Catalytic asymmetric addition of alkylzinc and functionalized alkylzinc reagents to ketones

We describe our full report of the catalytic asymmetric addition of simple and functionalized dialkylzinc reagents to a broad range of saturated ketones and enones. The functionalized organozinc reagents contain esters, silyl ethers, alkyl chlorides, and alkyl bromides. In general, the resulting tertiary alcohol products are isolated with high ee's. With some substrates, yields are low as a result of the formation of aldol byproducts. Most substrates undergo additions with good yields reaching as high as 91%.     

Synthesis and polymerization of coupled compounds of 1,11-dodecadiyne

The dimer, trimer, and tetramer of 1,11-dodecadiyne, HC?C? (CH₂)₈? C?CH, were synthesized. The solid-state polymerization of the dimer was investigated by infrared (IR) spectroscopy. IR bands due to the diacetylene moiety were identified through the comparison of the IR spectra of the dimer, trimer, and tetramer. The dimer was found to have two polymorphs, melt-crystallized and solution-crystallized. Both of the polymorphs undergo solid-state polymerization by exposure to γ-ray or UV irradiation. The former has higher polymerizability for the diacetylene moiety than the latter. The solid-state polymerization of the terminal acetylene group was not observed. It is shown that the previously reported dimer structure in which both the diacetylene and terminal acetylene groups are polymerized to form an inherently electrically conducting polymer is incorrect. © 1995 John Wiley & Sons, Inc.     

Protein posttranslational modifications: the chemistry of proteome diversifications

The diversity of distinct covalent forms of proteins (the proteome) greatly exceeds the number of proteins predicted by DNA coding capacities owing to directed posttranslational modifications. Enzymes dedicated to such protein modifications include 500 human protein kinases, 150 protein phosphatases, and 500 proteases. The major types of protein covalent modifications, such as phosphorylation, acetylation, glycosylation, methylation, and ubiquitylation, can be classified according to the type of amino acid side chain modified, the category of the modifying enzyme, and the extent of reversibility. Chemical events such as protein splicing, green fluorescent protein maturation, and proteasome autoactivations also represent posttranslational modifications. An understanding of the scope and pattern of the many posttranslational modifications in eukaryotic cells provides insight into the function and dynamics of proteome compositions.     

Resonance Raman studies of beta-substituted porphyrin systems with unusual electronic absorption properties.

Zn(II) and Cu(II) porphyrins with beta-conjugated barbiturate functional groups have low-energy electronic transitions which are unusual in that there are two strong bands in the Soret region. Resonance excitation of the two bands shows that each has features characteristic of both the porphyrin and barbiturate groups, with some perturbation to these features caused by the interaction of the two chromophores. The resonance Raman (RR) spectrum (lambda(exc)=413.1 nm) of the 412 nm band shows two bands at 1722 and 1743 cm(-1) attributable to C==O stretches in the substituent. Changes in frequency of porphyrin core modes due to the differing metal centres are reproduced by density functional theory calculations. The Q band RR spectra show modes with anomalous polarization which may be attributed to A(2g) modes, however no overtone or combination bands are observed.     

The three-gluon vertex of QCD

We show how the Q² evolution of gluon jets can be used to provide indirect but strong evidence for the three-gluon vertex of QCD. We propose looking for this evolution in the $Q\overline{Q}\to 3G\to$ hadrons decay of successive 1 ³S₁ quarkonium states. The results apply to other processes if G-jets can be isolated.     

The 3 gluon decay of quarkonium

We discuss the process $$e^ + e^ - \to Q\bar Q \to 3gluons \to 3jets$$ with attention to the kinematics and observability of the jets. We also show how to check the gluon spin through jet or hadron angular distributions. Gluon flavor can be checked by looking for quantum number correlations between opposite jets. We predict that correlations exist off resonance for \(e^ + e^ - \to q\bar q\) , but not on resonance for \(Q\bar Q \to 3g\) .     

Sustainable,mild and efficient p-methoxybenzyl ether deprotections utilizing catalytic DDQ

A procedure for the selective deprotection of p-methoxybenzyl ethers using catalytic amounts of DDQ and of sodium nitrite, with oxygen as the terminal oxidant, is reported.     

The miscibility of polyethersulfone with phenoxy resin

Polyethersulfone has been shown to be miscible with phenoxy resin. Cast films were found to be clear and show a single, composition-dependent glass transition-Blends were found to phase separate on heating with a lower critical solution temperature around 185°C. The heat of mixing of low molecular weight analogs was small and negative, suggesting a favorable interaction between the polymers. Phase diagrams were simulated using the equation-of-state theory of Flory and co-workers and were found to agree closely with the observed behavior. The water vapor sorption of the blends was investigated, and this also suggested a weak favorable interaction between the polymers.