Identification of a set of genes showing regionally enriched expression in the mouse brain

Background

We have recorded responses from single neurons in murine visual cortex to determine the effectiveness of the input from the two murine cone photoreceptor mechanisms and whether there is any unique selectivity for cone inputs at this higher region of the visual system that would support the possibility of colour vision in mice. Each eye was stimulated by diffuse light, either 370 (strong stimulus for the ultra-violet (UV) cone opsin) or 505 nm (exclusively stimulating the middle wavelength sensitive (M) cone opsin), obtained from light emitting diodes (LEDs) in the presence of a strong adapting light that suppressed the responses of rods.

Results

Single cells responded to these diffuse stimuli in all areas of striate cortex. Two types of responsive cells were encountered. One type (135/323 – 42%) had little to no spontaneous activity and responded at either the on and/or the off phase of the light stimulus with a few impulses often of relatively large amplitude. A second type (166/323 – 51%) had spontaneous activity and responded tonically to light stimuli with impulses often of small amplitude. Most of the cells responded similarly to both spectral stimuli. A few (18/323 – 6%) responded strongly or exclusively to one or the other spectral stimulus and rarely in a spectrally opponent manner.

Conclusion

Most cells in murine striate cortex receive excitatory inputs from both UV- and M-cones. A small fraction shows either strong selectivity for one or the other cone mechanism and occasionally cone opponent responses. Cells that could underlie chromatic contrast detection are present but extremely rare in murine striate cortex.     

Spectral coarse graining and synchronization in oscillator networks

Coarse graining techniques offer a promising alternative to large-scale simulations of complex dynamical systems, as long as the coarse-grained system is truly representative of the initial one. Here, we investigate how the dynamical properties of oscillator networks are affected when some nodes are merged together to form a coarse-grained network. Moreover, we show that there exists a way of grouping nodes preserving as much as possible some crucial aspects of the network dynamics. This coarse graining approach provides a useful method to simplify complex oscillator networks, and more generally, networks whose dynamics involves a Laplacian matrix.     

Triterpenes and limonoids of Cedrela: Distribution,biosynthesis, and 1H and 13C NMR data

Cedrela genus, a member of the Meliaceae family, presents both chemical characteristics associated with and those that distinguish it from the rest of its members. The presence of triterpenes and limonoids is the characteristic of the Meliaceae family, but the class and type of these chemical constituents are distinctive for each genus. Cedrela includes cycloartane, ursane, oleanane, tirucallane, butyrospermane, and apotirucallane triterpenes, and its limonoids belongs to six class and nine types, known as class Ia-type havanensines, class Ib-type delevoyin, class II-type gedunin, class IIIb-type andirobin, class IIIg-type mexicanolide, class IVa-type evoludone, class Va-type obacunol, class V-type limonin, and class VIII. Each of these structural arrangements includes specific traits, defined by their biosynthetic origin, which can be established by means of structural elucidation techniques, particularly ¹H and ¹³C NMR, which assisted by 2D NMR techniques, allowing to deduce their structures unequivocally. The constant presence of these skeletal arrangements in Cedrela ensures that they are its chemophenetic markers and their recurrence is an important criterion for their identity. This review is a compilation of the occurrence of triterpenes and limonoids in Cedrela genus, detailing their biosynthetic association and collecting and organizing their NMR data, with the purpose of facilitating its location, analysis, and use in the phytochemical study of species from this genus.     

