On the adsorption kinetics of surface-chemically pure n-dodecanoic acid at the air/water interface

The dynamic surface tension data for n-dodecanoic acid in 0.005 M hydrochloric acid, for as-received as well as for surface-chemically pure solutions, show the presence of a prolonged induction period, clearly indicating that the adsorption of this nonionic surfactant is not simply diffusion-controlled. A kinetic model for the reversible formation of monolayer islands, long known in the field of electrochemistry, is shown to also apply to the adsorption of n-dodecanoic acid at the air/water interface. The rate constant increases linearly with increasing bulk concentration, while the induction time decreases exponentially. The phenomenon of nucleation at the air/water interface is consistent with the direct experimental observation of the formation of solid-like patches as the interfacial region is drastically compressed.     

Shifts in protein charge state distributions with varying redox reagents in nanoelectrospray triple quadrupole mass spectrometry

The influence of a number of redox reagents on the charge state distribution in nanoelectrospray mass spectrometry was examined using cytochrome c and ubiquitin. The redox active species investigated were: 1,4-benzoquinone, quinhydrone, tetracyanoquinodimethane (TCNQ), hydroquinone, and ascorbic acid. The redox active species was mixed with the protein sample before injection into the nanoelectrospray emitter, and mass spectra were acquired using a triple quadrupole mass spectrometer. Under the same experimental conditions, the charge state distribution of cytochrome c was observed to shift from a weighted average charge state of 14.25 (in the absence of redox species) to 7.10 in the presence of 1,4-benzoquinone. When quinhydrone was mixed with cytochrome c, the charge state distribution of the protein also shifted to lower charge states (weighted average charge state = 9.43), indicative of less charge state reduction for quinhydrone than with 1,4-benzoquinone. Addition of the redox reagent had little effect on the conformation of cytochrome c, as indicated by far ultraviolet circular dichroism spectra. In contrast, the reagents TCNQ, hydroquinone, and ascorbic acid exhibited negligible effects on the observed charge state distribution of the protein. The differing results for these redox reagents can be rationalized in terms of the redox half reactions involving these species. The results observed with ubiquitin upon adding quinhydrone were analogous to those observed with cytochrome c.     

Allopurinol complexes with first row transition metal perchlorates

Summary Complexes of allopurinol (apH) with Fe^III and several 3d metal(II) (e.g. Fe, Co, Ni and Cu) perchlorates were prepared. The solid complexes isolated included two monomeric hexacoordinated adducts of the type [Fe(apH)₃-(OClO₃) (OH₂)₂]ClO₄ and [Fe(apH)₃(OClO₃)₂(OH₂)]ClO₄, involving N(8)-bound neutral apH ligands, and polymeric Co, Ni or Cu complexes containing both neutral apH and monoanionic ap^- ligands. The latter three complexes involved both N(8)-bound terminal apH and N(1), N(8)- or N(1), N(9)-bound bridging ap^- ligands, and were of the following types: [(apH)₂Cu(ap)] _n (ClO₄) _n , tetrahedral; [(apH)(H₂O)(OClO₃)Co(ap)] _n , pentacoordinated; and [(apH)₂(H₂O)(OClO₃)Ni(ap)] _n , hexacoordinated.Presented in part at the 203rd. American Chemical Society National Meeting; see Ref. 1.     

Polyaniline-coated nanoelectrospray emitters: performance characteristics in the negative ion mode

The increasing tendency to miniaturize analytical techniques has resulted in the widespread use of nanoelectrospray ionization mass spectrometry. A new polyaniline-coated nanoelectrospray emitter has shown increasing promise as a more durable and stable alternative to traditional metal-coated emitters. In this report, the utility of polyaniline-coated nanoelectrospray emitters in the negative ion mode is investigated. Here, oligonucleotides and peptides have been ionized in the negative mode using polyaniline-coated nanoelectrospray emitters. The emitters were found to be durable for at least an hour in the negative ion mode, during which time the signal was stable. The high amount of electrical discharge usually associated with negative ion mode nanoelectrospray was not problematic with the polyaniline-coated emitters. These characteristics make possible the reliable coupling of low-flow separations to negative ion nanoelectrospray without the worry of emitter failure during the course of the experiment.     

