Synthesis of isochrysohermidin-distamycin hybrids

The synthesis of the alkylating subunit of the DNA cross-linking agent, isochrysohermidin (2), and its subsequent incorporation into conjugates with distamycin A (1) are described. The DNA binding properties of these agents were compared to that of distamycin A, using a fluorescence intercalator displacement (FID) assay.     

Effects of water plasma immersion ion implantation on surface electrochemical behavior of NiTi shape memory alloys in simulated body fluids

Water plasma immersion ion implantation (PIII) was conducted on orthopedic NiTi shape memory alloy to enhance the surface electrochemical characteristics. The surface composition of the NiTi alloy before and after H₂O-PIII was determined by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) was utilized to determine the roughness and morphology of the NiTi samples. Potentiodynamic polarization tests and electrochemical impedance spectroscopy (EIS) were carried out to investigate the surface electrochemical behavior of the control and H₂O-PIII NiTi samples in simulated body fluids (SBF) at 37 °C as well as the mechanism. The H₂O-PIII NiTi sample showed a higher breakdown potential (E_b) than the control sample. Based on the AFM results, two different physical models with related equivalent electrical circuits were obtained to fit the EIS data and explain the surface electrochemical behavior of NiTi in SBF. The simulation results demonstrate that the higher resistance of the oxide layer produced by H₂O-PIII is primarily responsible for the improvement in the surface corrosion resistance.     

Enantioselective Generation of Adjacent Stereocenters in a Copper‐Catalyzed Three‐Component Coupling of Imines,Allenes, and Diboranes

A highly enantio‐ and diastereoselective copper‐catalyzed three‐component coupling affords the first general synthesis of homoallylic amines bearing adjacent stereocenters from achiral starting materials. The method utilizes a commercially available NHC ligand and copper source, operates at ambient temperature, couples readily available simple imines, allenes, and diboranes, and yields high‐value homoallylic amines that exhibit versatile amino, alkenyl, and boryl units.     

Elucidating Factors Manipulated the Formation of Multiply Charged Protein Homomultimeric Complexes by Electrospray Ionization

Native non‐covalently bonded protein‐protein and protein‐substrate complexes are of great interest and have been extensively studied by electrospray ionization mass spectrometry (ESI‐MS). Multiply charged protein homomultimeric complexes are shown to form by ESI‐MS. This study addresses factors that can artificially induce the formation of multiply charged protein homomultimeric complexes. Cytochrome c (Cyt c) and ubiquitin, which are monomers in solution, were found to generate (Cyt c)_mⁿ⁺ by electrospray ionization (ESI). The homomultimeric complexes were not limited to dimeric complexes but include also multiply charged trimers, tetramers, and pentamers. The observation of these homomultimeric complexes has never been revealed from a Cyt c solution at the concentration as low as 10 μM. Increasing the concentration of Cyt c enhanced the formation of (Cyt c)_mⁿ⁺ as expected; however, the protein concentration does not affect the relative intensities of monomeric and dimeric complexes. Additionally the enrichment of NH₄OH also promotes the formation of (Cyt c)_mⁿ⁺. Notably, source collision‐induced dissociations (source‐CID) of (Cyt c)_mⁿ⁺ alter the charge state distribution (CSD) and may lead to an incorrect interpretation of Cyt c conformations. Hence, extra care should be taken when using CSD to interpret the conformation of a protein derived from ESI‐MS.     

Two dimensional mapping of cancer cell extracts by liquid chromatography-capillary electrophoresis with ultraviolet absorbance detection

A two-dimensional liquid chromatography/capillary electrophoresis technique was developed for rapid and comprehensive mapping of cell extracts. The cell extracts were first separated by reversed-phase HPLC based on hydrophobicity. Fractions of the effluent from the HPLC system were collected into 96-well microtiter plates and dried under vacuum. The fractions were reconstituted with deionized water, separated by capillary array electrophoresis based on charge-to-size ratio, and detected by UV absorption at 214 nm. Prior to analysis by multiplexed capillary electrophoresis, the reconstituted fractions were concentrated on-column using large volume sample stacking with polarity switching. In this way, high-resolution analysis of even the minor components in the complicated mixture was possible.     

