Exploring the Limits of Frustrated Lewis Pair Chemistry with Alkynes: Detection of a System that Favors 1,1‐Carboboration over Cooperative 1,2‐P/B‐Addition

The zirconocene complex [{(C₆F₅)₂B‐(CH₂)₃‐Cp}(Cp‐PtBu₂)ZrCl₂] ( 6 ; Cp=cyclo‐C₅H₄) was prepared by hydroboration of [(allyl‐Cp)(Cp‐PtBu₂)ZrCl₂] ( 5 ) with HB(C₆F₅)₂ (“Piers’ borane”). It represents a frustrated Lewis pair (FLP) in which both the Lewis acid and the Lewis base were attached at the metallocene framework. Its reaction with 1‐pentyne did not result in the 1,2‐addition of or deprotonation reaction by the FLP, but rather in the 1,1‐carboboration of the triple bond, thereby obtaining a Z/E mixture (1.2:1) of the respective organometallic substituted alkenes 7 . The analogous reaction of 1‐pentyne with the phosphorous‐free system [{(C₆F₅)₂B‐(CH₂)₃‐Cp)}CpZrCl₂] ( 9 ) gave the respective 1,1‐carboboration products ( Z‐10 / E‐10 ≈1.3:1).     

Analysis of MS/MS fragmentation of taxoids

The fragmentation pathways of seven types of taxoids were investigated by using a LC-MS/MS method, namely: (1) neutral taxoids with a C-4(20) double bond; (2) taxoids with a C-4(20) double bond and oxygenation at C-14; (3) 5-cinnamoyl taxoids with a C-4(20) double bond; (4) a basic taxoid with a C-4(20) double bond; (5) a taxoid with a C-4(20) epoxide; (6) taxoids with an oxetane ring; and (7) taxoids with an oxetane ring and a phenylisoserine C-13 side chain. Depending on the class of core structure and the substitution pattern, each taxoid gave either the molecular adduct ion [M+NH4]+ or [M+H]+. In the MS/MS, the molecular adduct ion gave characteristic product ions corresponding to the loss of water, acetic acid, benzoic acid, and cinnamic acid or the phenylisoserine group. These could reflect the difference of the substitutions and structural modifications and should be utilized for the structure elucidation oftaxoids by LC-MS.     

RAMA stain: A fast,sensitive and less protein‐modifying CBB R250 stain

SDS‐PAGE and CBB staining are two of the most popular methods used for protein analysis. Although many reports that describe such staining methods have been published, these conventional protocols require several hours or days for staining and de‐staining. In this study we describe a recently developed, fast and sensitive CBB staining method that utilizes the staining solution of RAMA that consists of the low‐cost reagents: CBB R250, acetic acid, methanol and ammonium sulfate, and the destaining solution of water. Our method dose dependently detects 12 nanograms protein within 60 min and with a wide protein spectrum. Although the features of the dose‐dependent relationship depend upon protein amounts and protein types, for most of the protein samples tested, a linear relationship was observed in the region from 12 to 330 ng. Moreover, through further washing, the detection sensitivity of protein is enhanced and reaches a maximum at 1.4 ng and then gradually decreases in the de‐staining process. It has been shown recently through MS analyses that the sensitive colloidal CBB staining methods frequently result in artifactual methylations due to the strong acid and long contact during staining and the destaining processes. Such artifacts were reported to be reduced by the replacement of strong inorganic acid with acetic acid and because RAMA utilizes acetic acid and is in contact with the proteins for a short time during staining and de‐staining, it is expected that in vitro artifacts will be reduced. Finally, MS analyses of RAMA‐stained protein bands were revealed not to have been methylated.     

