Biomimetic synthesis routes towards the important natural d ‐mannosyl donor guanosine 5′‐diphospho‐d ‐mannose (GDP‐Man) rely on kinase‐catalyzed nucleotide triphosphate (NTP)‐dependent phosphorylations of d ‐mannose (Man), to give d ‐mannose 6‐phosphate or α‐d ‐mannose 1‐phosphate (αMan 1‐P) as an intermediate product. A GDP‐Man synthesis not requiring the kinase/NTP system would be practical and cost‐effective. Here, we have developed a multienzyme cascade towards GDP‐Man, characterized in that αMan 1‐P was obtained by a diastereoselective phosphatase‐catalyzed phosphorylation of Man. α‐d ‐Glucose 1‐phosphate (αGlc 1‐P), prepared in situ through phosphorylase‐catalyzed conversion of sucrose in the presence of inorganic phosphate, was used as an expedient phosphoryl donor. The incipient αMan 1‐P and guanosine triphosphate (GTP) were converted into GDP‐Man by a highly manno compared to gluco selective nucleotidyltransferase. Pyrophosphatase was additionally required to hydrolyze the pyrophosphate released from the GTP, thus driving the reaction towards GDP‐Man. The enzymatic cascade was operated with the αMan 1‐P and the GDP‐Man formation decoupled from one another (sequential mode) or having all steps run concurrently (simultaneous mode). Detailed time course analysis revealed that kinetic pull due to the constant removal of the intermediate αMan 1‐P in simultaneous‐mode reactions was important to promote phosphorylation of Man from αGlc 1‐P in high efficiency, avoiding loss of sugar 1‐phosphates by hydrolysis. Under optimized conditions for the one‐pot transformation involving four enzymes, 100 mM (67 g L−1) GDP‐Man was prepared from 140 mM sucrose and phosphate, using 400 mM Man as the phosphoryl acceptor. The product was recovered by anion‐exchange and size‐exclusion chromatography in ≥95% purity in about 50% yield (100 mg). These results demonstrate for the first time the practical use of a phosphorylase‐phosphatase combi‐catalyst as an alternative to the canonical kinase for the anomeric phosphorylation of the sugar substrate in nucleoside diphospho‐sugar synthesis. Phosphorylation from inorganic phosphate via the intermediate αGlc 1‐P rather than from NTP, particularly GTP, appears advantageous specifically in cases where the sugar acceptor is a bulk commodity that can be applied in suitable excess to the phosphatase reaction.
A one‐range and a two‐range model for the laminar velocity distribution in the entrance region of tubes and ducts are presented. These allow the calculation of the residence time distribution under the impact of the flow development in the hydrodynamic entrance region. For the dispersion‐free case, an analytical solution is given. A cell model with place‐changing probability (ZEMP) is applied for the consideration of dispersion. This approach allows the fast quantification of the influence of different parameters on the residence time distribution for relatively short pipes and ducts. The numerical results are compared with earlier presented results of semi‐empirical models. 相似文献
This review documents that, contrary to the general impression that molecular electrochemistry is mostly devoted to the analysis of reaction mechanisms induced by electron transfer into homogeneous solutions of molecules, its concepts and methods are perfectly suited to the investigation of extremely fast molecular events occurring within nano- and sub-nanometric distances from a working electrode surface. Ultrafast cyclic voltammetry (i.e., up to the range of a few megavolts per second) coupled to online electronic compensation of ohmic drop is thus shown to provide direct measurements of extremely fast electron transfer between redox centers tethered to electrodes, by conducting molecular bridges, or of dendrimers adsorbed onto the electrode surface. This allows discussing in particular the role of counterions in the process of electronic commutation of self-assembled monolayers. 相似文献
Sesquiterpenes (STs) from the Senecioneae have been found to be potent snail repellents. We investigated the range of activity of the STs petasin, isopetasin, furanopetasin, kablicin, and cacalol, which were isolated from Petasites hybridus, P. kablikianus, and Adenostyles alpina. We found the petasin content of leaves of P. hybridus to lie within the range of deterrence of the isolated compound. Furthermore, leaf extracts containing petasin proved to be deterrent, and leaf discs with low petasin content were preferred over discs with higher petasin content. The cacalol-containing fraction of a leaf extract of A. alpina was not deterrent to the snails. When the snails had experience with the relevant ST one week before a choice test, their sensitivity towards petasine and furanopetasine increased whereas for the other ST it remained at the same level. We speculate that this sensitivity increase could be the result of a rapid long-term associative learning process, but there is also the possibility that these STs are directly interfering with the feeding motor program of the snails, thereby eliciting a direct neurophysiological sensitization reaction which prevents them from further feeding. 相似文献
A systematic study of a ring‐closing metathesis towards a tetrasubstituted double bond as part of a seven‐membered ring in a 5.7.5‐tricyclic guaianolide system is described. By combining two techniques, namely sparging an inert gas through the solution together with dielectric heating via microwave irradiation a high‐yielding ring‐closing metathesis reaction in this particularly challenging case was achieved. The results obtained compare favorably with conventional heating conditions or with microwave irradiation in a closed system. The key aspects seem to be that rapid microwave irradiation diminishes catalyst decay by allowing the required high reaction temperature to be reached quickly and homogeneously and thereby providing enough energy for a successful metathesis reaction, while inert gas sparging is purging off evolving ethylene to shift the equilibrium to the product. 相似文献
It is well known that inorganic filler particles enhance the mechanical and tribological properties of polymers. The stiffness, toughness, and wear performance of the composites are extensively determined by the size, shape, volume content, and especially the dispersion homogeneity of the particles. In the present study, various amounts of micro‐ and nano‐scale particles (titanium dioxide TiO2, 200–400 nm, calcium silicate CaSiO3, 4–15 μm) were introduced into an epoxy polymer matrix for its reinforcement. The influence of these particles on the impact strength, dynamic mechanical thermal properties, and block‐on‐ring wear behavior was investigated. Using only the nano‐particles, the results demonstrate the best improvement in stiffness, impact strength, and wear resistance of the epoxy at a nano‐particle content of 4 vol% TiO2. Therefore, this nanocomposite was used to act as a matrix for the CaSiO3 micro‐particles, in the hope of finding synergistic effects between the micro‐ and the nano‐particles. Results show, in fact, a further improvement of wear resistance and stiffness, whereas the impact strength suffers. Geometrical properties of the particles, the homogeneous dispersion state, energy dissipating fracture mechanisms, and a transition of wear mechanisms mostly contribute to the increase in performance. 相似文献
