Thermodynamic profiles for CO photodissociation from heme model compounds: effect of proximal ligands

Here we present a comprehensive study of the thermodynamic parameters (enthalpy, entropy, and volume changes) associated with carbon monoxide photodissociation and rebinding to Fe(II) microperoxidase-11 (Fe(II)MP11) and Fe(ll) tetrakis(4-sulfonatophenyl)porphine complex (FeII4SP) with water and 2-methylimidazole as proximal ligands. CO photodissociation from FeII4SP complexes is accompanied by a positive volume change of approximately 17 mL mol(-1). A smaller volume change of approximately 12 mL mol(-1) was observed for CO dissociation from Fe(II)MP-11. We attribute the positive volume change to cleavage of the Fe-CO covalent bond and to solvent reorganization due to the low-spin to high-spin transition. CO binding is an exothermic reaction with an enthalpy change of -17 kcal mol(-1) for the CO-FeII4SP complexes and -13 kcal mol(-1) for the CO-Fe(II)MP11 complex. In all cases, the ligand recombination occurs as a single-exponential process indicating that CO dissociation is followed by direct CO rebinding to a high-spin five-coordinate complex without concomitant dissociation of the proximal base. In addition, observed negative activation entropies and volumes for ligand binding to (2-Melm)FeII4SP and MP-11, respectively, suggest that CO rebinding can be described by an associative mechanism with bond formation being the rate-limiting step.     

Structural properties of a series of photochromic fluorinated indolylfulgides

Fluorinated indolyl­fulgides are a class of photochromic organic compounds that meet many of the requirements for use as optical memory media and optical switches. The X‐ray crystal structures of a series of five photochromic fluorinated indolyl­fulgides have been determined, namely (3Z)‐3‐[1‐(1,2‐di­methyl‐1H‐indol‐3‐yl)‐2,2,2‐tri­fluoro­ethyl­idene]‐4‐(1‐methyl­ethyl­idene)­dihydrofuran‐2,5‐dione (tri­fluoro­methyl­iso­propyl­idene­indolyl­fulgide), C₁₉H₁₆F₃NO₃, (I), (3Z)‐3‐[1‐(1,2‐dimethyl‐1H‐indol‐3‐yl)‐2,2,3,3,3‐penta­fluoro­propyl­idene]‐4‐(1‐methyl­ethyl­idene)­dihydrofuran‐2,5‐dione (penta­fluoro­ethyl­iso­propyl­idene­indolyl­fulgide), C₂₀H₁₆F₅NO₃, (II), (3Z)‐3‐[1‐(1,2‐di­methyl‐1H‐indol‐3‐yl)‐2,2,3,3,4,4,4‐hepta­fluoro­butyl­idene]‐4‐(1‐methyl­ethyl­idene)­dihydrofuran‐2,5‐dione (hepta­fluoro­propyl­iso­propyl­idene­indolyl­fulgide), C₂₁H₁₆F₇NO₃, (III), (3Z)‐3‐[1‐(1,2‐di­methyl‐1H‐indol‐3‐yl)‐2,2,2‐tri­fluoro­ethyl­idene]‐4‐(tri­cyclo­[3.3.1.1^3,7]­decyl­idene­)dihydrofuran‐2,5‐dione (tri­fluoro­methyl­adamantyl­idene­indolyl­fulgide), C₂₆H₂₄F₃NO₃, (IV), and (3Z)‐3‐[1‐(1,2‐di­methyl‐1H‐indol‐3‐yl)‐2,2,3,3,4,4,4‐hepta­fluoro­butyl­idene]‐4‐(tri­cyclo­[3.3.1.1^3,7]­decyl­idene­)dihydrofuran‐2,5‐dione (hepta­fluoro­propyl­adamantylidenein­dolyl­fulgide), C₂₈H₂₄F₇NO₃, (V). The photochromic property of fulgides is based on the photochemically allowed electrocyclic ring closure of a hexatriene system to form a cyclo­hexa­diene. For each fulgide examined, the bond lengths within the hexatriene system alternate between short and long, as expected. Comparing the structures of the five fulgides with each other demonstrates no significant difference in bond lengths, bond angles or dihedral angles within the hexatriene systems. The distance between the bond‐forming C atoms at each end of the hexatriene system does vary. Correlations of structural properties with optical properties are addressed.     