Light-emitting diode-induced fluorescence detection of native proteins in capillary electrophoresis

A continuous-wave 280 nm light-emitting diode (LED) was used as the excitation source for native fluorescence detection of proteins in CE. The operating current and temperature of the LED were optimized in order to achieve high luminescence power. It was found that a forward current of 30 mA and a temperature of approximately 5 degrees C gave the best S/N. By using a set of two ball lenses to focus light from the LED, we achieved a spot of approximately 200 mum with a power of 0.1-0.2 mW on the detection window. Fluorescence was collected with a ball lens at 90 degrees angle through a bandpass filter onto a photomultiplier tube. In CZE an LOD of 20 nM for conalbumin was reached. In capillary gel electrophoresis all eight proteins from a commercial standard kit were detected with high S/N. For a 10 microg/mL total protein mixture, S/N was better than 3 for all proteins in solution. Further improvement in LOD should be possible on utilization of an LED with higher luminescence power.     

Exploiting in situ NMR to monitor the formation of a metal–organic framework

The formation processes of metal–organic frameworks are becoming more widely researched using in situ techniques, although there remains a scarcity of NMR studies in this field. In this work, the synthesis of framework MFM-500(Ni) has been investigated using an in situ NMR strategy that provides information on the time-evolution of the reaction and crystallization process. In our in situ NMR study of MFM-500(Ni) formation, liquid-phase ¹H NMR data recorded as a function of time at fixed temperatures (between 60 and 100 °C) afford qualitative information on the solution-phase processes and quantitative information on the kinetics of crystallization, allowing the activation energies for nucleation (61.4 ± 9.7 kJ mol⁻¹) and growth (72.9 ± 8.6 kJ mol⁻¹) to be determined. Ex situ small-angle X-ray scattering studies (at 80 °C) provide complementary nanoscale information on the rapid self-assembly prior to MOF crystallization and in situ powder X-ray diffraction confirms that the only crystalline phase present during the reaction (at 90 °C) is phase-pure MFM-500(Ni). This work demonstrates that in situ NMR experiments can shed new light on MOF synthesis, opening up the technique to provide better understanding of how MOFs are formed.

A new in situ NMR methodology for studying the formation processes of MOFs is reported, supported by SAXS and PXRD experiments. Synthesis of a phosphonate-based MOF is described, from molecular aggregation through to nucleation and crystallisation.     

Fluorescence detection in capillary arrays based on galvanometer step scanning.

A computer-controlled galvanometer scanner is adapted for scanning a focused laser beam across a 96-capillary array for laser-induced fluorescence detection. The signal at a single photomultiplier tube is temporally sorted to distinguish among the capillaries. The limit of detection for fluoresceins is 3 x 10(-11) M (S/N = 3) for 5 mW of total laser power scanned at 4 Hz. The observed cross-talk among capillaries is 0.2%. Advantages include the efficient utilization of light due to the high duty-cycle of step scan, good detection performance due to the reduction of stray light, ruggedness due to the small mass of the galvanometer mirror, low cost due to the simplicity of components, and flexibility due to the independent paths for excitation and emission.     

Polyplatinayne/polyoxometalate composite Langmuir‐Blodgett films: Preparation,structural characterization,and potential optoelectronic applications

A new family of organometallic/inorganic composite Langmuir‐Blodgett (LB) films consisting of rigid‐rod polyplatinayne polymer ([Pt‐T(OMe‐Fl)T]_∞ or [Pt‐T(F‐Fl)T]_∞, where the triplet bonds are abbreviated by T, and fluorene ring by Fl) as the π‐conjugated organometallic molecule, polyoxometalate (POM, POM = K₃PMo₁₂O₄₀, H₃PW₁₂O₄₀, or H₆P₂W₁₈O₆₂) of the Keggin and Dawson structures as the inorganic component, and dimethyldioctadecylammonium bromide (DODA) or a mixture of octadecanoic acid (OA) and docosanoic acid (DA) as the auxiliary film‐forming agent were prepared and characterized by π–A isotherms, UV–Vis absorption spectra, photoluminescence spectra, atomic force microscopy imaging, scanning tunneling microscopy, and low‐angle X‐ray diffraction. Our experimental results indicate that steady, even, and ordered Langmuir and LB films are formed in pure water and polyoxometalate subphases. It was shown that the POM molecules are probably embedded inside the polyplatinayne molecules in the LB film structure and they can quench the luminescence of the Pt polyyne. These Pt‐polyyne based LB films display interesting electric conductivity behavior. [Pt‐T(OMe‐Fl)T]_∞/DODA/HPW₁₂ monolayer film shows a good electrical conductivity, and the tunneling current amounts to ±100 nA when the voltage is set at ±8 V. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3193–3206, 2008