistry models which should help rationalise hitherto unexplained aspects of the atmospheric ethane/acetylene ratios revealed by the Cassini–Huygens fly-by of Jupiter.

The vacuum ultraviolet photodissociation dynamics of ethane provide clues for modelling the atmospheric chemistry of the gas giants.