Thermosensitive properties of poly(amidoamine) dendrimers with peripheral phenylalanine residues

Dendrimers are unique polymers with globular shapes and well-defined structures. We previously prepared poly(amidoamine) (PAMAM) dendrimers having phenylalanine (Phe) residues at every chain end of the dendrimer as efficient gene carriers. In this study, we found that Phe-derivatized PAMAM dendrimers change their water solubility depending on temperature. The dendrimers were soluble in aqueous solutions at low temperatures, but they became water-insoluble at temperatures above a specific threshold, which is termed the lower critical solution temperature (LCST). Although the LCST of Phe-modified dendrimers decreased with increasing dendrimer generation, these dendrimers exhibited an LCST of 20-30 degrees C under physiological conditions. In addition, the LCST of the dendrimers was controlled by introducing isoleucine (Ile) residues at chain ends of dendrimers at varying ratios with respect to Phe residues. The PAMAM dendrimers are known to encapsulate various drug molecules. For these reasons, temperature-sensitive dendrimers might be useful as efficient drug carriers with controlled size and temperature-responsive properties.     

Single-chain magnet behavior in an alternated one-dimensional assembly of a Mn(III) Schiff-base complex and a TCNQ radical

An alternated 1:1 chain compound of a Mn(III) salen derivative and the TCNQ monoradical was synthesized: [Mn(5-TMAMsaltmen)(TCNQ)](ClO(4))(2) (1) (TCNQ=tetracyano-p-quinodimethane; 5-TMAMsaltmen=N,N'-(1,1,2,2-tetramethylethylene) bis(5-trimethylammoniomethylsalicylideneiminato)). Compound 1 has a zigzag chain structure packed with adjacent chains with an interchain MnMn distance of over 8 Angatrom. As compound 1 contains no crystallization solvent, the void spaces between chains are occupied only by ClO(4) (-) counter ions. Compound 1 has a structure reminiscent of what has been observed in the family of Mn(III)(porphyrin)-TCNE or -TCNQ compounds reported previously by Miller and co-workers and we demonstrate herein its unique single-chain magnet behavior among this family of compounds. The direct current (dc) magnetic measurements established the one-dimensional nature of compound 1 with an antiferromagnetic exchange coupling, J/k(B) approximately -96 K, between the Mn(III) ion and TCNQ radical and with an activated correlation length (Delta(xi)=26.5 K) at low temperatures (50-15 K). The slow relaxation of the magnetization was shown in compound 1 by the field hysteresis of the magnetization observed below 3.5 K (with a coercive field up to 14 kOe at 1.8 K). Single-crystal magnetization measurements demonstrated the uniaxial symmetry of this compound and allowed an estimation of the anisotropy field, H(a) approximately 97 kOe. The absence of magnetic ordered phase or spin-glass behavior was established by heat-capacity calorimetry measurements that exhibit no abnormality of C(p) between 0.5 K and 10 K. The study of the magnetization relaxation by combined ac (alternating current) and dc techniques showed that compound 1 possesses a single relaxation time (tau). As the consequence of the finite size of the chain, the temperature dependence of tau presents two activated regimes above and below 4.5 K with tau(01)=2.1 x 10(-10) s, Delta(tau1)=94.1 K and tau(02)=6.8 x 10(-8) s and Delta(tau2)=67.7 K, respectively. The detailed analysis of these dynamics properties together with the correlation length, allows an unambiguous demonstration of the single-chain magnet behavior in 1.     

Direct structural assignment of neutral and sialylated N-glycans of glycopeptides using collision-induced dissociation MSn spectral matching

Mass spectrometric analyses of various N-glycans binding to proteins and peptides are highly desirable for elucidating their biological roles. An approach based on collision-induced dissociation (CID) MS(n) spectra acquired by electrospray ionization linear ion trap time-of-flight mass spectrometry (ESI-LIT-TOFMS) in the positive- and negative-ion modes has been proposed as a direct method of assigning N-glycans without releasing them from N-glycopeptides. In the positive-ion mode of this approach, the MS(2) spectrum of N-glycopeptide was acquired so that a glycoside-bond cleavage occurs in the chitobiose residue (i.e., GlcNAcbeta1-4GlcNAc, GlcNAc: N-acetylglucosamine) attached to asparagine (N), and two charges on the [M+H+Na](2+) precursor ion are shared with both of the resulting fragments. These fragments are sodiated B(n)-type fragment ions of oligosaccharide (N-glycan) and a protonated peptide ion retaining one GlcNAc residue on the asparagine (N) residue. The structure of N-glycan was assigned by comparing MS(3) spectra derived from both the sodiated B(n)-type fragment ions of N-glycopeptide and the PA (2-aminopyridine) N-glycan standard (i.e., MS(n) spectral matching). In a similar manner, the structural assignment of sialylated N-glycan was performed by employing the negative-ion CID MS(n) spectra of deprotonated B(n)-type fragment ions of N-glycopeptide and the PA N-glycan standard. The efficacy of this approach was tested with chicken egg yolk glycopeptides with a neutral and a sialylated N-glycan, and human serum IgG glycopeptides with neutral N-glycan isomers. These results suggest that the approach based on MS(n) spectral matching is useful for the direct and simple structural assignment of neutral and sialylated N-glycans of glycopeptides.     

Origin of p(2 x 1) phase on Si(001) by noncontact atomic force microscopy at 5 k

The controversial issue of the origin of the p(2 x 1) reconstruction of the Si(001) surface observed in recent low temperature scanning tunneling microscopy experiments is clarified here using 5 K noncontact atomic force microscopy. The c(4 x 2) phase is observed at separations corresponding to weak tip-surface interactions, confirming that it is the ground state of the surface. At larger frequency shifts the p(2 x 1) phase of symmetric dimers is observed. By studying the interaction of a reactive Si tip with the c(4 x 2) Si(001) surface using an ab initio method, we find that the observed change in the surface reconstruction is an apparent effect caused by tip induced dimer flipping resulting in a modification of the surface structure and appearance of the p(2 x 1) phase in the image. Using an appropriate scanning protocol, one can manipulate the surface reconstruction at will, which has significance in nanotechnology.     

Speech feature extraction method using subband-based periodicity and nonperiodicity decomposition

This paper proposes a speech feature extraction method that utilizes periodicity and nonperiodicity for robust automatic speech recognition. The method was motivated by the auditory comb filtering hypothesis proposed in speech perception research. The method divides input signals into subband signals, which it then decomposes into their periodic and nonperiodic components using comb filters independently designed in each subband. Both features are used as feature parameters. This representation exploits the robustness of periodicity measurements as regards noise while preserving the overall speech information content. In addition, periodicity is estimated independently in each subband, providing robustness as regards noise spectrum bias. The framework is similar to that of a previous study [Jackson et al., Proc. of Eurospeech. (2003), pp. 2321-2324], which is based on cascade processing motivated by speech production. However, the proposed method differs in its design philosophy, which is based on parallel distributed processing motivated by speech perception. Continuous digit speech recognition experiments in the presence of noise confirmed that the proposed method performs better than conventional methods when the noise in the training and test data sets differs.     

Development of a non-destructive isotopic analysis method by gamma-ray emission measurement after negative muon irradiation

Journal of Radioanalytical and Nuclear Chemistry - Variations in isotopic abundance provide useful information for various scientific fields. Herein we performed a feasibility study by...     

Development of Surface Fluorescence X‐Ray Absorption Fine Structure Spectroscopy Using a Laue‐Type Monochromator

Surface fluorescence X‐ray absorption fine structure (XAFS) spectroscopy using a Laue‐type monochromator has been developed to acquire structural information about metals with a very low concentrate on a flat highly oriented pyrolytic graphite (HOPG) surface in the presence of electrolytes. Generally, surface fluorescence XAFS spectroscopy is hindered by strong scattering from the bulk, which often chokes the pulse counting detector. In this work, we show that a bent crystal Laue analyzer (BCLA) can efficiently remove the scattered X‐rays from the bulk even in the presence of solution. We applied the technique to submonolayer (～10¹⁴ atoms cm^?2) Pt on HOPG and successfully obtained high signal/noise in situ XAFS data in combination with back‐illuminated fluorescence XAFS (BI‐FXAFS) spectroscopy. This technique allows in situ XAFS measurements of flat electrode surfaces to be performed in the presence of electrolytes.