Divergent kinetic control of classical versus ozonolytic lactonization: mechanism-based diastereoselection

A strategy has been developed in which mechanistically distinct lactonization reactions are used to prepare diastereomeric delta-lactones relevant to the C1-C9 fragment of (+)-peloruside A. Depending upon which of two reaction types is used, the central (C5) hydroxyl group can be directed to differentiate the C1 versus C9 termini of pseudosymmetric substrates to provide diastereomeric lactones. Thus, the 5-hydroxy-1,9-diester substrate 1 (an azelaic ester) cyclizes under classical (acid- or base-catalyzed) lactonization conditions to give a predominance of one diastereomer, whereas the 5-hydroxy-1,10-diene congener 2 provides the opposite sense of diastereoselectivity when subjected to ozonolytic lactonization (O3, MeOH, NaOH, at -78 degrees C). Thus, this under-utilized oxidative transformation is mechanistically orthogonal to the classical reaction.     

Spectroscopic evidence for the formation of a four-coordinate Co2+ cobalamin species upon binding to the human ATP:cobalamin adenosyltransferase

The human adenosyltransferase hATR converts exogenous cobalamin into coenzyme B12 by transferring the adenosyl group from cosubstrate ATP to a transiently formed Co1+cobalamin (Co1+Cbl) species. A particularly puzzling aspect of hATR function is that the midpoint potential for Co2+Cbl --> Co1+Cbl reduction is below that of readily available biological reductants. Our magnetic circular dichroism and electron paramagnetic resonance spectroscopic studies reported here reveal that, in the absence of ATP, the interaction between Co2+Cbl and hATR promotes partial conversion of the cofactor to its "base-off" form in which a water molecule occupies the lower axial position. This interaction becomes much stronger in the presence of ATP, leading to the formation of an unprecedented Co2+Cbl species with spectroscopic signatures consistent with an essentially four-coordinate, square-planar Co2+ center. This unusual Co2+Cbl coordination is expected to raise the Co2+/1+ reduction potential well into the physiological range.     

Fluctuation-dissipation theorem density-functional theory

Using the fluctuation-dissipation theorem (FDT) in the context of density-functional theory (DFT), one can derive an exact expression for the ground-state correlation energy in terms of the frequency-dependent density response function. When combined with time-dependent density-functional theory, a new class of density functionals results that use approximations to the exchange-correlation kernel fxc as input. This FDT-DFT scheme holds promise to solve two of the most distressing problems of conventional Kohn-Sham DFT: (i) It leads to correlation energy functionals compatible with exact exchange, and (ii) it naturally includes dispersion. The price is a moderately expensive O(N6) scaling of computational cost and a slower basis set convergence. These general features of FDT-DFT have all been recognized previously. In this paper, we present the first benchmark results for a set of molecules using FDT-DFT beyond the random-phase approximation (RPA)-that is, the first such results with fxc not equal to 0. We show that kernels derived from the adiabatic local-density approximation and other semilocal functionals suffer from an "ultraviolet catastrophe," producing a pair density that diverges at small interparticle distance. Nevertheless, dispersion interactions can be treated accurately if hybrid functionals are employed, as is demonstrated for He2 and HeNe. We outline constraints that future approximations to fxc should satisfy and discuss the prospects of FDT-DFT.     

Closed‐System One‐Pot Block Copolymerization by Temperature‐Modulated Monomer Segregation

A biphasic one‐pot polymerization method enables the preparation of block copolymers from monomers with similar and competitive reactivities without the addition of external materials. AB diblock copolymers were prepared by encapsulating a frozen solution of monomer B on the bottom of a reaction vessel, while the solution polymerization of monomer A was conducted in a liquid layer above. Physical separation between the solid and liquid phases permitted only homopolymerization of monomer A until heating above the melting point of the lower phase, which released monomer B, allowing the addition of the second block to occur. The triggered release of monomer B allowed for chain extension without additional deoxygenation steps or exogenous monomer addition. A method for the closed (i.e., without addition of external reagents) one‐pot synthesis of block copolymers with conventional glassware using straightforward experimental techniques has thus been developed.     

Hydrogen‐Abstraction/Acetylene‐Addition Exposed

Polycyclic aromatic hydrocarbons (PAHs) are omnipresent in the interstellar medium (ISM) and also in carbonaceous meteorites (CM) such as Murchison. However, the basic reaction routes leading to the formation of even the simplest PAH—naphthalene (C₁₀H₈)—via the hydrogen‐abstraction/acetylene‐addition (HACA) mechanism still remain ambiguous. Here, by revealing the uncharted fundamental chemistry of the styrenyl (C₈H₇) and the ortho‐vinylphenyl radicals (C₈H₇)—key transient species of the HACA mechanism—with acetylene (C₂H₂), we provide the first solid experimental evidence on the facile formation of naphthalene in a simulated combustion environment validating the previously postulated HACA mechanism for these two radicals. This study highlights, at the molecular level spanning combustion and astrochemistry, the importance of the HACA mechanism to the formation of the prototype PAH naphthalene.