An expedient synthesis of (+)-quinolactacin A2

An expedient synthesis of quinolactacin A2 from N-methylisatoic anhydride and N-Boc-(2S,3S)-isoleucine has been achieved. The key step involves the Friedländer-type annulation of isatoic anhydride and β-ketoester derived from isoleucine.     

Reduction of Chemical Reactions in Nitrogen and Nitrogen–Hydrogen Plasma Jets Flowing into Atmospheric Air

The large number of possible chemical reactions represents a severe burdenfor modeling of even relatively simple plasma systems. Reduced sets ofchemical reactions have been obtained for numerical simulations of nitrogenand nitrogen-hydrogen plasma jets flowing into an atmospheric airenvironment. The important or active reactions are determined based on asimplified reduction method. A reaction is considered active if it leadsto higher sensitivities than a specified cutoff sensitivity of 1%. Theactive reactions exert a significant influence on main plasma parameters,such as velocity, temperature, and species concentrations. The sensitivityanalysis for the specified systems shows that two NO reactions, known asZel'dovich reactions (N₂+ONO+N andNO+OO₂+N),⁽¹⁾ are both active in a nitrogenplasma jet. On the other hand, the latter is not active and may be omittedin a nitrogen–hydrogen plasma jet. A nitrogen–hydrogen plasmajet requires contribution of two active charge exchange reactions:N₂+N⁺N⁺ ₂+N andN+H+N+ +H, while only the former is needed in a nitrogen plasmajet. The dissociation reactions are all active in both plasma jets, exceptthe dissociation of OH.     

Anatase-Rutile Transition of Precipitated Titanium Oxide with Alcohol Rinsing

The effect of alcohol washing on the anatase-rutile transition of precipitated titanium oxide was investigated using X-ray powder diffraction, Fourier-transform IR spectroscopy, and thermogravimetry. Alcohol (butanol) rinsing accelerated the anatase-rutile transition of precipitated titanium oxide powder so that the onset temperature of transition decreased drastically from 800 degrees C for water-washed powder to 550 degrees C for alcohol-rinsed powder. Alternation of transition kinetics and mechanisms by rinsing media could be confirmed from the analysis of temperature and time dependence of rutile content. The attributability of the chemical state of anatase after crystallization, which contained H(2)O, OH, and organic residues, to the change of transition kinetics with alcohol rinsing will be discussed. Two mechanisms, the effect of residual organics and/or H(2)O(OH), could be suggested on the basis of analysis of the difference between chemical states of water-washed anatase and alcohol-rinsed powder. Copyright 2000 Academic Press.     

X-ray magnetic circular dichroism of Pseudomonas aeruginosa nickel(II) azurin

We show that X-ray magnetic circular dichroism (XMCD) can be employed to probe the oxidation states and other electronic structural features of nickel active sites in proteins. As a calibration standard, we have measured XMCD and X-ray absorption (XAS) spectra for the nickel(II) derivative of Pseudomonas aeruginosa azurin (NiAz). Our analysis of these spectra confirms that the electronic ground state of NiAz is high-spin (S = 1); we also find that the L(3)-centroid energy is 853.1(1) eV, the branching ratio is 0.722(4), and the magnetic moment is 1.9(4) mu(B). Density functional theory (DFT) calculations on model NiAz structures establish that orbitals 3d(x2-y2) and 3d(z2) are the two valence holes in the high-spin Ni(II) ground state, and in accord with the experimentally determined orbital magnetic moment, the DFT results also demonstrate that both holes are highly delocalized, with 3d(x2-y2) having much greater ligand character.     

Experimental and theoretical study on the olefin metathesis of alkenyl Baylis-Hillman adducts using second-generation Grubbs catalyst

[reaction: see text] We have investigated the olefin metathesis from alkenyl Baylis-Hillman adducts using second-generation Grubbs catalyst. In the experiment, the ring-closing metathesis (RCM) product could not be found, while the cross-metathesis (CM) products were found. The computational studies provided consistent explanations for the experimental result. The most limiting factor for the RCM process using second-generation Grubbs catalyst is caused by the high strain and steric effect in the metallacyclobutane intermediates.     

Toward the molecular flashlight: preparation,properties, and photophysics of a hypericin-luciferin tethered molecule

The synthesis of a molecule containing hypericin and luciferin moieties joined by a tether is reported. The light-induced (in vitro) antiviral activity as well as the photophysical properties of this new compound are measured and compared with those of the parent compounds, hypericin and pseudohypericin. This tethered molecule exhibits excited-state behavior that is very similar to that of its parent compounds and antiviral activity that is identical, within experimental error, to that of its more closely related parent compound, pseudohypericin. The implications for a photodynamic therapy that is independent of external light sources are discussed.     

