Enantiomerically pure alpha-amino acid synthesis via hydroboration-suzuki cross-coupling

The Garner aldehyde-derived methylene alkene 5 and the corresponding benzyloxycarbonyl compound 25 undergo hydroboration with 9-BBN-H followed by palladium-catalyzed Suzuki coupling reactions with aryl and vinyl halides. After one-pot hydrolysis-oxidation, a range of known and novel nonproteinogenic amino acids were isolated as their N-protected derivatives. These novel organoborane homoalanine anion equivalents are generated and transformed under mild conditions and with wide functional group tolerance: electron-rich and -poor aromatic iodides and bromides (and a vinyl bromide) all undergo efficient Suzuki coupling. The extension of this methodology to prepare meso-DAP, R,R-DAP, and R,R-DAS is also described.     

Flow-injection technique for the determination of low levels of phosphorus in natural waters

An inexpensive flow-injection instrument for determining low concentrations of dissolved reactive phosphorus in natural waters is reported. The unique feature is the use of an inexpensive detector consisting of a flow cell and a simple photometer that incorporates a super-bright light-emitting diode as the source and a photodiode as the detector. The tin(II) chloride-molybdate method was optimized using a modified simplex optimization method. Silicate interference up to 5 mg Si l^?1 was removed by addition of 0.10% (w/v) tartaric acid. Using the tartaric acid-modified optimized reagents, a detection limit of 0.6 μg P l^?1 was achieved. The method was linear over the range 0–100 μg P l^?1 with an excellent precision (r.s.d. 2.9% at 2.0 and 0.5% at 50 μg P l^?1). An in-line pre-concentration anion-exchange column was used to obtain an even lower detection limit of 0.1 μg P l^?1 and applied to the analysis of real samples.     

A near-infrared Fourier transform Raman spectroscopy of epidermal keratinocytes: changes in the protein-DNA structure following malignant transformation

We report here the use of near-infrared (NIR) Fourier transform (FT) Raman spectroscopy to analyze normal human epidermal keratinocytes prior to and following malignant transformation. Our analysis indicates specific Raman spectral differences between immortalized (HPK1A) and malignant ras transformed (HPK1A-ras) cells. In addition, striking spectral differences are seen in the DNA isolated from these cells and particularly in the 843/810 cm(-1) ratio with values of 1.6 +/- 0.13 in HPK1A cells and 0.68 +/- 0.09 in HPK1A-ras cells (mean +/- S.D., n = 12, P < 0.001) indicating specific alterations in the backbone conformation markers following malignant transformation. Subsequently, we analysed the effect of a strong inhibitor of keratinocyte growth, the Vitamin D analog EB1089, on the Raman spectra of intact cells and on the 843/810 cm(-1) ratio in the DNA isolated from both cell lines. Specific changes were observed in intact cells in the 1300-750 cm(-1) region. Furthermore, the 843/810 cm(-1) ratio of isolated DNA from HPK1A cells was not affected by EB1089 but significantly increased in DNA isolated from HPK1A-ras cells so much that it became closer to the value observed for HPK1A cells (1.07 +/- 0.10). Our data suggest that Raman analysis of DNA and in particular the 843/810 cm(-1) ratio can provide useful indices of malignant transformation and efficacy of anticancer agents.     

Ion cyclotron resonance studies of alkylsilyl ions: V—The reactions of alcohols and ethers with the allyldimethylsilyl cation

Diallyldimethylsilane provides a source of the allyldimethylsilyl cation in the ion cyclotron resonance spectrometer; reaction of this cation with alcohols (ROH) produces adducts which decompose by loss of C₃H₆ to yield the ion \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm Me}_2 \mathop {\rm S}\limits^{\rm + } {\rm i} - {\rm OR}} \right] $\end{document}. This elimination is thought to occur by a 1,5-hydrogen shift, together with either stepwise or concerted silicon-carbon bond cleavage. The corresponding aducts from ethers R? O? R¹ (R¹?R, R¹?Et) first lose (R¹? H˙) and then undergo the elimination described above.     

The involvement of metal-to-CO charge transfer and ligand-field excited states in the spectroscopy and photochemistry of mixed-ligand metal carbonyls. A theoretical and spectroscopic study of [W(CO)(4)(1,2-ethylenediamine)] and [W(CO)(4)(N,N'-bis-alkyl-1,4-diazabutadiene)

A new interpretation of the electronic spectroscopy, photochemistry, and photophysics of group 6 metal cis-tetracarbonyls [M(CO)(4)L(2)] is proposed, that is based on an interplay between M --> L and M --> CO MLCT excited states. TD-DFT and resonance Raman spectroscopy show that the lowest allowed electronic transition of [W(CO)(4)(en)] (en = 1,2-ethylenediamine) has a W(CO(eq))(2) --> CO(ax) charge-transfer character, whereby the electron density is transferred from the equatorial W(CO(eq))(2) moiety to pi orbitals of the axial CO ligands, with a net decrease of electron density on the W atom. The lowest, emissive excited state of [W(CO)(4)(en)] was identified as a spin-triplet W(CO(eq))(2) --> CO(ax) CT excited state both computationally and by picosecond time-resolved IR spectroscopy. This state undergoes 1.5 ps vibrational relaxation/solvation and decays to the ground state with a approximately 160 ps lifetime. The nu(CO) wavenumbers and IR intensity pattern calculated by DFT for the triplet W(CO(eq))(2) --> CO(ax) CT excited state match well the experimental time-resolved spectrum. For [W(CO)(4)(R-DAB)] (R-DAB = N,N'-bis-alkyl-1,4-diazabutadiene), the W(CO(eq))(2) --> CO(ax) CT transition follows in energy the W --> DAB MLCT transition, and the emissive W(CO(eq))(2) --> CO(ax) CT triplet state occurs just above the manifold of triplet W --> DAB MLCT states. No LF electronic transitions were calculated to occur in a relevant energetic range for either complex. Molecular orbitals of both complexes are highly delocalized. The 5d(W) character is distributed over many molecular orbitals, while neither of them contains a predominant metal-ligand sigma 5d(W) component, contrary to predictions of the traditional ligand-field approach. The important spectroscopic, photochemical, and photophysical roles of M(CO(eq))(2) --> CO(ax) CT excited states and the limited validity of ligand field arguments can be generalized to other mixed-ligand carbonyl complexes.     

Imine Derivatives of Fumaraldehyde From Oxidation of A β-Aziridinyl Alcohol

Oxidation of a β-aziridinyl alcohol with tetrapropylammonium perruthenate yields a pyrrole and two unusual imine derivatives of fumaraldehyde.     

Self-assembly and chemical processing of block copolymers: A roadmap towards a diverse array of block copolymer nanostructures

Block copolymers can yield a diverse array of nanostructures.Their assembly structures are influenced by their inherent structures,and the wide variety of structures that can be prepared especially becomes apparent when one considers the number of routes available to prepare block copolymer assemblies.Some examples include self-assembly,directed assembly,coupling,as well as hierarchical assembly,which can yield assemblies having even higher structural order.These assembly routes can also be complemented by processing techniques such as selective crosslinking and etching,the former technique leading to permanent structures,the latter towards sculpted and the combination of the two towards permanent sculpted structures.The combination of these pathways provides extremely versatile routes towards an exciting variety of architectures.This review will attempt to highlight destinations reached by LIU Guojun and coworkers following these pathways.