Ratiometric Detection of microRNA Using Hybridization Chain Reaction and Fluorogenic Silver Nanoclusters

miRNA (miR)-155 is a potential biomarker for breast cancers. We aimed at developing a nanosensor for miR-155 detection by integrating hybridization chain reaction (HCR) and silver nanoclusters (AgNCs). HCR serves as an enzyme-free and isothermal amplification method, whereas AgNCs provide a built-in fluorogenic detection probe that could simplify the downstream analysis. The two components were integrated by adding a nucleation sequence of AgNCs to the hairpin of HCR. The working principle was based on the influence of microenvironment towards the hosted AgNCs, whereby unfolding of hairpin upon HCR has manipulated the distance between the hosted AgNCs and cytosine-rich toehold region of hairpin. As such, the dominant emission of AgNCs changed from red to yellow in the absence and presence of miR-155, enabling a ratiometric measurement of miR with high sensitivity. The limit of detection (LOD) of our HCR-AgNCs nanosensor is 1.13 fM in buffered solution. We have also tested the assay in diluted serum samples, with comparable LOD of 1.58 fM obtained. This shows the great promise of our HCR-AgNCs nanosensor for clinical application.     

Multiplier ideal sheaves in complex and algebraic geometry

The application of the method of multiplier ideal sheaves to effective problems in algebraic geometry is briefly discussed. Then its application to the deformational invariance of plurigenera for general compact algebraic manifolds is presented and discussed. Finally its application to the conjecture of the finite generation of the canonical ring is explored, and the use of complex algebraic geometry in complex Neumann estimates is discussed.

     

Quantitation of homoharringtonine in plasma by high-performance liquid chromatography with amperometric detection

A high-performance liquid chromatographic procedure was developed for the quantitation of homoharringtonine in plasma. Harringtonine was used as an internal standard, and 1 ml of sample was required. The single-step extraction with dichloromethane resulted in almost 100% recovery for homoharringtonine and harringtonine. Analysis was performed on a reversed-phase CN column with amperometric detection. Chromatography was completed in 12 min. At an oxidation potential of +1.0 V, the detection limit was 1 ng/ml at a signal-to-noise ratio of 2. The mean analytical recovery for homoharringtonine was 99.5%. The within-run precision and between-run precision were both less than 11%. The method is equally applicable for plasma or serum, and it has been demonstrated to be applicable for study of the pharmacokinetics of homoharringtonine in patients suffering from acute non-lymphocytic leukaemia.     

Dispersion and distribution of organically modified montmorillonite in nylon‐66 matrix

Nylon‐66 nanocomposites were prepared by melt‐compounding nylon‐66 with an alkyl ammonium surfactant pretreated montmorillonite (MMT). The thermal stability of the organic MMT powders was measured by thermogravimetric analysis. The decomposition of the surfactant on the MMT occurred from 200 to 500 °C. The low onset decomposition temperature of the organic MMT is one shortcoming when it is used to prepare polymer nanocomposites at high melt‐compounding temperatures. To provide greater property enhancement and better thermal stability of the polymer/MMT nanocomposites, it is necessary to develop MMT modified with more thermally stable surfactants. The dispersion and spatial distribution of the organic MMT layers in the nylon‐66 matrix were characterized by X‐ray diffraction. The organic MMT layers were exfoliated but not randomly dispersed in the nylon‐66 matrix. A model was proposed to describe the spatial distribution of the organic MMT layers in an injection‐molded rectangular bar of nylon‐66/organic MMT nanocomposites. Most organic MMT layers were oriented in the injection‐molding direction. Layers near the four surfaces of the bar were parallel to their corresponding surfaces; whereas those in the bulk differed from the near‐surface layers and rotated themselves about the injection‐molding direction. The influence of the spatial distribution of the organic MMT on crystallization of nylon‐66 was also investigated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1234–1243, 2003     

Substituted m-phenylene bridges as strong ferromagnetic couplers for Cu(II)-bridge-Cu(II) magnetic interactions: new perspectives

Based on a combined theoretical-experimental study, we propose that substituted m-phenylene ligands (m-N-Phi-N) can act as tuneable strong ferromagnetic couplers connecting Cu(II) ions; a new complex presenting that bridge with J close to +15 cm(-1) has been suggested and synthesized.     

Gas-phase fragmentation of the Ag+—phenylalanine complex: Cation—π interactions and radical cation formation

Collision-induced dissociation experiments on the Ag+-phenylalanine complex using several collision energies were shown to yield ten different fragment ions. Unambiguous assignment of these fragment ions were made by careful analysis of deuterium labeling experiments. The losses of H2O, CO, CO2, and AgH were commonly observed; also encountered were the losses of H2, Ag, and H. Deuterium labeling experiments and density functional calculations have been employed to probe fragmentation mechanisms that account for all experimental results.     

Existence of doubly charged lead monohydrate: experimental evidence and theoretical examination

Despite reports to the contrary, doubly charged lead monohydrate is a stable species against both proton and charge transfers. [Pb(H(2)O)](2+) has been observed as a minor product in the ligand-exchange reaction of [Pb(CH(3)CN)](2+) with H(2)O after collisional activation. Density functional theory has been used to examine reaction profiles of [Pb(H(2)O)(n)](2+) where n = 1, 2, and 3.     

Ultrafast time-resolved study of photophysical processes involved in the photodeprotection of p-hydroxyphenacyl caged phototrigger compounds

A combined femtosecond Kerr gated time-resolved fluorescence (fs-KTRF) and picosecond Kerr gated time-resolved resonance Raman (ps-KTR(3)) study is reported for two p-hydroxyphenacyl (pHP) caged phototriggers, HPDP and HPA, in neat acetonitrile and water/acetonitrile (1:1 by volume) solvents. Fs-KTRF spectroscopy was employed to characterize the spectral properties and dynamics of the singlet excited states, and the ps-KTR(3) was used to monitor the formation and subsequent reaction of triplet state. These results provide important evidence for elucidation of the initial steps for the pHP deprotection mechanism. An improved fs-KTRF setup was developed to extend its detectable spectral range down to the 270 nm UV region while still covering the visible region up to 600 nm. This combined with the advantage of KTRF in directly monitoring the temporal evolution of the overall fluorescence profile enables the first time-resolved observation of dual fluorescence for pHP phototriggers upon 267 nm excitation. The two emitting components were assigned to originate from the (1)pipi (S(3)) and (1)npi (S(1)) states, respectively. This was based on the lifetime, the spectral location, and how these varied with the type of solvent. By correlating the dynamics of the singlet decay with the triplet formation, a direct (1)npi --> (3)pipi ISC mechanism was found for these compounds with the ISC rate estimated to be approximately 5 x 10(11) s(-)(1) in both solvent systems. These photophysical processes were found to be little affected by the kind of leaving group indicating the common local pHP chromophore is largely responsible for the fluorescence and relevant deactivation processes. The triplet lifetime was found to be approximately 420 and 2130 ps for HPDP and HPA, respectively, in the mixed solvent compared to 150 and 137 ns, respectively, in neat MeCN. The solvent and leaving group dependent quenching of the triplet is believed to be associated with the pHP deprotection photochemistry and indicates that the triplet is the reactive precursor for pHP photorelease reactions for the compounds examined in this study.