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Organic Letters Feb 2020Amines such as 1,2,3,4-tetrahydroisoquinoline undergo redox-neutral annulations with -cyanomethylbenzaldehydes. These amine α-C-H bond functionalization reactions are...
Amines such as 1,2,3,4-tetrahydroisoquinoline undergo redox-neutral annulations with -cyanomethylbenzaldehydes. These amine α-C-H bond functionalization reactions are promoted by acetic acid. The resulting β-aminonitriles can be converted to the corresponding β-aminoalcohols in diastereoselective fashion.
Topics: Acetic Acid; Amino Alcohols; Benzaldehydes; Molecular Structure; Oxidation-Reduction; Stereoisomerism; Tetrahydroisoquinolines
PubMed: 31984752
DOI: 10.1021/acs.orglett.9b04506 -
Organic Letters May 2019A chemoselective primary amine modification strategy that enables the three-component, one-pot bioconjugation is described. The specifically designed,...
A chemoselective primary amine modification strategy that enables the three-component, one-pot bioconjugation is described. The specifically designed, mercaptobenzaldehyde-based bifunctional linker achieves highly selective and robust amine labeling under biocompatible conditions. This linker demonstrates wide functional group tolerance and is simple to prepare, which allowed facile payload incorporation. Finally, our studies have shown that the introduction of linker does not impair the function of modified protein such as insulin.
Topics: Amines; Benzaldehydes; Molecular Structure; Protein Processing, Post-Translational; Sulfhydryl Compounds
PubMed: 31058515
DOI: 10.1021/acs.orglett.9b01294 -
Molecular Plant Jan 2015In recent years, biotechnology-derived production of flavors and fragrances has expanded rapidly. The world's most popular flavor, vanillin, is no exception. This review... (Review)
Review
In recent years, biotechnology-derived production of flavors and fragrances has expanded rapidly. The world's most popular flavor, vanillin, is no exception. This review outlines the current state of biotechnology-based vanillin synthesis with the use of ferulic acid, eugenol, and glucose as substrates and bacteria, fungi, and yeasts as microbial production hosts. The de novo biosynthetic pathway of vanillin in the vanilla orchid and the possible applied uses of this new knowledge in the biotechnology-derived and pod-based vanillin industries are also highlighted.
Topics: Benzaldehydes; Bioengineering; Biosynthetic Pathways; Propanols; Synthetic Biology; Vanilla
PubMed: 25578271
DOI: 10.1016/j.molp.2014.11.008 -
Food Chemistry Nov 2022Vicia sativa (Common Vetch) is currently an underutilised leguminous crop species with high protein content and superior drought tolerance. This study aimed to...
Vicia sativa (Common Vetch) is currently an underutilised leguminous crop species with high protein content and superior drought tolerance. This study aimed to understand the mechanisms behind vetch flavor development following processing to facilitate its uptake as a future source of dietary protein. A total of 95 volatile compounds were identified by solid-phase microextraction gas chromatography-mass spectrometry (SPME GC-MS) for a range of vetches processed by dehulling, soaking, germination, microwaving, and fermentation.2-pentyl furan, benzyl alcohol, benzaldehyde, 1-octen-3-ol and 1-hexanol were found to be characteristic aroma compounds of V. sativa. Analysis of a V. sativa landrace demonstrated significant intraspecies variation in volatile abundance, three-fold that of commercial varieties. Both natto and tempeh fermentation produced significant quantities of alcohols, esters, and carboxylic acids with specifically natto generating significant pyrazines. Concentrations of 1-octen-3-ol significantly decreased after tempeh fermentation indicating its potential to reduce documented off flavor generating volatiles within V. sativa.
Topics: Alcohols; Benzaldehydes; Fermentation; Gas Chromatography-Mass Spectrometry; Odorants; Solid Phase Microextraction; Vicia; Volatile Organic Compounds
PubMed: 35780668
DOI: 10.1016/j.foodchem.2022.133569 -
Molecules (Basel, Switzerland) May 2020In this report, the streptavidin-biotin technology was applied to enable organocatalytic aldol addition. By attaching pyrrolidine to the valeric motif of biotin and...
In this report, the streptavidin-biotin technology was applied to enable organocatalytic aldol addition. By attaching pyrrolidine to the valeric motif of biotin and introducing it to streptavidin (Sav), a protein-based organocatalytic system was created, and the aldol addition of acetone with -nitrobenzaldehyde was tested. The conversion of substrate to product can be as high as 93%. Although the observed enantioselectivity was only moderate (33:67 er), further protein engineering efforts can be included to improve the selectivity. These results have proven the concept that Sav can be used to host stereoselective aldol addition.