PHOTOSENSITIZED OXIDATION OF BIOMATERIALS and RELATED MODEL COMPOUNDS

Aluminium trisulfonatophthalocyanine (A1PCS), a dye being widely advocated for use in photodynamic therapy, produces singlet oxygen with a quantum yield of 0.34 in oxygenated water at pH 7. Triplet A1PCS abstracts an electron from a variety of amines and phenols, the rate of electron transfer depending upon the thermodynamic driving force, forming the A1PCS radical anion. This latter species reduces molecular oxygen to superoxide ions with high efficiency. The triplet state also abstracts an electron from biological components, including NADH, vitamin C, cysteine, methionine, tyrosine, tryptophan, uracil, and guanine, but not from DNA. These results suggest that photoinduced electron abstraction from appropriate biomaterials could compete with singlet oxygen production under in vivo conditions.     

Comparison of experimental and calculated peak shapes for three cylindrical geometry FAIMS prototypes of differing electrode diameters

High-field asymmetric waveform ion mobility spectrometry (FAIMS) separates ions at atmospheric pressure and room temperature based on the difference of the mobility of ions in strong electric fields and weak electric fields. This field-dependent mobility of an ion is reflected in the compensation voltage (CV) at which the ion is transmitted through FAIMS, at a given asymmetric waveform dispersion voltage (DV). Experimental CV, relative peak ion intensity, and peak width data were compared for three FAIMS prototypes with concentric cylindrical electrodes having inner/outer electrode radii of: (1) 0.4/0.6 cm, (2) 0.8/1.0 cm, and (3) 1.2/1.4 cm. The annular analyzer space was 0.2 cm wide in each case. A finite-difference numerical computation method is described for evaluation of peak shapes and widths in a CV spectrum collected using cylindrical geometry FAIMS devices. Simulation of the radial distribution of the ion density in the FAIMS analyzer is based upon calculation of diffusion, electric fields, and the electric fields introduced by coulombic ion-ion repulsion. Excellent agreement between experimental and calculated peak shapes were obtained for electrodes of wide diameter and for ions transmitted at low CV.     

Low-dimensional intrinsic material functions for nonlinear viscoelasticity

Rheological material functions are used to form our conceptual understanding of a material response. For a nonlinear rheological response, the possible deformation protocols and material measures span a high-dimensional space. Here, we use asymptotic expansions to outline low-dimensional measures for describing leading-order nonlinear responses in large amplitude oscillatory shear (LAOS). This amplitude-intrinsic regime is sometimes called medium amplitude oscillatory shear (MAOS). These intrinsic nonlinear material functions are only a function of oscillatory frequency, and not amplitude. Such measures have been suggested in the past, but here, we clarify what measures exist and give physically meaningful interpretations. Both shear strain control (LAOStrain) and shear stress control (LAOStress) protocols are considered, and nomenclature is introduced to encode the physical interpretations. We report the first experimental measurement of all four intrinsic shear nonlinearities of LAOStrain. For the polymeric hydrogel (polyvinyl alcohol - Borax) we observe typical integer power function asymptotics. The magnitudes and signs of the intrinsic nonlinear fingerprints are used to conceptually model the mechanical response and to infer molecular and microscale features of the material.     

Linear stability of radially-heated circular Couette flow with simulated radial gravity

The stability of circular Couette flow between vertical concentric cylinders in the presence of a radial temperature gradient is considered with an effective “radial gravity.” In addition to terrestrial buoyancy − ρg e _z we include the term − ρg _m f(r)e _r where g _m f(r) is the effective gravitational acceleration directed radially inward across the gap. Physically, this body force arises in experiments using ferrofluid in the annular gap of a Taylor–Couette cell whose inner cylinder surrounds a vertical stack of equally spaced disk magnets. The radial dependence f(r) of this force is proportional to the modified Bessel function K ₁(κr), where 2π/κ is the spatial period of the magnetic stack and r is the radial coordinate. Linear stability calculations made to compare with conditions reported by Ali and Weidman (J. Fluid Mech., 220, 1990) show strong destabilization effects, measured by the onset Rayleigh number R, when the inner wall is warmer, and strong stabilization effects when the outer wall is warmer, with increasing values of the dimensionless radial gravity γ = g _m /g. Further calculations presented for the geometry and fluid properties of a terrestrial laboratory experiment reveal a hitherto unappreciated structure of the stability problem for differentially-heated cylinders: multiple wavenumber minima exist in the marginal stability curves. Transitions in global minima among these curves give rise to a competition between differing instabilities of the same spiral mode number, but widely separated axial wavenumbers.     

