A method for improving separations of peptides and other positively charged species in capillary zone electrophoresis with untreated capillaries using acidic buffers containing tetraalkylammonium cations is described. Tetramethylammonium and tetrabutylammonium cations dynamically modify the capillary surface, leading to a reversal in the direction of the electroosmotic flow. As a result, the adsorption of positively charged peptides and proteins is minimized, and resolution and peak capacity are improved as the migration of cationic analytes is counterbalanced by the electroosmotic flow. The combining effect of reversing electroosmotic flow and cyclodextrin inclusion complexation on separations of closely related peptides and a protein mixture, as well as tryptic digest of hemoglobin is demonstrated. 相似文献
Nocardicin A analogues 30, 34 , and 38 as well as the highly strained quinone methide 43 were synthesized. β -Lactam 34 was found biologically active against several Gram-negative microorganisms in vitro; pyridinium N-oxide derivative 38 possessed activity against Gram-positive S. aureus bacterium. Masked p-quinone methide β -lactam 43 exhibited significant antimicrobial activity in vitro. A mechanism involving an oxidation in vivo is proposed for the unprecedented biological properties of nocardicins. 相似文献
Crystalline ninhydrin (1) undergoes waste-free solid-state cascade reactions with dimedone, L-proline, three o-phenylenediamines, o-mercaptoaniline, two ureas, three thioureas, and methyl 3-aminocrotonate. The yields are quantitative and give pure crystalline products without workup just by milling stoichiometric mixtures of the crystalline reagents. The structures of the new and the previously obtained products with lower yields from solutions are established or confirmed by spectroscopic data and density functional calculations at the B3LYP/6-31G* level. The success of 3- and 4-cascade reactions in the crystal without melting is unusual and of unmatched atom economy. They are mechanistically investigated with atomic force microscopy techniques (AFM) on six different faces of 1 when o-phenylenediamine was the reagent (substitution, elimination, cyclization, elimination) and interpreted on the basis of known crystal structure data. Strict correlations to the crystal packings are observed. The characteristic surface features grow to microm heights in some cases at distances of 0.5 mm from the contact edge of the reacting crystals. The waste-free and easy syntheses of highly functionalized (C=O; O-H; C=N) heterocycles or of a tetraketone are also of interest for synthetic use. 相似文献
Ricerche di Matematica - Let G be a finite group and $$N \unlhd G$$ . The normal subgroup based power graph of G, $$\Gamma _N(G)$$ , is an undirected graph with vertex set $$(G{\setminus }N) \cup... 相似文献
In the manufacturing of fattening pigs, pig marketing refers to a sequence of culling decisions until the production unit is empty. The profit of a production unit is highly dependent on the price of pork, the cost of feeding and the cost of buying piglets. Price fluctuations in the market consequently influence the profit, and the optimal marketing decisions may change under different price conditions. Most studies have considered pig marketing under constant price conditions. However, because price fluctuations have an influence on profit and optimal marketing decisions it is relevant to consider pig marketing under price fluctuations. In this paper we formulate a hierarchical Markov decision process with two levels which model sequential marketing decisions under price fluctuations in a pig pen. The state of the system is based on information about pork, piglet and feed prices. Moreover, the information is updated using a Bayesian approach and embedded into the hierarchical Markov decision process. The optimal policy is analyzed under different patterns of price fluctuations. We also assess the value of including price information into the model.
Living cells can process rapidly and simultaneously multiple extracellular input signals through the complex networks of evolutionary selected biomolecular interactions and chemical transformations. Recent approaches to molecular computation have increasingly sought to mimic or exploit various aspects of biology. A number of studies have adapted nucleic acids and proteins to the design of molecular logic gates and computational systems, while other works have affected computation in living cells via biochemical pathway engineering. Here we report that de novo designed synthetic peptide networks can also mimic some of the basic logic functions of the more complex biological networks. We show that segments of a small network whose graph structure is composed of five nodes and 15 directed edges can express OR, NOR, and NOTIF logic. 相似文献
In some works on the lattice Monte Carlo simulation of amphiphilic systems additional peaks in the cluster size distribution
has been interpreted as a clue for the phase or shape transition of micellar aggregates. On the other hand, some other works
showed that the additional peaks are a result of finite size of the lattice box. In this paper using calculating energy-auto-correlation
function and statistical error in correlated data, it is shown that how these apparently contradictory results are the same.
To do this, we have simulated a pure system containing amphiphile and water molecules. A simple model of potential containing
the main feature for these systems (the hydrophobicity of surfactant molecules) that cause the aggregates to be formed is
considered to avoid any synthetic results due to additional non-real parameters. To relax the initial configuration faster,
configurational bias Monte Carlo move is used in addition to reptation move. Periodic boundary condition and self-avoiding
walks are used as former published works in this field. It is shown that the additional peaks is a result of the statistical
errors for averaged cluster size distribution and can not be interpreted as a clue for shape or phase transition. 相似文献
Summary. Thioamides and thioureas were reacted with tetrabutylammonium periodate at room temperature to afford the corresponding amides and ureas, respectively, under aprotic conditions. 相似文献
InP(100) surfaces treated with Na2Sx9H20 and CnH(2n+1)SH are examined by contact angle measurement, X-ray photoelectron spectroscopy, and atomic force microscopy to determine the chemical and thermal behavior of these passivated surfaces. The surfaces coated by octadecanethiol (n = 18) self-assembled monolayers (SAMs) are found to be more stable toward oxidation than the S-passivated surface. The chemical stability of octadecanethiol SAMs in various environments is examined. The thiol monolayer is found to be stable in 0.1 M HCl but degrades in 0.1 M NaOH, boiling chloroform, and water. The behavior of these surfaces at elevated temperatures under a vacuum is also investigated. The octadecanethiol-coated InP(100) is stable up to 473 K, above which the films begin to degrade. Unlike other substrates on which the entire molecule including the sulfur headgroup desorbs together, on InP, the sulfur headgroup remains on the surface even after annealing to 673 K. These observations suggest that the desorption occurs by S-C bond cleavage as well as In-S bond cleavage. The sulfur of S-passivated InP is found to be more thermally stable than that of the octadecanethiol monolayer, perhaps due to their different bonding geometries and hence energies. 相似文献
Summary. A short facile synthesis of the fungal metabolite (±)-3,4-dihydro-3,6,8-trihydroxy-3- pentadecylisocoumarin (peniolactol)
has been achieved. Condensation of hexadecanoyl chloride with 3,5-dimethoxyhomophthalic acid afforded 6,8-dimethoxy-3-pentadecylisocoumarin,
which on sequential saponification and demethylation furnished rac-peniolactol in 31% overall yield. The ring-chain tautomerism was studied in solution by 1H NMR and the mass fragmentation pattern. 3-Pentadecyl- isocoumarin was also synthesized and saponified to the corresponding
keto acid as a model compound for comparative studies.
E-mail: aamersaeed@yahoo.com
Received May 23, 2002; accepted May 30, 2002 相似文献