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REACTION OF TRYPTOPHAN WITH TRIFLUOROACETIC ANHYDRIDE

Trifluoroacetic anhydride (TFAA) in ether quickly (=5-10 min) converted tryptophan to the crystalline 2-trifluoromethyl-5(4H)-oxazolone (2) without racemization.Dissolution of optically active 2 in acetonitrile gave racemic 2, whereas treatment with hot aqueous dioxane gave the isomeric oxazolone (3).Both 2 and 3, could on heating be further isomerized to the conjugated oxazolone (4).These oxazolones are interesting starting materials for the preparation of tryptophan containing peptides.

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Metal catalyst and ligand design,
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A concise synthesis of (+)-geissoschizine (1), a biosynthetic precursor of a variety of monoterpenoid indole alkaloids, from D-tryptophan (19) was performed as a critical prelude to achieving the first biomimetic, enantioselective synthesis of the sarpagine alkaloid (+)-Namethylvellosimine (5). The approach to (+)-geissoschizine was designed to address the dual problems of stereocontrolled formation of the E-ethylidene moiety and the correct relative configuration at C(3) and C(15). Key steps in the synthesis involve a vinylogous Mannich reaction to prepare the carboline 22, which has the absolute stereochemistry at C(3) corresponding to that in 1 and 5, and an intramolecular Michael addition that leads to the tetracyclic corynantheane derivative 24, which possesses the correct stereochemical relationship between C(3) and C(15). Compound 24 was then transformed into 27, the pivotal intermediate in the syntheses of 1 and 5, by a sequence that allowed the stereospecific introduction of the E-ethylidene moiety. Selective reduction of the lactam in 27 followed by removal of the C(5) carboxyl group by radical decarbonylation gave deformylgeissoschizine (2) that was converted into (+)-geissoschizine (1) by formylation. The common intermediate 27 was then converted via a straightforward sequence of reactions into the alpha-amino nitrile 39. The derived silyl enol ether 40 underwent ionization upon exposure to BF3·OEt2 to give the intermediate iminium ion 41 that then cyclized in a biomimetically inspired intramolecular Mannich reaction to deliver (+)-Na-methylvellosimine (5). This transformation provides experimental support for the involvement of such a cyclization as one of the key steps in the biosynthesis of the sarpagine and ajmaline alkaloids.

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Metal catalyst and ligand design,
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Attosecond pump-probe experiments performed in small molecules have allowed tracking charge dynamics in the natural time scale of electron motion. That this is also possible in biologically relevant molecules is still a matter of debate, because the large number of available nuclear degrees of freedom might destroy the coherent charge dynamics induced by the attosecond pulse. Here we investigate extreme ultraviolet-induced charge dynamics in the amino acid tryptophan. We find that, although nuclear motion and nonadiabatic effects introduce some decoherence in the moving electron wave packet, these do not significantly modify the coherence induced by the attosecond pulse during the early stages of the dynamics, at least for molecules in their equilibrium geometry. Our conclusions are based on elaborate theoretical calculations and the experimental observation of sub-4 fs dynamics, which can only be reasonably assigned to electronic motion. Hence, attosecond pump-probe spectroscopy appears as a promising approach to induce and image charge dynamics in complex molecules.

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Metal catalyst and ligand design,
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Feeding a diet with a decreased protein content reduces both nitrogen content in the gastrointestinal tract and post-weaning diarrhoea, but does not affect apparent nitrogen digestibility in weaner pigs challenged with an enterotoxigenic strain of Escherichia coli

This study evaluated possible nutritional and physiological mechanisms to explain why feeding a diet of decreased protein content reduces PWD. A total of 48 male pigs weaned at 21 d (initial BW 6.9±0.11kg; mean±SEM) was used in a 2×2×2 factorial arrangement of treatments with the respective factors being: (1) PL (HP 239g/kg vs. LP 190g/kg CP); (2) presence or absence of an ETEC challenge; and (3) duration of feeding after weaning until euthanasia (D; 7 d vs. 14 d). No dietary antimicrobial compounds were used, and diet LP contained crystalline AA including isoleucine and valine to achieve an ideal AA pattern. Pigs were offered the experimental diets on an ad libitum basis. Feeding a LP diet decreased total N intake, ileal N flow, PUN and NH3-N contents at the ileum and all sites in the large intestine (P<0.05-0.001), but did not alter (P>0.05) the AID of N and AA at either d 7 or d 14, except for serine which was lower in pigs fed the LP diet (P<0.001). Feeding diet HP increased the incidence of PWD, and ETEC infection increased PWD only in pigs fed the HP diet (PL×ETEC interaction, P<0.05). Pigs fed diet HP had more PWD at d 7 but not at d 14 after weaning (PL×D interaction, P<0.05). Experimental ETEC infection increased (P<0.001) faecal Escherichia coli score compared to non-infected pigs, and decreased AID of some AA at d 7 (ETEC×D interaction, P<0.05-0.001). Feeding diet LP reduced the molar proportion of BCFA in the caecum and proximal colon (P<0.001 and P<0.05, respectively), but total VFA concentrations in this organ were unaffected by PL (P>0.05). Pigs fed diet LP had decreased pH in the jejunum and ileum (P<0.05 and P<0.01, respectively), while ETEC infection increased pH in the caecum and proximal colon at d 7 (ETEC×D interaction, P<0.05). Feeding diet LP did not alter GIT weight, but ETEC infection adversely affected the proportional weight of the GIT at d 7 (ETEC×D interaction, P<0.01). The PL did not alter small intestinal morphology and growth. These results suggest that feeding a LP diet immediately after weaning reduces the flow of N into the large intestine, thereby decreasing protein fermentation without altering apparent AA digestibility at the ileum. We’ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 153-94-6, and how the biochemistry of the body works.Synthetic Route of 153-94-6

Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Chiral molecular recognition in a tripeptide benzylviologen cyclophane host

A cationic chiral cyclophane was synthesized and studied as a host for chiral and racemic pi-donor molecules. The cyclophane host has a rigid binding cavity flanked by (S)-(valine-leucine-alanine) and N,N’-dibenzyl- 4,4′-bipyridinium subunits, which allow for hydrogen-bonding and pi-stacking interactions with included aromatic guest molecules. 1H NMR binding titrations were performed with several different pharmaceutically interesting guest molecules including beta-blockers, NSAIDs, and amino acids and amino acid derivatives. The host-guest complexation constants were generally small for neutral and cationic guests (0-39 M-1 at 20 C in water/acetone mixtures. However, a (R)/(S) enantioselectivity ratio of 13 ± 5 was found for DOPA, a strongly pi-donating cationic guest. Two-dimensional NOESY 1H NMR spectra confirm that (R)-DOPA binds inside the cavity of the host and that there is no measurable interaction of the cavity with (S)-DOPA under the same conditions.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Growth and aluminum tolerance of maize roots mediated by auxin- and cytokinin-producing Bacillus toyonensis requires polar auxin transport

Plant Growth Promotion Rhizobacteria (PGPR) control plant development by modulation of their phytohormone activities. To probe how PGPR trigger plant growth and mitigate stress induced by aluminum (Al), the beneficial effect of Bacillus toyonensis strain Bt04 (Bt04), isolated from the Algerian Sahara rhizosphere, on maize roots was assessed. Our results revealed that the strain Bt04 is producing indole-3-acetic acid (IAA) both endogenously and from tryptophan (Trp). Surprisingly, the production of another endogenous auxin, a non-indole phenylacetic acid (PAA), was found at higher concentrations than IAA. Additionally, the production of cytokinins (CKs) by Bt04 has been demonstrated. Inoculation with Bt04 resulted in a promotion of maize growth and an enhancement of root development under aluminium (Al) toxicity condition. Importantly, Bt04 reduced Al accumulation in the young maize roots. Moreover, we could demonstrate that Bt04 itself exhibits tolerance to high concentrations of AlCl3. Bt04 might exert its growth promoting effect partially by increasing protection against oxidative stress since bacterial treatment reduced lipid peroxidation in maize seedlings under Al toxicity. To investigate a possible mechanism of this growth induction of maize seedlings we treated them under control and stress conditions with auxin transport inhibitors and demonstrated that the auxin transport pathway is needed for the Al induced stress response after inoculation with the PGPR.

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Reference:
Metal catalyst and ligand design,
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Release of small bioactive molecules from physical gels

Pharmaceutical drugs with low water solubility have always received great attention within the scientific community. The reduced bioavailability and the need of frequent administrations have motivated the investigation of new drug delivery systems. Within this context, drug carriers that release their payload in a sustained way and hence reduce the administration rate are highly demanded. One interesting strategy to meet these requirements is the entrapment of the drugs into gels. So far, the most investigated materials for such drug-loaded gels are derived from polymers and based on covalent linkages. However, over the last decade the use of physical (or supramolecular) gels derived from low molecular weight compounds has experienced strong growth in this field, mainly due to important properties such as injectability, stimuli responsiveness and ease of synthesis. This review summarizes the use of supramolecular gels for the encapsulation and controlled release of small therapeutic molecules.

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Metal catalyst and ligand design,
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Total synthesis of chondramide C and its binding mode to F-actin

(Chemical Equation Presented) Actin glue: An E-selective ring-closing metathesis as the key step allowed the solid-phase-based total synthesis of the F-actin stabilizer chondramide C as well as the establishment of its hitherto unknown stereochemistry. A strong influence of the polyketide configuration was revealed in cellular assays. Docking studies on the F-actin filament structure led to a detailed model of the binding site.

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Metal catalyst and ligand design,
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ACYLATED ACTIVE AGENTS AND METHODS OF THEIR USE FOR THE TREATMENT OF AUTOIMMUNE DISORDERS

Disclosed herein are acylated active agents (e.g., acylated catechin polyphenols, acylated carotenoids, acylated mesalamines, acylated sugars, acylated shikimic acids, acylated ellagic acid, acylated ellagic acid analogue, and acylated hydroxybenzoic acids), active agent combinations (e.g., with a second agent that is a fatty acid) and methods of their use, e.g., for modulating an autoimmunity marker or for treating an autoimmune disorder.

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Metal catalyst and ligand design,
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Multicomponent cascade reactions of unprotected carbohydrates and amino acids

Herein an operationally simple multicomponent reaction of unprotected carbohydrates with amino acids and isonitriles is presented. By the extension of this Ugi-type reaction to an unprotected disaccharide a novel glycopeptide structure was accessible.

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI