The chemical behaviour of cobalt-stabilized carbenes having a trisubstituted silyl or germyl ligand. Stereospecific formation of benzoylsilanes from the reaction of organosilyl-cobalt tetracarbonyl derivatives with phenyllithium

We report the chemical behavior of cobalt-stabilized carbenes, R₃M(CO)₃CoC(OEt)R′, and their parent anions, R₃M(CO)₃CoC(O^?)R′, where M = Si or Ge. The anions where M = Si, R′ = Ph decompose thermally into the corresponding benzoylsilanes; when the silicon atom is chiral (R₃ = MePh-1-Np) optically active R₃SiCOPh is obtained with complete retention of configuration.     

A concise asymmetric synthesis of the ADE fragment of nakadomarin A

The ADE fragment of nakadomarin A has been synthesized in nine linear steps from commercial material. The key transformation is an asymmetric azomethine ylide [1,3]-dipolar cycloaddition to establish the AD-spirocyclic system containing three of the four stereocenters of the natural product. [reaction: see text]     

ENHANCEMENT OF THE SENSITIVITY OF RADIATIVE and NON-RADIATIVE DETECTION TECHNIQUES IN THE STUDY OF PHOTOSENSITIZATION BY WATER SOLUBLE SENSITIZERS USING A REVERSE MICELLE SYSTEMS*,†

The study of photosensitization processes in aqueous solution is complicated by the unsuit-ability of water as solvent for the commonly used techniques for monitoring radiative and non-radiative relaxation processes. The infrared luminescence method is hampered by the relatively weak intensity of emission and short lifetime of singlet molecular oxygen, O₂(¹Δ_g), in water. Photoacoustic and photothermal detection of the dominant non-radiative relaxation process for O₂(¹Δ_g) is also inhibited by the unfavorable physico-chemical properties of water which reduce the sensitivities of these techniques for the study of sensitizers in aqueous with respect to non-aqueous media. Such problems have been alleviated by incorporating the sensitizer in the aqueous core of aerosol OT reverse micelles. It is demonstrated that the sensitivity of both radiative and non-radiative detection depends not on the local environment of the sensitizer but on the overall composition of the medium, which, in the case of reverse micelle solutions, is predominantly hydrocarbon. This produces a 4.5 and 6-fold enhancement of the sensitivity of luminescence and optoacoustic detection, respectively, in comparison to purely aqueous solution. The utility of the method is demonstrated for Rose Bengal, where quantum yields of intersystem crossing (φ_isc) of 0.78 (LIOAC) and singlet oxygen generation (φ_δ) of 0.81 (LIOAC) and 0.80 (TRLD) were measured. Phenazine was also studied for comparative purposes and to corroborate values obtained for Rose Bengal.     

An efficient preparation of isosteric phosphonate analogues of sphingolipids by opening of oxirane and cyclic sulfamidate intermediates with alpha-lithiated alkylphosphonic esters

D-erythro-(2S,3R,4E)-Sphingosine-1-phosphonate (1), the isosteric phosphonate analogue of naturally occurring sphingosine 1-phosphate (1a), and D-ribo-phytosphingosine 1-phosphonate (2), the isosteric phosphonate analogue of D-ribo-phytosphingosine-1-phosphate (2a), were synthesized starting with methyl 2,3-O-isopropylidene-d-glycerate (4) and D-ribo-phytosphingosine (3), respectively. Oxirane 12 was formed in eight steps from 4, and cyclic sulfamidate 22 was formed in five steps from 3. The phosphonate group was introduced via regioselective ring-opening reactions of oxirane 12 and cyclic sulfamidate 22 with lithium dialkyl methylphosphonate, affording 13 and 23, respectively. The synthesis of 1 was completed by S(N)2 displacement of chloromesylate intermediate 14b with azide ion, followed by conversion of the resulting azido group to a NHBoc group and deprotection. The synthesis of 2 was completed by cleavage of the acetal, N-benzyl, and alkyl phosphonate ester groups.     

