Mild and General Protocol for Selective Deacetylation of Acetyl/Benzoyl-Protected Carbohydrates.

Herein, we report a mild and general protocol for chemoselective deacetylation of mixed acetyl- and benzoyl-protected carbohydrates under mild acidic conditions. The protocol allows quick access to partially protected carbohydrates, which serve as versatile synthetic intermediates during the total synthesis of various mono- and oligosaccharide targets. The applicability of the developed protocol was successfully demonstrated on a range of carbohydrate substrates of various configurations and substitution patterns featuring functionalized aliphatic and aromatic aglycones. The protocol has shown excellent compatibility with the widely used O-anomeric protecting groups, prespacer aglycones, and thioglycoside glycosyl donors.

Aromaticity of biphenylene networks.

Magnetically induced ring-currents and magnetic susceptibilities have been calculated for the series of biphenylene sheets and biphenylene nanoribbons with armchair and zigzag edges with hydrogen atoms, as well as with bromine and fluorine atoms. Calculations have been performed at the density functional level of theory. It has been shown that biphenylene sheets and nanoribbons are characterized by dominant paratropic ring current, resulting in antiaromatic character. The global electron delocalization in biphenylene networks favors the edges of molecular structures, passing through cyclobutadiene units avoiding the outer contour of benzene. Replacing the hydrogen atoms with bromine and fluorine atoms slightly reduces the global ring-current strength and increases the diamagnetic property. The B3LYP functional overestimates the paramagnetic contribution of magnetic susceptibility in large molecular structures, compared with the BHandHLYP functional, which is recommended for magnetic property calculations.

Construction of Phenanthridinone Skeletons through Palladium-Catalyzed Annulation.

Herein, a straightforward synthetic approach for the construction of phenanthridin-6(5H)-one skeletons is disclosed. The developed protocol relies on palladium catalysis, providing controlled access to a range of functionalized phenanthridin-6(5H)-ones in 59-88% yields. Furthermore, plausible reaction pathways are proposed based on mechanistic experiments.

Synthesis of Salicaceae Acetyl Salicins Using Selective Deacetylation and Acetyl Group Migration.

In the present work, the synthesis of acetylated salicins, which occur naturally in many Salicaceae species, is reported. The preparation of 2-O-acetylsalicin, 2-O-acetylchlorosalicin, and 2-O-acetylethylsalicin from peracetylated bromosalicin with selective acid-catalyzed deacetylation and one-pot nucleophilic substitution of bromine as the key steps is described. The base-catalyzed O-2 → O-6 acetyl migration afforded 6-O-acetylsalicin derivatives in good yields. Thus, the first synthesis of 6-O-acetylsalicin (fragilin) using acetyl group migration is reported as well as the synthesis of 6-O-acetylchlorosalicin and 6-O-acetylethylsalicin. The NaOMe-catalyzed deacetylation of acetylated glycosides gave salicin, chlorosalicin, and ethylsalicin recently reported from Alangium chinense.

Divergent Synthesis of Natural Benzyl Salicylate and Benzyl Gentisate Glucosides.

Herein is reported the first total synthesis of benzyl salicylate and benzyl gentisate glucosides present in various plant species, in particular the Salix genus, such as Populus balsamifera and P. trichocarpa. The method permits the synthesis of several natural phenolic acid derivatives and their glucosides starting from salicylic or gentisic acid. The divergent approach afforded access to three different acetylated glucosides from a common synthetic intermediate. The key step in the total synthesis of naturally occurring glycosides-the selective deacetylation of the sugar moiety-was achieved in the presence of a labile benzyl ester group by employing mild deacetylation conditions. The protocol permitted synthesis of trichocarpine (4 steps, 40% overall yield), isotrichocarpine (3 steps, 51% overall yield), trichoside (6 steps, 40% overall yield), and deoxytrichocarpine (3 steps, 42% overall yield) for the first time (>95% purity). Also, the optimized mild deacetylation conditions allowed synthesis of 2-O-acetylated derivatives of all four glycosides (5-17% overall yield, 90-95% purity), which are rare plant metabolites.

The role of feature-based discrimination in driving health disparities among Black Americans.