Topics: Acetone; Aldehydes; Benzaldehydes; Biotin; Chemistry Techniques, Synthetic; Humans; Models, Molecular; Protein Conformation; Pyrrolidines; Stereoisomerism; Streptavidin
PubMed: 32466220
DOI: 10.3390/molecules25102457 -
Nutrients Apr 2019Microbial communities are responsible for the unique functional properties of chocolate. During microbial growth, several antimicrobial and antioxidant metabolites are... (Review)
Review
Microbial communities are responsible for the unique functional properties of chocolate. During microbial growth, several antimicrobial and antioxidant metabolites are produced and can influence human wellbeing. In the last decades, the use of starter cultures in cocoa fermentation has been pushed to improve nutritional value, quality, and the overall product safety. However, it must be noted that unpredictable changes in cocoa flavor have been reported between the different strains from the same species used as a starter, causing a loss of desirable notes and flavors. Thus, the importance of an accurate selection of the starter cultures based on the biogenic effect to complement and optimize chocolate quality has become a major interest for the chocolate industry. This paper aimed to review the microbial communities identified from spontaneous cocoa fermentations and focused on the yeast starter strains used in cocoa beans and their sensorial and flavor profile. The potential compounds that could have health-promoting benefits like limonene, benzaldehyde, 2-phenylethanol, 2-methylbutanal, phenylacetaldehyde, and 2-phenylethyl acetate were also evaluated as their presence remained constant after roasting. Further research is needed to highlight the future perspectives of microbial volatile compounds as biomarkers to warrant food quality and safety.
Topics: Acetaldehyde; Acetates; Aldehydes; Anti-Infective Agents; Antioxidants; Benzaldehydes; Cacao; Chocolate; Cooking; Fermentation; Food Microbiology; Functional Food; Humans; Limonene; Phenylethyl Alcohol; Taste; Volatile Organic Compounds; Yeasts
PubMed: 31010207
DOI: 10.3390/nu11040884 -
The Biochemical Journal Oct 1988The apparent Km and maximum velocity values of benzyl alcohol dehydrogenase and benzaldehyde dehydrogenase II from Acinetobacter calcoaceticus were determined for a...
The apparent Km and maximum velocity values of benzyl alcohol dehydrogenase and benzaldehyde dehydrogenase II from Acinetobacter calcoaceticus were determined for a range of alcohols and aldehydes and the corresponding turnover numbers and specificity constants were calculated. Benzyl alcohol was the most effective alcohol substrate for benzyl alcohol dehydrogenase. Perillyl alcohol was the second most effective substrate, and was the only non-aromatic alcohol oxidized. The other substrates of benzyl alcohol dehydrogenase were all aromatic in nature, with para-substituted derivatives of benzyl alcohol being better substrates than other derivatives. Coniferyl alcohol and cinnamyl alcohol were also substrates. Benzaldehyde was much the most effective substrate for benzaldehyde dehydrogenase II. Benzaldehydes with a single small substituent group in the meta or para position were better substrates than any other benzaldehyde derivatives. Benzaldehyde dehydrogenase II could also oxidize the aliphatic aldehydes hexan-1-al and octan-1-al, although poorly. Benzaldehyde dehydrogenase II was substrate-inhibited by benzaldehyde when the assay concentration exceeded approx. 10 microM. Benzaldehyde dehydrogenase II, but not benzyl alcohol dehydrogenase, exhibited esterase activity with 4-nitrophenyl acetate as substrate. Both benzyl alcohol dehydrogenase and benzaldehyde dehydrogenase II were inhibited by the thiol-blocking reagents iodoacetate, iodoacetamide, 4-chloromercuribenzoate and N-ethylmaleimide. Benzyl alcohol or benzaldehyde respectively protected against these inhibitions. NAD+ also gave some protection. Neither benzyl alcohol dehydrogenase nor benzaldehyde dehydrogenase II was inhibited by the metal-ion-chelating agents EDTA, 2,2'-bipyridyl, pyrazole or 2-phenanthroline. Neither enzyme was inhibited by a range of plausible metabolic inhibitors such as mandelate, phenylglyoxylate, benzoate, succinate, acetyl-CoA, ATP or ADP. Benzaldehyde dehydrogenase II was sensitive to inhibition by several aromatic aldehydes; in particular, ortho-substituted benzaldehydes such as 2-bromo-, 2-chloro- and 2-fluoro-benzaldehydes were potent inhibitors of the enzyme.
Topics: Acinetobacter; Alcohol Oxidoreductases; Alcohols; Aldehyde Oxidoreductases; Aldehydes; Benzaldehydes; Chelating Agents; Esterases; Isoenzymes; Kinetics; Substrate Specificity; Sulfhydryl Compounds
PubMed: 3060114
DOI: No ID Found -
Journal of the American Chemical Society Nov 2022Aziridines are readily available C(sp) precursors that afford valuable β-functionalized amines upon ring opening. In this article, we report a Ni/photoredox methodology...
