Sucrose preculture to simplify cryopreservation of banana meristem cultures

A simple cryopreservation method is described for proliferating meristem cultures of banana (Musa spp.). It relies on a 2-week preculture on media containing 0.4 M sucrose followed by rapid cooling in liquid nitrogen. Different preculture media were screened for efficient protection of banana meristems against cryopreservation. Sucrose can be replaced by both fructose and glucose without significantly affecting post-thaw survival rates. A high BA concentration (0.1 mM) in the preculture medium results in less material available for cryopreservation, but does not affect cryoprotection. Culture in liquid media significantly improved post-thaw regeneration. The optimized cryopreservation protocol was applied on 36 banana accessions belonging to 8 different genomic groups. It is shown that post-thaw regeneration frequencies (ranging between 0 and 66 percent) are highly dependent on the genomic constitution of the banana cultivar.     

Identification of ethyl pyruvate and dihydrocinchonidine adducts by electrospray ionization mass spectrometry

Several ethyl pyruvate and dihydrocinchonidine adducts, formed by non-covalent interactions with alkali cations, have been identified for the first time using electrospray ionization mass and tandem mass spectrometry. This type of adduct may have an important role in asymmetric reactions of pyruvates in the presence of cinchonas.     

Ultrasonics in heterogeneous metal catalysis: sonochemical chemo- and enantioselective hydrogenations over supported platinum catalysts

Sonochemical chemo- and enantioselective hydrogenations over supported platinum catalysts are described. We disclose our results with respect to a sonochemical modification of the chemoselective hydrogenation of cinnamaldehyde over supported platinum catalysts, and the asymmetric hydrogenation of ethyl pyruvate promoted by various ultrasonic pretreatments. The ultrasonic pretreatment of the supported platinum catalysts was found to be highly beneficial in almost every case, improving both the catalytic activity and selectivity. The effect of additional experimental variables, such as hydrogen pressure, catalyst support, temperature and the ultrasonic insonation time were also studied. The enantioselectivity of the hydrogenation of ethyl pyruvate increased up to 97.1% ee. In the case of cinnamaldehyde hydrogenation, the selective preparation of cinnamyl alcohol became possible. The theoretical aspects of the working mechanisms in comparison with 'silent' reactions will also be provided.     

Investigation of chiral reactions: the structural detection of new hydrogenated isocinchona alkaloids from mixtures without isolation using electrospray ionization tandem mass spectrometry

The reaction mixture for the hydrogenation of ethyl pyruvate on Pt-alumina catalyst modified with isocinchona alkaloids (alpha-ICN (I) and beta-ICN (II)) was studied by electrospray ionization tandem mass spectrometry (ESI-MS/MS). It was established that part of the chiral modifiers themselves are converted into ions of m/z 299, 305 and 309 in the course of chiral hydrogenation. The experimental data allowed the determination of the probable structure of the ions mentioned. According to ESI-MS/MS spectra the structure of the new cinchona alkaloids was assumed: tetrahydro-isocinchonines (III-VI), decahydro-isocinchonines (VII, VIII) and hydrogenated compounds of VII and VIII by scission of their C--N and C--O bonds (IX/1, IX/2, X). Fragmentation pathways are proposed for these new compounds.     

Dynamic Global Constraints in Backtracking Based Environments

Global constraints provide strong filtering algorithms to reduce the search space when solving large combinatorial problems. In this paper we propose to make the global constraints dynamic, i.e., to allow extending the set of constrained variables during search. We describe a generic dynamisation technique for an arbitrary monotonic global constraint and we compare it with the semantic-based dynamisation for the alldifferent constraint. At the end we sketch a dynamisation technique for non-monotonic global constraints. A comparison with existing methods to model dynamic problems is given as well.     

Synthesis of the dibenzo[f,h]phthalazine and dibenzo[f,h]cinnoline skeleton via a ‘Suzuki-Pd-catalyzed intramolecular arylation’ and a ‘Suzuki-Pschorr’ approach

Palladium-catalyzed intramolecular arylation of 2-benzyl-5-(2-bromophenyl)-4-phenylpyridazin-3(2H)-one yielded hitherto unknown 2-benzyldibenzo[f,h]phthalazin-1(2H)-one. The synthesis of this new tetracyclic pyridazinone from 2-benzyl-5-(2-aminophenyl)-4-phenylpyridazin-3(2H)-one via a Pschorr type reaction was also investigated. Similarly, the construction of 2-methyldibenzo[f,h]cinnolin-3(2H)-one from 2-methyl-5-(2-bromophenyl)-6-phenylpyridazin-3(2H)-one and 2-methyl-5-(2-aminophenyl)-6-phenylpyridazin-3(2H)-one is also reported. Removal of the N-benzyl protective group of 2-benzyl-dibenzo[f,h]phthalazin-1(2H)-one with AlCl₃ yielded unsubstituted dibenzo[f,h]phthalazin-1(2H)-one.     

Non-neural BOLD variability in block and event-related paradigms

Block and event-related stimulus designs are typically used in fMRI studies depending on the importance of detection power or estimation efficiency. The extent of vascular contribution to variability in block and event-related fMRI-BOLD response is not known. With scaling, the extent of vascular variability in the fMRI-BOLD response during block and event-related design tasks was investigated. Blood oxygen level-dependent (BOLD) contrast data from healthy volunteers performing a block design motor task and an event-related memory task requiring performance of a motor response were analyzed from the regions of interest (ROIs) surrounding the primary and supplementary motor cortices. Average BOLD signal change was significantly larger during the block design compared to the event-related design. In each subject, BOLD signal change across voxels in the ROIs had higher variation during the block design task compared to the event-related design task. Scaling using the resting state fluctuation of amplitude (RSFA) and breath-hold (BH), which minimizes BOLD variation due to vascular origins, reduced the within-subject BOLD variability in every subject during both tasks but significantly reduced BOLD variability across subjects only during the block design task. The strong non-neural source of intra- and intersubject variability of BOLD response during the block design compared to event-related task indicates that study designs optimizing for statistical power through enhancement of the BOLD contrast (for, e.g., block design) can be affected by enhancement of non-neural sources of BOLD variability.     

180 degree unidirectional bond rotation in a biaryl lactone artificial molecular motor prototype

A bifunctional biaryl lactone has been synthesized that should be capable of iterative unidirectional aryl-aryl bond rotation via: (1) a diastereoselective lactone ring opening, (S)-1 to (P,S)-2 or (M,S)-2; (2) a chemoselective lactonization, (P,S)-2 or (M,S)-2 to (S)-3; and (3) a chemoselective hydrolysis, (S)-3 to (S)-1. Preliminary results of a racemic sample have indicated unidirectional 180 degrees rotation with very high directional selectivity per individual artificial molecular motor molecule through the first two steps of this sequence. [reaction: see text]     

Synthetically accessible, high-affinity phosphate anion receptors

We report synthetically accessible receptors with protonated amines attached to a conformationally constrained backbone including amide units, and demonstrate that these receptors have high affinities (log K > 5) for phosphate anions in aqueous media at pH 7 in the presence of high concentrations of competitive chloride anions (ca. 100-fold excess).