Chemo-enzymatic synthesis of 4-methylumbelliferyl beta-(1-->4)-D-xylooligosides: new substrates for beta-D-xylanase assays

Transglycosylation catalyzed by a beta-D-xylosidase from Aspergillus sp. was used to synthesize a set of 4-methylumbelliferyl (MU) beta-1-->4-D-xylooligosides having the common structure [beta-D-Xyl-(1-->4)]2-5-beta-D-Xyl-MU. MU xylobioside synthesized chemically by the condensation of protected MU beta-D-xylopyranoside with ethyl 2,3,4-tri-O-acetyl-1-thio-beta-D-xylopyranoside was used as a substrate for transglycosylation with the beta-D-xylosidase from Aspergillus sp. to produce higher MU xylooligosides. The structures of oligosaccharides obtained were established by 1H and 13C NMR spectroscopy and electrospray tandem mass spectrometry. MU beta-D-xylooligosides synthesized were tested as fluorogenic substrates for the GH-10 family beta-D-xylanase from Aspergillus orizae and the GH-11 family beta-D-xylanase I from Trichoderma reesei. Both xylanases released the aglycone from MU xylobioside and the corresponding trioside. With substrates having d.p. 4 and 5, the enzymes manifested endolytic activities, splitting off MU, MUX, and MUX2 primarily.     

The shear modulus of the human vocal fold in a transverse direction

The aim of this study was to measure the shear modulus of the vocal fold in a human hemilarynx, such that the data can be related to direction of applied stress and anatomical context. Dynamic spring rate data were collected using a modified linear skin rheometer using human hemilarynges, and converted to estimated shear modulus via application of a simple shear model. The measurement probe was attached to the epithelial layer of the vocal fold cover using suction. A sinusoidal force of 3g was applied to the epithelium, and the resultant displacement logged at a rate of 1kHz. Force measurement accuracy was 20microg and position measurement accuracy was 4microm. The force was applied in a transverse direction at the midmembranous point between the vocal process and the anterior commissure. The shear modulus of the three female vocal folds ranged from 814 to 1232Pa. The shear modulus of the three male vocal folds ranged from 1021 to 1796Pa. These data demonstrate that it is possible to obtain estimates for the shear modulus of the vocal fold while preserving anatomical context. The modulus values reported here are higher than those reported using parallel plate rheometry. This is to be expected as the tissue is attached to surrounding structures, and is under natural tension.     

In situ solid-state NMR spectroscopy of protein in heterogeneous membranes: the baseplate antenna complex of Chlorobaculum tepidum

A clever combination: an in situ solid-state NMR analysis of CsmA proteins in the heterogeneous environment of the photoreceptor of Chlorobaculum tepidum is reported. Using different combinations of 2D and 3D solid-state NMR spectra, 90?% of the CsmA resonances are assigned and provide on the basis of chemical shift data information about the structure and conformation of CsmA in the CsmA-bacteriochlorophyll a complex.     

Microbial Sulfatases

The capacity for cleaving off modifying sulfated molecules is related to the presence of sulfatase enzymes in all organisms. Sulfatases (EC 3.1.6.) remove sulfate groups from a set of diverse molecules and constitute a quite heterogeneous group of enzymes characterized by diverse catalytic mechanisms. Human sulfatases are characterized in most detail due to their important role in certain physiological processes. Microbial sulfatases remain virtually uncharacterized on the biochemical level and their potential remains unexplored. The present review summarizes the results of research on sulfatases from bacteria and lower eukaryotes, addresses the connection between these results and the established regularities in the current classification of sulfatases, and considers the potential applications for the use of sulfatases.     

A Disilene Base Adduct with a Dative Si–Si Single Bond

An experimental and theoretical study of the base‐stabilized disilene 1 is reported, which forms at low temperatures in the disproportionation reaction of Si₂Cl₆ or neo‐Si₅Cl₁₂ with equimolar amounts of NMe₂Et. Single‐crystal X‐ray diffraction and quantum‐chemical bonding analysis disclose an unprecedented structure in silicon chemistry featuring a dative Si→Si single bond between two silylene moieties, Me₂EtN→SiCl₂→Si(SiCl₃)₂. The central ambiphilic SiCl₂ group is linked by dative bonds to the amine donor and the bis(trichlorosilyl)silylene acceptor, which leads to push–pull stabilization. Based on experimental and theoretical examinations a formation mechanism is presented that involves an autocatalytic reaction of the intermediately formed anion Si(SiCl₃)₃^? with neo‐Si₅Cl₁₂ to yield 1 .     

COMPOSITION OF INDOOR AEROSOLS AT EMPEROR QIN''''S TERRA-COTTA MUSEUM, XI''''AN, CHINA, DURING SUMMER, 2004

Particle samples were collected in August 2004 both inside and outside Emperor Qin's Terra-Cotta Museum in Xi'an, China. Mass and chemical composition of total suspended particles (JSP, particles with aerodynamic diameter less than-30μm), PM2.5(particles with aerodynamic diameter <2.5μm) were determined. The average levels of indoor PM2.5 and TSP were 108.4 and 172.4 μg·m-3, respectively, with PM2.5 constituting 62.9% of the TSP mass. Sulfate ((32.4±6.2)%), organics ((27.7±8.0)%), and geological material ((12.5±3.4)%) dominated indoor PM2.5, followed by ammonium ((8.9±2.8)%), nitrate ((7.0±2.9)%), and elemental carbon (EC, (3.9±1.5)%). Particle size distribution varied with the number of tourists in the museum. The size of sulfate, organics, EC, nitrate, and ammonium was found to vary in the range of 0.43 to 3.3 μm in fraction. Ion balance indicated that the aerosol was acidic, with insufficient ammonium ions to neutralize the sulfuric and nitric acids. High concentrations of acidic aerosols will erode the Terra-cotta warriors and horses especially in the summer season with high temperature (30℃) and relative humidity (70%) and undesirable solar radiation inside the museum. More attention should be paid to protecting these precious antiques made 2000 years ago.     

An ultra-low hydrolysis sol-gel route for titanosilicate xerogels and their characterization

In this work TiO₂-SiO₂ xerogels were prepared through an ultra low hydrolysis method using titanium and silicon alkoxide. The samples were heat treated to 500°C. The xerogels were characterized using TGA/DTA, FTIR, XRD and TEM. The samples showed the formation of Si–O–Ti bridges by its characteristic vibration within 925–960 cm⁻¹ range. Si–O–Si bond angles were calculated using the central force network model. The TiO₂ in all the samples crystallized on heat treatment to 500°C. The crystallite size calculated using the Scherer formula from the XRD was verified from the Transmission Electron Micrograph. Samples heat treated to 350°C remained amorphous and hence could be used as hosts for biomaterials and organic optical materials.