Decreased in vitro interaction between p53 and nuclear stress proteins in the p53-deficient mouse

In a previous study, the strength of the interaction between the nuclear stress proteins (sps) 25a, 70i, 72c, and 90 and the tumor suppressor protein p53 was determined by an in vitro fluorescence binding assay. The relative binding of the individual sps with p53, derived from the bone marrow of transgenic mice heterozygous at the p53 locus (p53+/-), was reduced compared to the interaction of sps and p53 derived from wild-type (p53+/+) mice. In order to determine if the genotype of the p53 donor or the genotype of the sp donor determined the binding efficiency, p53 expression was induced by retinoic acid and sp synthesis by bleomycin. P53 derived from either wild-type or heterozygous animals was cross-reacted with nuclear sps obtained from either wild-type or heterozygous animals. Each of the sps, 25a, 70i, 72c, and 90, bound to wild-type p53 with a similar efficiency, irrespective of the genotype of the sp donor mouse (p53+/+ or p53+/-). In contrast, when the sp interaction with p53 obtained from the heterozygous mouse was measured, the relative value of the fluorescence complex was significantly reduced. The data suggest that the strength of the interaction between p53 and nuclear sps is related to the genotype of the p53 donor, and not to the genotype of the animals from which the sps are derived.     

Cancer cells undergoing epigenetic transition show short-term resistance and are transformed into cells with medium-term resistance by drug treatment

To elucidate the epigenetic mechanisms of drug resistance, epigenetically reprogrammed H460 cancer cells (R-H460) were established by the transient introduction of reprogramming factors. Then, the R-H460 cells were induced to differentiate by the withdrawal of stem cell media for various durations, which resulted in differentiated R-H460 cells (dR-H460). Notably, dR-H460 cells differentiated for 13 days (13dR-H460 cells) formed a significantly greater number of colonies showing drug resistance to both cisplatin and paclitaxel, whereas the dR-H460 cells differentiated for 40 days (40dR-H460 cells) lost drug resistance; this suggests that 13dR-cancer cells present short-term resistance (less than a month). Similarly, increased drug resistance to both cisplatin and paclitaxel was observed in another R-cancer cell model prepared from N87 cells. The resistant phenotype of the cisplatin-resistant (CR) colonies obtained through cisplatin treatment was maintained for 2–3 months after drug treatment, suggesting that drug treatment transforms cells with short-term resistance into cells with medium-term resistance. In single-cell analyses, heterogeneity was not found to increase in 13dR-H460 cells, suggesting that cancer cells with short-term resistance, rather than heterogeneous cells, may confer epigenetically driven drug resistance in our reprogrammed cancer model. The epigenetically driven short-term and medium-term drug resistance mechanisms could provide new cancer-fighting strategies involving the control of cancer cells during epigenetic transition.Subject terms: Tumour heterogeneity, Epigenetics     

Performance of hollow-fiber flow field-flow fractionation in protein separation

Since hollow-fiber flow field-flow fractionation (HF FIFFF) utilizes a cylindrical channel made of a hollow-fiber membrane, which is inexpensive and simple in channel assembly and thus disposable, interests are increasing as a potential separation device in cells, proteins, and macromolecules. In this study, performance of HF FIFFF of proteins is described by examining the influence of flow rate conditions and length of fiber (polyacrylonitrile or PAN in this work) on sample recovery as well as experimental plate heights. The interfiber reproducibility in terms of separation time and recovery was also studied. Experiments showed that sample recovery was consistent regardless of the length of fiber when the effective field strength (equivalent to the mean flow velocity at the fiber wall) and the channel void time were adjusted to be equivalent for channels of various fiber lengths. This supported that the majority of sample loss in HF FIFFF separation of apoferritin and their aggregates may occur before the migration process. It is finally demonstrated that HF FIFFF can be applied for characterizing the reduction in Stokes' size of low density lipoproteins from blood plasma samples obtained from patients having coronary artery disease and from healthy donors.     

Photocatalytic synthesis of copper colloids from CuII by the ferrihydrite core of ferritin

The iron-storage protein ferritin encapsulates a nanoparticle of iron oxide. The size and properties of these nanoparticles can be adjusted by controlled oxidative hydrolysis reactions of Fe(II). This mineralized ferritin protein cage has previously been shown to act as an effective photocatalyst for reduction of Cr(VI). In the present work, we demonstrate that Fe(O)OH-mineralized ferritin catalyzes the photoreduction of Cu(II) to form a stable, air-sensitive, colloidal dispersion of Cu(0). In addition, the particle sizes of the Cu colloids can be controlled by varying the ratio of Cu(II) to ferritin. This illustrates an important principle, namely that the properties of one preformed material can be utilized for the specific synthesis of a second material, thus tailoring the desired physical properties of the final products. This procedure represents a multistep materials synthesis: the formation of a new nanomaterial from a catalytic precursor.