Evidence for acyl-iron ligation in the active site of [Fe]-hydrogenase provided by mass spectrometry and infrared spectroscopy

[Fe]-hydrogenase catalyzes the reversible heterolytic cleavage of H(2) and stereo-specific hydride transfer to the substrate methenyltetrahydromethanopterin in methanogenic archaea. This enzyme contains a unique iron guanylylpyridinol (FeGP) cofactor as a prosthetic group. It has recently been proposed-on the basis of crystal structural analyses of the [Fe]-hydrogenase holoenzyme-that the FeGP cofactor contains an acyl-iron ligation, the first one reported in a biological system. We report here that the cofactor can be reversibly extracted with acids; its exact mass has been determined by electrospray ionization Fourier transform ion cyclotron resonance mass-spectrometry. The measured mass of the intact cofactor and its gas-phase fragments are consistent with the proposed structure. The mass of the light decomposition products of the cofactor support the presence of acyl-iron ligation. Attenuated total reflection infrared spectroscopy of the FeGP cofactor revealed a band near wave number 1700 cm(-1), which was assigned to the C=O (double bond) stretching mode of the acyl-iron ligand.     

Personal and atmospheric concentrations of ozone in southeastern hyogo prefecture, Japan

Twenty-one data sets composed of readings collected by atmospheric ozone monitors worn by individuals on their clothing and installed outside their home or office were collected using Ogawa passive ozone samplers in southeastern Hyogo prefecture, Japan from September 12 to 13, 2011. The concentrations of personal and outdoor ozone ranged from not detectable to 23.2?ppb and from 4.7 to 38.3?ppb, respectively. The mean concentration of personal exposure to ozone was 3.7?ppb and was significantly lower than that of outdoor ozone (18.5?ppb). This suggests that the concentrations of outdoor ozone affect personal ozone exposure. However, in this study, we found no correlation between the concentrations of personal ozone and the total time spent outdoors or the time of day the individual was outside. In contrast, the mean concentrations of outdoor ozone were similar to those of ozone measured at the 12 nearest Ambient Monitoring Stations (AMSs). However, when the AMS was situated near a main road, the regional ozone levels were underestimated.     

Anomalous enhancement in the infrared phonon intensity of a one-dimensional uneven peanut-shaped C60 polymer

A one-dimensional (1D) uneven peanut-shaped C(60) polymer formed from electron-beam (EB)-induced polymerization of C(60) molecules showed an anomalous increase in two characteristic infrared (IR) peak intensities, which are respectively due to the radial and tangential motion of the 1D polymer, when compared to the IR peaks of pristine C(60) films. This anomaly was analyzed on the basis of the vibrational van Hove singularity (VHS), using an extended thin-shell elastic model fully considering the effects of periodic radius modulation inherent to the 1D uneven peanut-shaped C(60) polymer. We succeeded in explaining the enhancement in the tangential peak intensity by VHS, whereas the origin to cause that in the radial peak intensity is still unclear.     

Enhancing endothelial differentiation of human mesenchymal stem cells by culture on a nanofibrous polycaprolactone/(poly-glycerol sebacate)/gelatin scaffold

Cardiovascular diseases have always been one of the main causes of death worldwide and eventually one of the major medical concerns. Tissue engineering is promising strategies of treating cardiovascular, which can be an effective approach with the design of appropriate scaffold. In this study, to develop engineering basement membrane for endothelial differentiation with good cell attachment, we produced polycaprolactone (PCL)/poly (glycerol sebacate) (PGS)/gelatin nanofibrous scaffold via electrospinning. Attenuated total reflectance-Fourier transform infrared and the proton nuclear magnetic resonance results confirmed the chemical structure of synthesized PGS. Scanning electron microscope images of the electrospun scaffold revealed that the nanofibers are smooth, continues and uniform. Moreover, due to the presence of hydrophilic functional groups in the scaffold, the contact angle is in the appropriate range for cell adhesion especially endothelial cells. The elastic modulus and ultimate tensile stress of electrospun scaffold were calculated 1.32 ± 0.27 MPa and 1.23 ± 0.18 MPa respectively. Quantitative polymerase chain reaction was performed for evaluation of endothelial differentiation of mesenchymal stem cells cultured on standard plate and fibrous scaffold under chemical stimulation with growth factor. Specific endothelial gene expression results postulated that our modified scaffold could support and significantly promote endothelial differentiation of MSCs.     

The pummerer and the thio-claisen–type rearrangements of naphtho[1,8-bc]-1,5-dithiocin monooxide and N-p-tosylsulfilimine

Naphtho[1,8-bc]-1,5-dithiocin N-p-tosylsulfilimine ( 8 ) and monosulfoxide ( 9 ) were prepared. On treatment with conc. H₂SO₄, both the sulfilimine ( 8 ) and sulfoxide ( 9 ) gave the dithia dication which was converted to the sulfoxide by hydrolysis. The H–D exchange reaction of ( 8 ) took place highly regioselectively to afford the monodeuterated ( 8–D ) at the a-position of the N-tosyl group. The Pummerer rearrangement reaction of monooxide ( 9 ) with acetic anhydride gave the a-acetoxy derivative by the dication ( 10b ), while a new thio-Claisen rearrangement of sulfilimine ( 8 ) t-BuOK in CH₂Cl₂ gave 2-allyl-naphtho[1,8-bc]-1,5-dithiole. © John Wiley & Sons, Inc.     

Improved Swelling Property of Tissue Adhesive Hydrogels Based on α-Cyclodextrin/Decyl Group-Modified Alaska Pollock Gelatin Inclusion Complexes

Adhesives/sealants are used after suturing to prevent leakage of cerebrospinal fluid from an anastomotic site. Commercial adhesives/sealants have been used to close the cerebral dura. However, swelling of the cured adhesives/sealants induces increased intracranial pressure and decreases the strength of the seal. In the present study, tissue adhesive hydrogels with improved swelling property using inclusion complex composed of α-cyclodextrin (αCD) and decyl group (C10)-modified Alaska pollock-derived gelatin (C10-ApGltn) with a high degree of substitution (DS) (>20 mol%) are developed. Viscosity of C10-ApGltn with a high DS solution remarkably decreased by the addition of αCD. The resulting αCD/C10-ApGltn adhesive hydrogel composed of αCD/C10-ApGltn inclusion complexes and poly(ethylene glycol) (PEG)-based crosslinker showed improved swelling property after immersion in saline. Also, the resulting adhesive has a significantly higher burst strength than fibrin-based adhesives and is as strong as a PEG-based adhesive. Quantitative analysis of αCD revealed that the improved swelling property of the resulting adhesive hydrogels is induced by the release of αCD from cured adhesive, and the subsequent assembly of decyl groups in the saline. These results suggest that adhesives developed using the αCD/C10-ApGltn inclusion complex can be useful for closing the cerebral dura mater.