Challenges in quantitative analyses for volatile organic compounds bound to lipocalins

In this communication, I describe the challenges in quantitative analyses for volatile organic compounds in mouse urine, which are primarily caused by the presence of the major urinary proteins, a lipocalin subfamily, that sequester volatile ligands. The analyses of volatile compounds in mouse urine have been performed since the late 1970s. However, none of them considered the binding interactions of the quantified compounds with the urinary proteins. Some volatile ligands are tightly bound to the proteins and may not be extracted completely by organic solvents. The amounts of volatile ligands measured by external standard calibration represent those of the unbound ligands in the headspace, not the total amounts in urine. Addition of internal standards displaces ligands bound to the proteins, resulting in a completely different volatile profile. Normalization of volatile compounds using relative peak area (or height) ratios may not be used in the conditions where displacement of ligands bound to the proteins occurs. Because of the unique chemical properties of mouse urine, I have not been able to find a good quantification method for the volatile compounds released from mouse urine. I hope that the identification of these issues will stimulate others to come up with novel approaches.     

Lasonolide A: structural revision and total synthesis

The proposed structure of lasonolide A was synthesized employing radical cyclization reactions of beta-alkoxyacrylates for preparation of the tetrahydropyranyl units A and B, but the spectroscopic data did not match those of the natural product. Both enantiomers of a revised structure featuring 17E,25Z double bonds were synthesized, and the (-)-isomer was found to be the biologically active enantiomer.     

Biomedical significance of endothelial cell specific growth factor, angiopoietin

Until recently, vascular endothelial growth factor (VEGF) was the only growth factor proven to be specific and critical for blood vessel formation. Other long-known factors, such as the fibroblast growth factors (FGFs), platelet-derived growth factor, or transforming growth factor-beta, had profound effects in endothelial cells. But such factors were nonspecific, in that they could act on many other cells, and it seemed unlikely that these growth factors would be effective targets for treatment of endothelial cell diseases. A recently discovered endothelial cell specific growth factor, angiopoietin, has greatly contributed to our understanding of the development, physiology, and pathology of endothelial cells (Davis et al., 1996; Yancopoulos et al., 2000). The recent studies that identified and characterized the physiological and pathological roles of angiopoietin have allowed us to widen and deepen our knowledge about blood vessel formation and vascular endothelial function. Therefore, in this review, we describe the biomedical significance of these endothelial cell growth factors, the angiopoietins, in the vascular system under normal and pathological states.     

Weak noncovalent Si···F?C interactions stabilized fluoroalkylated rod-like polysilanes as ultrasensitive chemosensors

Noncovalent interactions, such as hydrogen bonding, metal coordination, and π-π stacking, are increasingly being utilized to develop well-ordered and self-organized supramolecular materials. Recently, new types of nonclassical weak interactions, such as C H···π, C H···F C, and C H···O, have been exploited in stabilizing the specific conformations of molecules and molecular assemblies in the solid state. These noncovalent interactions play an important role in materials comprised of polymer chains, because cooperative effects from a large number of weak interactions can lead to drastic changes in its conformation, several properties, and functionalities. The programmed design of synthetic helical polymer with well-defined molecular conformation has been the main subject in modern polymer science and engineering. Silicon-catenated polysilane is an ideal helical silicon quantum wire and polymers with unique photophysical properties. The present review highlights the spectroscopic evidences for through-space weak Si···F C interaction in poly(methyl-3,3,3-trifluoropropylsilane) ( 1 ) in noncoordinating and coordinating solvents by means of NMR (²⁹Si and ¹⁹F) and IR spectroscopies, and viscometric measurement. It was found that 1 is applicable for chemosensors with an extremely high sensitivity and selectivity toward fluoride ions in tetrahydrofuran (THF) and with high sensitivity for nitroaromatic compounds, detected by a decrease in the photoluminescence intensity in THF and in thin solid film. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5060–5075, 2006     

Real-time observation of temperature-dependent protein-protein interactions using real-time dual-color detection system

This study examined the ability of a real-time dual-color detection system to allow direct observations of the kinetics of temperature-dependent protein-protein interaction at a single-molecule level. The primary target protein was an Alexa Fluor^® 488-labeled actin conjugate, which had been pre-incubated with an unlabeled rabbit anti-actin antibody (IgG). The complementary fluorescent protein was Alexa Fluor^® 633-labeled goat anti-rabbit IgG antibody, which interacts with the rabbit anti-actin antibody (IgG) bound to the Alexa Fluor^® 488-labeled actin conjugate. The individual protein molecules labeled with different fluorescent dyes in solution were effectively focused, interacted with the other protein molecules at 500 aM, and detected directly in real-time using the dual-wavelength (λ_ex = 488 and 635 nm) laser-induced fluorescence detection system. The kinetics of the protein-protein interactions were examined at different temperatures (12-32 °C). At concentrations in the aM range, the number of bound complex molecules through the protein-protein interaction decreased gradually with time at a given temperature, and increased with decreasing temperature at a set time. A high concentration (above 500 pM) of the protein sample caused aggregation and nonspecific binding of the protein molecules, even though the protein molecules were not an example of complementary binding. The results demonstrated that the real-time kinetics of a protein-protein interaction could be analyzed effectively at the single-molecule level without any time delay using the real-time dual-color detection system.     

