Direct evaluation of DLVO theory for predicting long-range forces between a yeast cell and a surface

Using a combined gradient optical trap and evanescent wave light-scattering force-measurement technique, long-range colloidal forces were measured between a single Candida albicans yeast cell and a flat, bare glass surface in electrolyte concentrations ranging from 0.1 to 100 mM NaCl. The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was compared to experimentally measured equilibrium force curves and found to provide a close approximation to the decay length of the measured forces for electrolyte concentrations up to about 0.23 mM NaCl. At higher electrolyte concentrations (>/=0.5 mM NaCl), decay lengths of force curves in experimental measurements were consistently longer than Debye lengths calculated from the electrolyte concentrations. In electrolyte concentrations of 10 and 100 mM NaCl, most cells attached rapidly, which prevented measurements of long-range forces. The small fraction of cells remaining unattached in these higher electrolyte concentrations displayed purely repulsive forces. These results show that the DLVO theory accurately describes cell-surface interactions when the Debye length is in the range of 20-30 nm but underpredicts the decay length of the interactions at higher electrolyte concentrations.     

A survey of acid catalysis and oxidation conditions in the two-step, one-flask synthesis of meso-substituted corroles via dipyrromethanedicarbinols and pyrrole

The reaction of dipyrromethanedicarbinols with pyrrole leading to meso-substituted corroles was investigated to determine whether mild acid catalysts [Dy(OTf)(3), Yb(OTf)(3), Sc(OTf)(3), and InCl(3)] known to provide porphyrins from dipyrromethanecarbinol species while suppressing undesired reversibility (resulting in scrambling) are applicable to reactions affording corrole, and to explore the requirements of the oxidation step. We examined a model reaction leading to meso-triphenylcorrole (TPC) to survey the effect of acid catalyst, acid concentration, ratio of pyrrole to dipyrromethanedicarbinol, oxidant, oxidant quantity, and reaction time on the yield of TPC (by UV-vis) in reactions performed at room temperature in CH(2)Cl(2). Key to this survey was a modification of the well-known spectrophotometric method for monitoring reactions leading to porphyrin. The survey revealed that TPC could be prepared via a subset of the mild acid catalysts [Dy(OTf)(3) and Yb(OTf)(3)], and a preparative-scale reaction afforded an isolated yield of TPC of 49%, devoid of porphyrin. Suppression of reversible processes was further demonstrated by the synthesis of three corroles bearing different meso substituents in defined locations in isolated yields ranging from 50% to 80%. The reaction conditions were applicable to a dipyrromethanedicarbinol bearing electron-withdrawing pentafluorophenyl substituents-provided that the reaction time of the condensation step was increased. We identified circumstances under which DDQ can cause severe interference with the detection and isolation of some corroles, we found that the yield and purity of the corrole depend on judicious selection of oxidation conditions, and we assessed the sensitivity toward light of dilute solutions of the corroles prepared in this study.     

Synthesis and reactivity of the hydrido- and alkylrhenium methylidene complexes Cp*(PMe3)2(R)Re=CH2 (R = H, CH3)

Protonolysis of the dimethylrhenium(III) compound Cp(PMe(3))(2)Re(CH(3))(2) (3) led to formation of the highly reactive hydridorhenium methylidene compound [Cp(PMe(3))(2)Re(CH(2))(H)][OTf] (4), which was characterized spectroscopically at low temperature. Although 4 decomposed above -30 degrees C, reactivity studies performed at low temperature indicated it was in equilibrium with the coordinatively unsaturated methylrhenium complex [Cp(PMe(3))(2)Re(CH(3))][OTf] (2). Methylidene complex 4 was found to react with PMe(3) to afford [Cp(PMe(3))(3)Re(CH(3))][OTf] (6) and with chloride anion to give Cp(PMe(3))(2)Re(Me)Cl (7). When BAr(f) anion was added to 4, the thermally stable methylrhenium methylidene complex [Cp(PMe(3))(2)Re(CH(2))(CH(3))][BAr(f)] (8) was isolated upon warming to room temperature. The mechanisms of formation of both 4 and 8 are discussed in detail, including DFT calculations. The novel carbonyl ligated complex Cp(CO)(2)Re(CH(3))OTf (12) was prepared, isolated, and found to not undergo migration reactions to form methylidene complexes.     