Objective: A growing body of research finds that darker skin tone is often associated with poorer physical and mental health in Blacks. However, the psychosocial mechanisms underlying the skin tone-health link remain elusive. The present study seeks to address this knowledge gap by investigating the direct and indirect (through perceived discrimination, socioeconomic status, and self-esteem) effects of skin tone on self-reported physical and mental health.Design: An urban sample of 130 Blacks aged 35 and above completed a self-administered computerized survey as a part of larger cross-sectional study.Results: Self-esteem played a particularly important role in mediating the associations between skin tone and self-reported physical and mental health. This suggests that self-esteem could be a point of intervention to help Blacks with darker skin tone achieve better health.Conclusion: The present study highlights the important role feature-based discrimination plays in determining mental and physical health outcomes among Blacks.

The development of race-based perceptual categorization: skin color dominates early category judgments.

Prior research on the development of race-based categorization has concluded that children understand the perceptual basis of race categories from as early as age 4 (e.g. Aboud, 1988). However, such work has rarely separated the influence of skin color from other physiognomic features considered by adults to be diagnostic of race categories. In two studies focusing on Black-White race categorization judgments in children between the ages of 4 and 9, as well as in adults, we find that categorization decisions in early childhood are determined almost entirely by attention to skin color, with attention to other physiognomic features exerting only a small influence on judgments as late as middle childhood. We further find that when skin color cues are largely eliminated from the stimuli, adults readily shift almost entirely to focus on other physiognomic features. However, 6- and 8-year-old children show only a limited ability to shift attention to facial physiognomy and so perform poorly on the task. These results demonstrate that attention to 'race' in younger children is better conceptualized as attention to skin color, inviting a reinterpretation of past work focusing on children's race-related cognition.

Humic substances enhance growth and respiration in the basidiomycetes Trametes maxima under carbon limited conditions.

Humic substances (HS) represent the major reservoir of carbon (C) in ecosystems, and their turnover is crucial for understanding the global C cycle. Although basidiomycetes clearly have a role in HS degradation, much less is known about the effect of HS on fungal traits. We studied the alteration of physiological, biochemical, and morphological characteristics of Trametes maxima in the presence of HS. Both complete medium and minimal (C-limited) medium mimicking natural environmental conditions were used. Adding HS led to increased biomass yield, but under C-limited conditions the effect was more apparent. This result indicated that HS were used as an additional substrate and agreed with data showing a greater penetration of tritium-labeled HS into the cell interior under C-limited conditions. Humic substances induced ultra-structural changes in fungal cells, especially under C limitation, including reducing the thicknesses of the hyphal sheath and cell wall. In the minimal medium, cellular respiration increased nearly three-fold under HS application, while the corresponding effect in complete medium was lower. In addition, in the presence of inhibitors, HS stimulated either the cytochrome or the alternative pathway of respiration, depending on presence or absence of glucose in the medium. Our results suggest that, under conditions mimicking the natural environment, HS may play three major roles: as a surplus substrate for fungal growth, as a factor positively affecting cell morphology, and as an activator of physiological respiration.

Asymmetric synthesis of unnatural α-amino acids through photoredox-mediated C-O bond activation of aliphatic alcohols.

Unnatural α-amino acids constitute a fundamental class of biologically relevant compounds. However, despite the interest in these motifs, synthetic strategies have traditionally employed polar retrosynthetic disconnections. These methods typically entail the use of stoichiometric amounts of toxic and highly sensitive reagents, thereby limiting the substrate scope and practicality for scale up. In this work, an efficient protocol for the asymmetric synthesis of unnatural α-amino acids is realized through photoredox-mediated C-O bond activation in oxalate esters of aliphatic alcohols as radical precursors. The developed system uses a chiral glyoxylate-derived N-sulfinyl imine as the radical acceptor and allows facile access to a range of functionalized unnatural α-amino acids through an atom-economical redox-neutral process with CO2 as the only stoichiometric byproduct.

General Approach to Amides through Decarboxylative Radical Cross-Coupling of Carboxylic Acids and Isocyanides.

Herein, we report a silver-catalyzed protocol for decarboxylative cross-coupling between carboxylic acids and isocyanides, leading to linear amide products through a free-radical mechanism. The disclosed approach provides a general entry to a variety of decorated amides, accommodating a diverse array of radical precursors, including aryl, heteroaryl, alkynyl, alkenyl, and alkyl carboxylic acids. Notably, the protocol proved to be efficient for decarboxylative late-stage functionalization of several elaborate pharmaceuticals, demonstrating its potential applications.

Task measuring implicit attractiveness as a function of skin tone and facial features: a failed replication.