Calculation of the 1J(PP) angular dependence in P2H4

Using the results obtained from an MO SCF ab initio calculation on P₂H₄ in four different conformations, the ¹J(PP) NMR coupling constants have been calculated. The ¹J(PP) values are highly dependent upon the rotational angle φ (?238.0 Hz in the eclipsed conformation, 10.9 Hz in the staggered one). The shape of the theoretical ¹J(PP) plot seems to be in good agreement with experimentally measured ¹J(PP) values.     

Characterization of dynamic and steady-state protein phosphorylation using a fluorescent phosphoprotein gel stain and mass spectrometry

Protein phosphorylation plays a vital role in the regulation of most aspects of cellular activity, being key to propagating messages within signal transduction pathways and to modulating protein function. Pro-Q Diamond phosphoprotein gel stain is suitable for the fluorescence detection of phosphoserine-, phosphothreonine-, and phosphotyrosine-containing proteins directly in sodium dodecyl sulfate (SDS)-polyacrylamide gels. The technology is especially appropriate for profiling steady-state and dynamic phosphorylation on a proteome-wide scale, as demonstrated through detection of the native phosphorylation of cardiac mitochondrial phosphoproteins and changes in this profile arising from the activity of a protein kinase. For example, Pro-Q Diamond phosphoprotein gel stain was employed to demonstrate that among the 46 subunits of the mitochondrial respiratory chain complex, NADH:ubiquinone oxidoreductase (complex I), a 42 kDa subunit is phosphorylated in the steady-state. However, exposure of mitochondria to cAMP-dependent protein kinase increases phosphorylation of this 42 kDa subunit and results in de novo phosphorylation of an 18 kDa subunit as well. Since Pro-Q Diamond dye binds to phosphorylated residues noncovalently, the staining technology is fully compatible with modern microchemical analysis procedures, such as peptide mass profiling by matrix assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry and post-source decay analysis of peptide phosphorylation.     

Bistable ferroelectric liquid crystal photoswitch triggered by a dithienylethene dopant

The spontaneous polarization (PS) of a ferroelectric liquid crystal is modulated reversibly by photocyclization of the dopant 1,2-bis[5'-(4' '-heptyloxyphenyl)-2'-methylthien-3'-yl]perfluorocyclopentene. The magnitude of PS photomodulation increases with dopant concentration up to 3 mol %, and the resulting photoswitch is fatigue resistant and bistable. To the best of our knowledge, this is the first example of a bistable ferroelectric liquid crystal photoswitch to be reported in the literature.     

Diverse redox-active molecules bearing O-, S-, or Se-terminated tethers for attachment to silicon in studies of molecular information storage

A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols.     

A rapid access to chiral alkylidene cyclopentenone prostaglandins involving ring-closing metathesis reaction

A synthesis of the alkylidene cyclopentenone prostaglandin TEI 9826 has been realized. The synthesis involved the preparation of the chiral 1,5-diene 8 using a stereoselective Claisen rearrangement from the allylic alcohol 6 giving the ester 7 after vinylation. Then a key RCM reaction allowed the preparation of the cyclopentenol 9 which, after oxidation, gave the cyclopentenone 10, precursor of the prostaglandin.     

Potentiometric response of graphite electrodes coated with modified polymer films

Graphite electrodes coated with chemically-modified polymer films are described. Several different polymers were used, including poly(acrylic acid), poly[triethyl(vinylbenzyl)ammonium chloride], poly[trihexyl(vinylbenzyl)ammonium chloride], and poly[trihexyl(vinylbenzyl)ammonium thiocyanate]. A cation-responsive electrode can be prepared from poly(acrylic acid)-coated graphite. Anion-responsive electrodes can be prepared from graphite coated with polymeric quaternary amines. In these electrodes, the ion-sensing species is irreversibly attached to the polymer (rather than physically entrapped within a polymer matrix); this factor eliminates leaching of the active component, and the addition of a plasticizer is unnecessary. A selective sensor for thiocyanate is described; it yields a Nernstian response over the concentration range 1 × 10^?1–1 × 10^?5 M sodium thiocyanate.