Collisionally activated decomposition of poly(ethylene glycol)s: An investigation of high-mass ion abundances in the collisional activation technique with large molecules

The utility of the collisional activation technique in structure determination of ions is limited as parent ion mass increases. Optimum collisionally activated dissociation yield is often obtained at parent masses of 1000–2000 u, after which daughter ion yield decreases. The apparent decrease in the efficiency of the collisional activation process has been thought of as a degree-of-freedom effect: as new rotational-vibrational modes are added to the parent ion, its lifetime with respect to dissociation increases. We have investigated this effect using an easily characterized system of several poly(ethylene glycol) homologs from the 15-mer to the 35-mer. Observed trends in the collisional activation spectra as parent mass increases support the postulated ‘degree-of-freedom’ effect in general. The loss of C₂H₄O from the [M ? H]^? parents, a fragmentation which has a high activation barrier, however, actually becomes more favored as the parent ion becomes larger. This effect is explained in terms of statistical rate theory.     

Singlet-Oxygen Generation from Liposomes: A Comparison of 6β-Cholesterol Hydroperoxide Formation with Predictions from a One-Dimensional Model of Singlet-Oxygen Diffusion and Quenching

Abstract— We measured 6β-cholesterol hydroperoxide (6β-CHP), a specific singlet-oxygen (O₂(δg)) product, during irradiation of unilamellar dimyristoyl 1-α-phosphatidylcholine liposomes containing cholesterol and zinc phthalocyanine (ZnPC). The effects of liposome size, the hydrophobic (O₂(¹δ_g)) quencher, β-carotene, and hydrophilic O₂(¹δ_g) quenchers upon the amount of 6β-CHP formed were determined and interpreted in terms of a one dimensional model of ₂(¹δ_g) quenching and diffusion. The model correctly predicted (1) that the amount of 6β-CHP was increased with increasing liposome size, (2) that P-carotene was more effective at reducing 6β-CHP formation in 400 nm diameter liposomes than 100 nm diameter liposomes and (3) that the hydrophilic quencher, water, was also more effective in large liposomes than in small liposomes.
The hydrophobic quencher, β-carotene, was more effective at reducing the formation of 6β-CHP than at reducing the 1270 nm O₂(¹δ_g) emission. This difference was found to be due to the size distribution present in the liposome preparations because the difference between the 6β-CHP data and the 1270 nm emission data was much smaller in liposome preparations with a narrow size distribution. When a significant size distribution was present, the 6β-CHP data were weighted more heavily with large-diameter liposomes, while the 1270 nm emission data were weighted more heavily with small-diameter liposomes.     

Stability of voids formed in cavities at liquid-solid interfaces

A thermodynamic model is developed of the free energy of gas-filled voids formed within cavities on solid surfaces covered by a liquid. Capillary effects are assumed to be the only important contributions to the free energy, and expressions are derived for the free energy of the system as a function of the void size, the relative surface free energy densities involved, and the geometry of the cavity. The results of the model are (1) construction of a stability diagram that maps the most stable void configuration versus the wetting properties of the various solid surfaces involved, and (2) rough estimates of the work required to liberate a void of a given size and position. The model can give qualitative insight into the stability of coating defects on uneven surfaces, and also can be used to prescribe possible surface treatments for reducing the work required to remove voids from the system.     

Ambient Solar Radiation-Induced Photodamage in Marine Bacterioplankton

Abstract— There has been much recent concern about the effects of increased UV radiation at certain locations on the earth's surface. There have been extensive studies of ultraviolet radiation effects on phytoplankton and primary production, yet the effects of UVB upon bacterioplankton have been largely overlooked. Bacteria play a central role in the cycling of nutrients and energy flow to higher trophic levels, serving as both mineralizers and secondary producers that are consumed by higher organisms. We have begun to investigate the induction of DNA photodamage by UVB in marine planktonic communities using a highly specific radioimmunoassay to measure cyclobutane pyrimidine dimers in samples collected from the northern Gulf of Mexico. DNA damage in the bacterioplankton size-fraction (< 0.8 μ.m) was greater than in the larger eukaryotic size fraction (>0.8 μm <120 μm) in 9 of 10 samples. Diel patterns of dimer accumulation and repair were observed in surface waters over a 48 h period in the bacterioplankton size fraction and in the larger eukaryotic plankton size fraction. Depth profiles of DNA damage in the bacterioplankton size fraction appear to be dependent on surface water mixing. Damage was greatest in surface waters, decreased with depth and could be detected to 10 m in calm seas. No net accumulation of damage was observed in moderate seas, even at the surface. Solar radiation was found to inhibit significantly both ³H-thymidine and ¹⁴C-leucine incorporation. Ultraviolet B was responsible for approximately half of the total inhibition of ³H-thymidine incorporation, UVA contributing the other half of the inhibition. The vast majority of ¹⁴C-leucine incorporation inhibition was due to UVB, suggesting that protein synthesis is less affected by UVA. The results demonstrate that direct measures of DNA damage can be made of indigenous planktonic communities and that bacterioplankton are highly susceptible to UVB damage and may serve as a more sensitive indicator of UVR stress than other microorganisms.     