A Comparative Study of the Semiconductor Behavior of Organic Thin Films: TCNQ-Doped Cobalt Phthalocyanine and Cobalt Octaethylporphyrin

The structure formed by cobalt phthalocyanine (CoPc) and cobalt octaethylporphyrin (CoOEP) with electron-acceptor tetracyano-π-quinodimethane (TCNQ), was studied by Density Functional Theory (DFT) methods. According to theoretical calculations, both cobalt systems can establish dispersion forces related to TCNQ and also in both cases the link between them is built by means of hydrogen bonds. Based on the results of these DFT calculations, we developed experimental work: the organic semiconductors were doped, and the thermal evaporation technique was used to prepare semiconductor thin films of such compounds. The structure of the films was studied by FTIR and Raman spectroscopy. The optical properties of the CoPc-TCNQ and CoOEP-TCNQ films were investigated by means of UV-Vis measurements. The results obtained were used to estimate the type of transitions and the optical bandgap. The results were compared to the previously calculated theoretical bandgap. The CoOEP-TCNQ film presented the smallest theoretical and experimental bandgap. Finally, the electrical properties of the organic semiconductors were evaluated from a PET (polyethylene terephthalate)/indium tin oxide (ITO)/cobalt macrocycle-TCNQ/silver (Ag) device we prepared. The CoOEP-TCNQ-based device showed an ohmic behavior. The device manufactured from CoPc-TCNQ also showed an ohmic behavior at low voltages, but significantly changed to SCLC (space-charge limited conductivity) at high voltage values.     

Colorless, non-luminescent; colorless, luminescent; and yellow, luminescent crystals of the cation [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](+). The roles of anions and hydrogen bonding in determining the aggregation of two-coordinate gold(I) cations

Crystallographic and luminescence studies on salts of the two-coordinate carbene cation, [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](+), demonstrate the ability of the cation to exist in three different states of aggregation. In colorless, non-luminescent [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)]Cl the cation crystallizes as a monomer with the nearest gold(i) center 6.7890(11) A away. Colorless, luminescent [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)]AsF(6) forms dimers with an AuAu separation of 3.1288(4) A. These dimers form weakly associated extended chains of cations with additional AuAu separations of 3.6625(5) A. [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)]PF(6) is isostructural. Yellow, luminescent [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](3)(AsF(6))(2)Cl.0.5(H(2)O)(2) and [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](3)(PF(6))(2)Cl.0.5(H(2)O)(2) form trimers that further aggregate into extended chains with rather short AuAu separations of 3.1301(14) A, 3.1569(14) A and 3.1415(14) A. Absorption, emission and excitation spectra are reported for these salts. The excitation and emission results from the interactions between the gold centers and involves transitions between the filled d(z)((2)) band and the empty p(z) bands with the z axis pointing along the chain of cations.     

Synthesis of a fluorescent xanthenic derivative useful for labeling amine residues

The 2,5-dioxopyrrolidin-1-yl-4-(3-hydroxy-6-oxo-6H-xanthen-9-yl)-3-methylbenzoate has been synthesized as an amine-reactive derivative able to yield stable covalently labeled biopolymers. The new derivative has been used to label polyribocytidilic acid (5'), poly(C), amine residues. TG-II-poly(C) exhibits monoexponential decay at the physiological pH range. In addition, both steady-state fluorescence intensity and fluorescence decay are also sensitive to solution pH. The large decrease in steady-state fluorescence upon hybridization allows it to be used as a nucleic acid probe in a homogeneous assay format. In summary, we report an efficient synthesis to obtain labeled RNA from commercially available materials in excellent yields.     

Supercritical fluid extraction as an on-line clean-up technique for rapid amperometric screening and alternative liquid chromatography for confirmation of paraquat and diquat in olive oil samples

A rapid and simple method for the direct screening of paraquat (PQ) and diquat (DQ) in olive oil samples is proposed. The sample screening method involves supercritical fluid extraction (SFE) (clean-up followed by the extraction of the analytes) followed by continuous flow electrochemical detection. Those samples for which the total concentration is close to or above the threshold limit established by the Columbian Society for Social Protection (0.05mugg(-1)) are subsequently analyzed by liquid chromatography (LC) with diode array detection (DAD). This confirmation method allows the determination of PQ and DQ in the range between 0.04 and 1.0mugg(-1), with average relative standard deviations lower than 3.5%, and 0.003 and 0.002mugg(-1) detection limits for PQ and DQ, respectively. The proposed arrangement opens up interesting prospects for the direct determination of polar pesticides in complex samples with a good throughput and a high level of automation.     