Aziridines are readily available C(sp) precursors that afford valuable β-functionalized amines upon ring opening. In this article, we report a Ni/photoredox methodology for C(sp)-C(sp) cross-coupling between aziridines and methyl/1°/2° aliphatic alcohols activated as benzaldehyde dialkyl acetals. Orthogonal activation modes of each alkyl coupling partner facilitate cross-selectivity in the C(sp)-C(sp) bond-forming reaction: the benzaldehyde dialkyl acetal is activated via hydrogen atom abstraction and β-scission via a bromine radical (generated in situ from single-electron oxidation of bromide), whereas the aziridine is activated at the Ni center via reduction. We demonstrate that an Ni(II) azametallacycle, conventionally proposed in aziridine cross-coupling, is not an intermediate in the productive cross-coupling. Rather, stoichiometric organometallic and linear free energy relationship studies indicate that aziridine activation proceeds via Ni(I) oxidative addition, a previously unexplored elementary step.
Topics: Acetals; Catalysis; Benzaldehydes; Nickel; Aziridines
PubMed: 36256882
DOI: 10.1021/jacs.2c09294 -
Chemical Senses Sep 2017Natural olfactory stimuli are volatile-chemical mixtures in which relative perceptual saliencies determine which odor-components are identified. Odor identification also...
Natural olfactory stimuli are volatile-chemical mixtures in which relative perceptual saliencies determine which odor-components are identified. Odor identification also depends on rapid selective adaptation, as shown for 4 odor stimuli in an earlier experimental simulation of natural conditions. Adapt-test pairs of mixtures of water-soluble, distinct odor stimuli with chemical features in common were studied. Identification decreased for adapted components but increased for unadapted mixture-suppressed components, showing compound identities were retained, not degraded to individual molecular features. Four additional odor stimuli, 1 with 2 perceptible odor notes, and an added "water-adapted" control tested whether this finding would generalize to other 4-compound sets. Selective adaptation of mixtures of the compounds (odors): 3 mM benzaldehyde (cherry), 5 mM maltol (caramel), 1 mM guaiacol (smoke), and 4 mM methyl anthranilate (grape-smoke) again reciprocally unmasked odors of mixture-suppressed components in 2-, 3-, and 4-component mixtures with 2 exceptions. The cherry note of "benzaldehyde" (itself) and the shared note of "methyl anthranilate and guaiacol" (together) were more readily identified. The pervasive mixture-component dominance and dynamic perceptual salience may be mediated through peripheral adaptation and central mutual inhibition of neural responses. Originating in individual olfactory receptor variants, it limits odor identification and provides analytic properties for momentary recognition of a few remaining mixture-components.
Topics: Benzaldehydes; Female; Guaiacol; Humans; Male; Pyrones; Sensory Thresholds; Smell; Young Adult; ortho-Aminobenzoates
PubMed: 28641388
DOI: 10.1093/chemse/bjx031 -
CPT: Pharmacometrics & Systems... Jun 2022Oxbryta (voxelotor) is a small-molecule inhibitor of sickle hemoglobin (Hb) polymerization approved for patients with sickle cell disease (SCD) aged greater than or...
Oxbryta (voxelotor) is a small-molecule inhibitor of sickle hemoglobin (Hb) polymerization approved for patients with sickle cell disease (SCD) aged greater than or equal to 12 years at a dose of 1500 mg once daily (q.d.). Voxelotor binds preferentially to Hb, and voxelotor partitioning into red blood cells is an effective predictor of Hb occupancy. The objectives of these analyses were to develop a population pharmacokinetic (PopPK) model for voxelotor in both plasma and whole blood in adults and adolescents to support the dose selection for optimal target engagement and to identify covariates that have a significant effect on voxelotor pharmacokinetics (PK) in plasma and whole blood. An integrated plasma and whole blood PopPK model with two compartments, first-order absorption and elimination, and a site-of-action effect compartment adequately described the concentration-time profiles of voxelotor in plasma and whole blood in patients treated up to 72 weeks. Covariates with significant effects on voxelotor PK included baseline blood volume on apparent volume of the central compartment and time-varying hematocrit and dose on whole blood partitioning, indicating that clinical markers of voxelotor effect can, in turn, influence its PK. Furthermore, the model confirmed that voxelotor PK in plasma and whole blood is linear with dose and time and comparable for adults and adolescents. No clinically important covariate effects on voxelotor PK that warranted dose adjustment were identified in this analysis. Overall, the PopPK analyses contributed significantly to the voxelotor label and support 1500 mg q.d. as the therapeutic dose in adults and adolescents with SCD.
Topics: Adolescent; Adult; Aged; Anemia, Sickle Cell; Benzaldehydes; Drug Development; Humans; Models, Biological; Pyrazines; Pyrazoles
PubMed: 35447014
DOI: 10.1002/psp4.12731