Simultaneous analysis of prostanoids using liquid chromatography/high-field asymmetric waveform ion mobility spectrometry/tandem mass spectrometry

A liquid chromatography/high-field asymmetric waveform ion mobility spectrometry/tandem mass spectrometry (LC-FAIMS-MS/MS) semi-quantitative method was developed for the simultaneous determination of prostaglandin (PG) E2, PGD2, PGF(2alpha), 6-keto-PGF(1alpha), and thromboxane (TX) B2. Diluted samples containing these prostanoids and their tetra-deuterium-substituted internal standards were analyzed by LC followed by either selected reaction monitoring (LC-SRM) or FAIMS and selected reaction monitoring (LC-FRM). FAIMS reduced background noise, separated the isobaric ions PGE2 and PGD2, and separated dynamically interchanging TXB2 anomers. This is the first report of the separation of interconverting anomers by FAIMS. Generally, the LC-FRM chromatograms were more selective than the LC-SRM chromatograms. Its potential was demonstrated by analysis of prostanoids in guinea pig lumbar spinal cord homogenate.     

Electrospray mass spectrometry of neuac oligomers associated with the c fragment of the tetanus toxin

The Clostridial neurotoxins, botulinum and tetanus, gain entry into motor neurons by binding to the sialic or N-acetylneuraminic acid (NeuAc) residues of gangliosides and specific protein receptors attached to the cell's surface. While the C-fragment of tetanus toxin (TetC) has been identified to be the ganglioside binding domain, remarkably little is known about how this domain discriminates between the structural features of different gangliosides. We have used electrospray ionization mass spectrometry (ESI-MS) to examine the formation of complexes between TetC and carbohydrates containing NeuAc groups to determine how NeuAc residues contribute to ganglioside binding. ESI-MS was used to obtain an estimate of the dissociation constants (KD values) for TetC binding to a number of related NeuAc-containing carbohydrates (sialyllactose and disialyllactose), as well as six (NeuAc)n oligomers (n = 1-6). KD values were found to range between approximately 10-35 microM. The strength of the interactions between the C fragment and (NeuAc)n are consistent with the topography of the targeting domain of tetanus toxin and the nature of its carbohydrate binding sites. These results suggest that the targeting domain of tetanus toxin contains two binding sites that can accommodate NeuAc (or a dimer) and that NeuAc may play an important role in ganglioside binding and molecular recognition, a process critical for normal cell function and one frequently exploited by toxins, bacteria, and viruses to facilitate their entrance into cells.     

Effect of side-chain substituents on self-assembly of perylene diimide molecules: morphology control

Effect of side-chain substitutions on the morphology of self-assembly of perylene diimide molecules has been studied with two derivatives modified with distinctly different side-chains, N,N'-di(dodecyl)-perylene-3,4,9,10-tetracarboxylic diimide (DD-PTCDI) and N,N'-di(nonyldecyl)-perylene-3,4,9,10-tetracarboxylic diimide (ND-PTCDI). Due to the different side-chain interference, the self-assembly of the two molecules results in totally different morphologies in aggregate: one-dimensional (1D) nanobelt vs zero-dimensional (0D) nanoparticle. The size, shape, and topography of the self-assemblies were extensively characterized by a variety of microscopies including SEM, TEM, AFM, and fluorescence microscopy. The distinct morphologies of self-assembly have been obtained from both the solution-based processing and surface-supported solvent-vapor annealing. The nanobelts of DD-PTCDI fabricated in solution can feasibly be transferred to both polar (e.g., glass) and nonpolar (e.g., carbon) surfaces, implying the high stability of the molecular assembly (due to the strong pi-pi stacking). The side-chain-dependent molecular interaction was comparatively investigated using various spectrometries including UV-vis absorption, fluorescence, X-ray diffraction, and differential scanning calorimetry. Compared to the emission of ND-PTCDI aggregate, the emission of DD-PTCDI aggregate was significantly red-shifted (ca. 30 nm) and the emission quantum yield decreased about three times, primarily due to the more favorable molecular stacking for DD-PTCID. Moreover, the aggregate of DD-PTCDI shows a pronounced absorption band at the longer wavelength, whereas the absorption of ND-PTCDI aggregate is not significant in the same wavelength region. These optical spectral observations are reminiscent of the previous theoretical investigation on the side-chain-modulated electronic properties of PTCDI assembly.