Ultraviolet photodissociation at 266 nm of phosphorylated peptide cations

Ultraviolet (UV) photodissociation (PD) experiments using 266 nm light were performed for a series of phosphopeptide cations in a Fourier transform mass spectrometer. The objective of the experiments was to determine whether 266 nm UV irradiation on the phosphopeptide cations would induce unique peptide backbone dissociation. In addition, the general behavior of the phosphate loss (?80 or ?98 Da) was monitored, particularly for those phosphopeptides with a phosphotyrosine residue that itself is a UV chromophore. For phosphopeptides with a UV chromophore, their photodissociation behavior was very similar to that of low‐energy sustained off‐resonance irradiation collisionally activated dissociation (SORI‐CAD), with a few exceptions. For example, b‐ and y‐type peptide backbone fragments were prevalent, and their dephosphorylation behavior was consistent with that of the SORI‐CAD results. For phosphoserine peptides, the loss of a phosphate group was always observed. On the other hand, for phosphotyrosine peptides, the phosphate loss was found to be dependent on the presence of a basic amino group in the sequence and the charge state of the precursor ions, in agreement with the CAD results in the literature. However, hydrogen atom loss or aromatic side chain loss, which is known to be the excited state specific fragmentation pathway, was rarely observed in our 266 nm UV PD experiments, in contrast to the previous UV PD literature (particularly at 220 nm). The mechanism for these observations is described in terms of dominant internal conversion followed by intramolecular vibrational energy redistribution (IVR). Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation and characterization of crosslinked cellulose/sulfosuccinic acid membranes as proton conducting electrolytes

A series of crosslinked polymer electrolyte membranes were prepared by blending cellulose and sulfosuccinic acid (SA) for fuel cell applications. The crosslinking reaction of membranes occurred via the esterification between –OH of cellulose and –COOH of SA, as confirmed by FT-IR spectroscopy. Both the ion exchange capacity and the proton conductivity increased in proportion to the increase of SA concentrations due to the increasing portion of charged groups in the membrane. In contrast, the water uptake linearly increased up to 25 wt.% of SA concentration, above which it decreased abruptly. The maximum behavior of water uptake may be a result of competitive effect between the increasing number of ionic sites and the increasing degree of crosslinking with the SA concentrations. Wide angle X-ray scattering also showed that the crystalline structures of cellulose disappeared upon the introduction of SA. The mechanical properties of cellulose/SA membranes, i.e., tensile strength at break and Young’s modulus, showed a maximum at 15 wt.% of SA, as revealed by universal testing machine. These membranes exhibited good thermal stability up to 250 °C, as revealed by thermal gravimetric analysis.     

Response time and vendor–assembler relationship in a supply chain

Relationships between an assembler and a vendor in a supply chain are investigated in two-period models when the assembler wants to reduce response time by incentive systems. The assembler may offer myopic or farsighted incentive contracts to the vendor, under short-term or long-term relationships. Incentive schemes, effort levels, and expected payoffs under different perspectives and relationships are examined. We find that a farsighted assembler provides the vendor with a higher incentive than a myopic assembler in the first period. A long (short)-term relationship is preferred if the value of farsightedness under a long-term relationship is greater (less) than the switching option value under a short-term relationship. We propose several sufficient conditions regarding which perspectives and relationships are preferred.     

Practical synthesis of (S)‐7‐(2‐isopropylamino)ethylcamptothecin hydrochloride,potent topoisomerase I inhibitor

A practical semi‐synthetic method of (S)‐7‐(2‐isopropylamino)ethylcamptothecin hydrochloride has been developed. The Mannich reaction of (S)‐7‐methylcamptothecin with isopropylamine hydrochloride in dimethyl sulfoxide as a formaldehyde source gave the desired product in moderate yield.     

Hydrodechlorination of chlorophenols over Pd catalysts supported on zeolite Y,MCM-41 and graphene