Free radical-mediated aryl amination and its use in a convergent [3 + 2] strategy for enantioselective indoline alpha-amino acid synthesis

The scope of aryl radical additions to the nitrogen of azomethines is described. Aryl, trifluoromethyl alkyl, and alpha,beta-unsaturated ketimines engage in regioselective aryl-nitrogen bond formation via 5-exo cyclizations of an aryl radical to azomethine nitrogen. Selectivity for carbon-nitrogen over carbon-carbon bond formation is generally high (>95:5) and competes only with direct aryl radical reduction by stannane (0-10%). Alpha-ketoimines are a promising new class of carbon radical acceptors for which no competitive aryl radical reduction is observed. The reaction conditions are pH-neutral and are therefore among the mildest methods available for amination of an aromatic ring. The ketimines examined did not suffer from competitive reduction by stannane, offering an advantage over the use of diazo and azide functional groups as nitrogen sources for carbon radicals. The free radical-mediated aryl amination was sequenced with the O'Donnell phase transfer-catalyzed enantioselective alkylation strategy of glycinyl imine to provide either enantiomer of indoline alpha-amino acids with high ee. These new constrained phenyl alanine derivatives are now readily available for evaluation across a variety of applications.     

Synthesis and NMD A Antagonistic Properties of the Enantiomers of 4-(3-phosphonopropyl)piperazine-2-carboxylic acid (CPP) and of the unsaturated analogue (E)-4-(3-phosphonoprop-2-enyl)piperazine-2-carboxylic acid (CPP-ene)

The (R)- and (s)-enantiomers of 4-(3-phosphonopropyl)piperazine-2-carboxylic acid (D - and L -CPP, resp.; 15 and 16 , resp.), and of its unsaturated analogue (E)-4-(3-phosphonoprop-2-enyl)piperazine-2-carboxylic acid (D - and L -CPP-ene, resp.; 13 and 14 , resp.) were prepared. The absolute configuration of the enantiomers was determined by a chemical correlation of the menthyl ester 7 with D -asparagine. The affinity of these derivatives for the NMDA receptor was determined by displacement of [³H]CPP in rat cerebral cortical membranes. In two functional tests (the frog hemisected spinal cord preparation and the sodium efflux test from rat brain slices), D -CPP-ene appears to be the most potent, enantiomerically pure, competitive NMDA antagonist known to date.     

Distinct electronic structures and bonding interactions in inverse-sandwich samarium and ytterbium biphenyl complexes

Inverse-sandwich samarium and ytterbium biphenyl complexes were synthesized by the reduction of their trivalent halide precursors with potassium graphite in the presence of biphenyl. While the samarium complex had a similar structure as previously reported rare earth metal biphenyl complexes, with the two samarium ions bound to the same phenyl ring, the ytterbium counterpart adopted a different structure, with the two ytterbium ions bound to different phenyl rings. Upon the addition of crown ether to encapsulate the potassium ions, the inverse-sandwich samarium biphenyl structure remained intact; however, the ytterbium biphenyl structure fell apart with the concomitant formation of a divalent ytterbium crown ether complex and potassium biphenylide. Spectroscopic and computational studies were performed to gain insight into the electronic structures and bonding interactions of these samarium and ytterbium biphenyl complexes. While the ytterbium ions were found to be divalent with a 4f¹⁴ electron configuration and form a primarily ionic bonding interaction with biphenyl dianion, the samarium ions were in the trivalent state with a 4f⁵ electron configuration and mainly utilized the 5d orbitals to form a δ-type bonding interaction with the π* orbitals of the biphenyl tetraanion, showing covalent character.

Inverse-sandwich samarium and ytterbium biphenyl complexes were synthesized and characterized by X-ray crystallography. Combined experimental and computational studies indicated that they have distinct electronic structures and bonding interactions.