All-solid-state carbonate-selective electrode based on a molecular tweezer-type neutral carrier with solvent-soluble conducting polymer solid contact

Carbonate-selective membranes were prepared by incorporating a molecular tweezer-type carbonate-selective neutral carrier [N,N-dioctyl-3alpha,12alpha-bis(4-trifluoroacetylbenzyloxy)-5beta-cholan-24-amide] into a room temperature vulcanizing-type silicone rubber (3140 RTV-SR) matrix, and deposited on the planar-type electrodes (Pt containing Ag/AgCl electrodes formed on a ceramic plate) with and without an intermediary conducting polymer layer. Two types of solvent-soluble conducting polymers [poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene) or poly(3-octylthiophene-2,5-diyl)] have been examined as the solid contact material. Potentiometric properties of the resultant all-solid-state electrodes were evaluated in terms of their carbonate selectivity, response slope, potential stability and reproducibility. The sensitivity and carbonate selectivity of the SR membrane-based all-solid-state electrodes with conducting polymer solid contact were comparable to those of conventional electrodes. Experimental results also showed that the intermediary conducting polymer layer used in the all-solid-state electrodes greatly reduces the interference from dissolved oxygen.     

Piezochromic fluorescence in liquid crystalline conjugated polymers

Liquid crystalline diphenylacetylene polymer derivatives showed piezochromic fluorescence via order-to-disorder phase transition.     

Conductivity‐Dependent Completion of Oxygen Reduction on Oxide Catalysts

The electric conductivity‐dependence of the number of electrons transferred during the oxygen reduction reaction is presented. Intensive properties, such as the number of electrons transferred, are difficult to be considered conductivity‐dependent. Four different perovskite oxide catalysts of different conductivities were investigated with varying carbon contents. More conductive environments surrounding active sites, achieved by more conductive catalysts (providing internal electric pathways) or higher carbon content (providing external electric pathways), resulted in higher number of electrons transferred toward more complete 4e reduction of oxygen, and also changed the rate‐determining steps from two‐step 2e process to a single‐step 1e process. Experimental evidence of the conductivity dependency was described by a microscopic ohmic polarization model based on effective potential localized nearby the active sites.     

Metal-directed supramolecular assembly of metal(II) benzoates (M = Co,Ni, Cu,Zn, Mn,and Cd) with 4,4′-bipyridine: Effects of metal coordination modes and novel catalytic activities

Six polymeric metal(II)-benzoate complexes of formula [Co₂(O₂CPh)₄(4,4′-bpy)₂]_n (1-Co), [Ni(O₂CPh)₄(H₂O)₂(4,4′-bpy)]_n (2-Ni), [Cu₂(O₂CPh)₄(4,4′-bpy)]_n (3-Cu), [Zn₂(O₂CPh)₂(OH)₂(4,4′-bpy)₂]_n (4-Zn), [Zn₃(O₂CPh)₄(μ-OH)₂(4,4′-bpy)₂]_n (5-Zn), and [Cd₂(O₂CPh)₄(4,4′-bpy)₂]_n (6-Cd) have been synthesized and characterized (4,4′-bpy = 4,4′-bipyridine). 1-Co and 6-Cd show ladder-type double chains, 2-Ni does a helical structure, 3-Cu does a one-dimensional chain containing paddle-wheel units, 4-Zn does a zigzag chain, and 5-Zn does two-dimensional sheets. Since different structures provide different coordination geometry of each metal ion, it is clear that selection of appropriate metal ions can control the coordination geometry of each metal ion to form different crystal structures. Reactivity study of the compounds 1–7 for the transesterification of a variety of esters has shown that 4-Zn and 5-Zn are very efficient and the best among them. The catalyst 6-Cd containing Cd ion, well known as an inert metal ion for the ligand substitution, also catalyzed efficiently the transesterification of a variety of esters, and its reactivity is comparable to 4-Zn and 5-Zn. Moreover, the redox-active metal-containing polymers, 1-Co, 3-Cu, and 7-Mn, have shown efficient catalytic reactivities for the transesterification reactions, while 2-Ni has displayed a very slow conversion. The reactivities of the compounds used in this study are in the order of 5-Zn > 4-Zn > 6-Cd > 7-Mn ∼ 3-Cu > 1-Co > 2-Ni, indicating that the non-redox metal-containing compounds (5-Zn, 4-Zn, and 6-Cd) show better activity than the redox-active metal-containing compounds (7-Mn, 3-Cu, 1-Co, and 2-Ni). These results suggest that it is possible to tune the catalytic activities by changing from Zn to those metals such as Cd, a kinetically inert metal, or Cu, Mn, and Co, the redox-active metals.