Hydrodechlorination (HDC) reaction of chlorophenols was carried out using Pd catalysts supported over zeolite Y, MCM-41 or graphene. Pd-MCM-41 and Pd-Y zeolite were prepared by impregnation and ion-exchange method, respectively. Pd-graphene (Pd-G) was prepared by hydrazine hydrate reduction of palladium ion dispersed on graphene oxide. The catalysts were characterized by several analytical tools such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). These catalysts were subjected to HDC reaction of chlorophenols, such as 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP) and 3,4-dichlorophenol (3,4-DCP). The reaction rate of HDC of chlorophenols catalyzed by Pd catalysts with various solid bases, such as KF/Al₂O₃ (alumina), sodium acetate (NaOAc) and K₂CO₃ was compared. First, Pd-MCM-41 and Pd-Y catalysts were compared. 2,4- and 3,4-DCPs were completely decomposed within 6 h, in the case of Pd-MCM-41 with NaOAc. Using Pd-Y instead of Pd-MCM-41 with NaOAc, much faster decomposition was observed. Faster decomposition of 4-CP and DCPs was observed with NaOAc base than K₂CO₃ or KF/Al₂O₃ under the same condition. In the case of Pd-Y with KF/Al₂O₃, slower decomposition of 4-CP and DCPs was observed. These base effects were interpreted using the solubility of NaCl and KCl in alcohol and the basic sites of KF/Al₂O₃. Because the solubility of NaCl is known to be larger than KCl solubility in alcohol, byproduct NaCl could be easily dissolved and ionized in solvents. For Pd-Y with KF/Al₂O₃, the small pore size of Y zeolite can interfere with the diffusion of HCl to KF/Al₂O₃ basic site. Second, three catalysts, including Pd-graphene, were compared. 2,4-DCP was decomposed within 2 h using Pd-G with either K₂CO₃, NaOAc or KF/Al₂O₃. Pd-G catalyst showed the highest catalytic activity among Pd-G, Pd-MCM-41 and Pd-Y catalysts. The high activity and stability of the Pd-G could be attributed to the strong metal–support interaction with an electron-deficient site and a critical Pd particle size (ca. 3.5 nm) of Pd-G nanocatalyst with a stronger resistance to the deactivation and good affinity toward aromatic organic molecules, especially phenols. The progress of HDC reaction was monitored by gas chromatography with flame ionization detection (GC/FID), and a feasible degradation process could be explained by analyzing the degradation products such as phenol, cyclohexanone and cyclohexanol from resulting GC chromatograms. The effect of reaction temperature on HDC in Pd-G catalyst was also discussed. In conclusion, Pd-G is an efficient catalyst for decomposition of chlorophenols and can be applied to remediation of chlorophenol-contaminated water under mild conditions.     

Interfacial change on morphological transitions in styrene-isoprene diblock copolymer

The specific interfacial area (S/V) and interfacial thickness in each microstructure of styrene-isoprene diblock copolymer were estimated by analyzing the deviations from Porod’s law. The thermally induced phase transitions proceeded from lamellae (L) to hexagonally ordered cylinder (HEX), via hexagonally perforated layer (HPL) and gyroid (G). The S/V ratio increased stepwise at the order-order transition (OOT) from L to HEX, via HPL and G. The S/V data can be utilized for OOT determination.     

High-frequency SPICE model of anisotropic conductive film flip-chipinterconnections based on a genetic algorithm

This paper firstly reports on the high-frequency SPICE model of the ACF flip-chip interconnections up to 13 GHz. The extraction process is based on an optimization procedure, called a genetic algorithm, which is known as a robust optimization tool. The proposed equivalent circuit model of the ACF interconnection can readily be used in SPICE circuit simulations for signal integrity analysis of high-frequency packages. Two different ACF interconnections were studied using the Au-coated polymer ball and Ni-filled ball. The extracted models of the two ACFs were found strongly dependent on not only size and rigidity of the conducting balls, but also on their magnetic permeability     

Biological functionalization of the amine-terminated Si(100) surface by glycine

A peptide reaction of glycine on an amine-terminated Si(100) surface was investigated using C 1s, N 1s, O 1s, and Si 2p core-level spectroscopy, where the amine-terminated Si(100) surface was prepared using NH₃. In-situ thermal treatments at a mild temperature of 50 °C after the adsorption of glycine on a room-temperature amine-terminated Si(100) surface induced the peptide reaction between the carboxyl group of glycine and the amine group of the surface. This suggests that the amine-terminated Si(100) surface can be an excellent template for constructing a junction between a biomaterial and a Si surface using a dry process.     

Full software analysis and impedance matching of radio frequencyCMOS integrated circuits

We present a systematic analysis technique of complementary metal-oxide-semiconductor (CMOS) radio-frequency (RF) integrated circuits (ICs). A full simulation program with integrated circuit emphasis (SPICE) simulation of the whole chip including the package and the die, with the parameters extracted from purely software analysis, has been performed. It is shown that the RF impedance matching without S-parameter based techniques is possible and the measured results agree well with our SPICE-only software based technique