Elaboration,characterization and study of a new hybrid chitosan/ceramic membrane for affinity membrane chromatography

A new kind of metal affinity membrane based on a ceramic support was prepared. It was elaborated in four steps: (i) deposition of a chitosan layer in order to functionalize the ceramic support, (ii) cross-linking with epichlorohydrin to stabilise the polymer layer and to enable the grafting, (iii) iminodiacetic acid grafting, (iv) Cu²⁺ adsorption. Due to the ceramic support, this membrane is highly resistant and the chitosan layer brings its biocompatibility properties. Each step of the membrane elaboration was studied and the membrane structure was characterized. Both thin coating of the polymer on the alumina grains of the support and the chemical modification of the membrane were proved. Then, bovine serum albumin (BSA) was used as a model protein to test protein retention of the affinity membrane. The protein/membrane interactions were investigated showing that some non-specific ones are involved. Finally, the effect of buffer concentration was checked and it appears that, in the studied range, an increase of the buffer concentration entailed a limitation of the non-specific interactions inducing a better BSA recovering and a higher selectivity.     

One-pot organocatalytic domino Michael/alpha-alkylation reactions: direct catalytic enantioselective cyclopropanation and cyclopentanation reactions

The development of one-pot organocatalytic domino Michael/alpha-alkylation reactions between bromomalonates or bromoacetoacetate esters and alpha,beta-unsaturated aldehydes is presented. The chiral-amine-catalyzed reactions with bromomalonates as substrates give access to the corresponding 2-formylcyclopropane derivatives in high yields with excellent diastereoselectivity and up to 99 % ee. The catalytic domino Michael/alpha-alkylation reactions between 4-bromo-acetoacetate and enals provide a route for the synthesis of functionalized cyclopentanones in good to high yields with 93-99 % ee. The products from the organocatalytic reactions were also reduced with high diastereoselectivity to the corresponding cyclopropanols and cyclopentanols, respectively. Moreover, one-pot combinations of amine and heterocyclic carbene catalysis (AHCC) enabled the highly enantioselective synthesis of beta-malonate esters (91-97 % ee) from the reaction between bromomalonates and enals. The tandem catalysis included the catalytic domino reaction followed by catalytic in situ chemoselective ring-opening of the 2-formylcyclopropane intermediates.     

Glycine enolates: the effect of formation of iminium ions to simple ketones on alpha-amino carbon acidity and a comparison with pyridoxal iminium ions

Equilibrium constants in D2O were determined by 1H NMR analyses for formation of imines/iminium ions from addition of glycine methyl ester to acetone and from addition of glycine to phenylglyoxylate. First-order rate constants, also determined by 1H NMR, are reported for deuterium exchange between solvent D2O and the alpha-amino carbon of glycine methyl ester and glycine in the presence of increasing concentrations of ketone and Br?nsted bases. These rate and equilibrium data were used to calculate second-order rate constants for deprotonation by DO- and by Br?nsted bases of the alpha-imino carbon of the ketone adducts. Formation of the iminium ion between acetone and glycine methyl ester and between phenylglyoxylate and glycine is estimated to cause 7 unit and 15 unit decreases, respectively, in the pKa's of 21 and 29 for deprotonation of the parent carbon acids. The effect of formation of iminium ions to phenylglyoxylate and to 5'-deoxypyridoxal (DPL) [Toth, K.; Richard, J. P. J. Am. Chem. Soc. 2007, 129, 3013-3021] on the carbon acidity of glycine is similar. However, DPL is a much better catalyst than phenylglyoxylate of deprotonation of glycine, because of the exceptionally large thermodynamic driving force for conversion of the amino acid and DPL to the reactive iminium ion.