In two studies, participants completed an implicit attractiveness task with faces as primes varying on (a) facial features from Afrocentric to Eurocentric and (b) skin tone from dark to light, and target pictures of environmental scenes varying in attractiveness. On each trial, participants were briefly primed with a face. Next, they categorized a target picture as either attractive or unattractive as quickly as possible. In addition, in Study 2, participants rated the same faces on an attractiveness scale. While results of Study 1 showed that when faces were medium in skin tone, participants were more accurate when primed with a Eurocentric face responding to attractive targets, but also more accurate when primed with an Afrocentric face responding to unattractive targets, a more powerful Study 2 failed to replicate this effect. There was no relationship between participants' explicit ratings of attractiveness and accuracy rates in the implicit attractiveness task.

Sweetened Alkylated Verdazyls Effectively Kill Cancer Cells under Light Irradiation.

The development of novel photo-dynamic therapy (PDT) agents enabling to treat the oxygen-deficient tumors is the emerging tasks for the modern medicinal chemistry. Herein, we describe the design and preparation of water-soluble agents for PDT which generate active radical species upon light irradiation. Two conjugates of carbohydrates with 1,2,4,6-substituted-1,4-dihydro-1,2,4,5-tetrazin-3(2H)-ones (AlkVZs) demonstrated high oxygen-independent cytotoxicity on PC-3 and Jurkat cancer cells under light irradiation combining with low toxicity in the dark. The efficacy of prepared compounds was estimated using MTT and Alamar Blue tests as well as microscopic dead/live colored images and flow cytometry. The analysis of obtained results reveals the influence of sugar moiety on the activity of AlkVZs. We believe that obtained compounds have high potency as platform for design of new agents for photo-dynamic therapy.

What's in a face? The role of skin tone, facial physiognomy, and color presentation mode of facial primes in affective priming effects.

Participants (N = 106) performed an affective priming task with facial primes that varied in their skin tone and facial physiognomy, and, which were presented either in color or in gray-scale. Participants' racial evaluations were more positive for Eurocentric than for Afrocentric physiognomy faces. Light skin tone faces were evaluated more positively than dark skin tone faces, but the magnitude of this effect depended on the mode of color presentation. The results suggest that in affective priming tasks, faces might not be processed holistically, and instead, visual features of facial priming stimuli independently affect implicit evaluations.

Exploiting photoredox catalysis for carbohydrate modification through C-H and C-C bond activation.

Photoredox catalysis has recently emerged as a powerful synthetic platform for accessing complex chemical structures through non-traditional bond disconnection strategies that proceed through free-radical intermediates. Such synthetic strategies have been used for a range of organic transformations; however, in carbohydrate chemistry they have primarily been applied to the generation of oxocarbenium ion intermediates in the ubiquitous glycosylation reaction. In this Review, we present more intricate light-induced synthetic strategies to modify native carbohydrates through homolytic C-H and C-C bond cleavage. These strategies allow access to glycans and glycoconjugates with profoundly altered carbohydrate skeletons, which are challenging to obtain through conventional synthetic means. Carbohydrate derivatives with such structural motifs represent a broad class of natural products integral to numerous biochemical processes and can be found in active pharmaceutical substances. Here we present progress made in C-H and C-C bond activation of carbohydrates through photoredox catalysis, focusing on the operational mechanisms and the scope of the described methodologies.

Scalable total synthesis of natural vanillin-derived glucoside ω-esters.

The first total synthesis of vanilloloside, calleryanin, and a series of naturally occurring ω-esters of vanilloloside was realized through direct glycosylation of vanillin-based aglycones or late-stage derivatization of vanilloloside. All aglycones and their fragments were synthesized from vanillin as the sole aromatic precursor. Subsequently, these intermediates were used to construct various vanillin-derived glucoside ω-esters using a mild acidic deacetylation as the key synthetic step, providing the final products in the total yields of 10-50% and general purity of >95%. Additionally, the first operationally simple and sustainable synthesis of litseafoloside B was realized on large scale, avoiding the use of toxic solvents and reagents, providing an attractive alternative to isolation of this and other similar compounds from plant sources.

Alcohol Priming and Attribution of Blame in an Acquaintance Rape Vignette.

Research on nonpharmacological effects of alcohol shows that exposure to alcohol-related cues (i.e., alcohol priming) can increase behaviors associated with actual alcohol consumption. Attributions of responsibility to female victims in sexual assault scenarios are affected by whether or not alcohol was consumed by a victim and/or perpetrator. Victims often receive higher levels of blame if they consume alcohol prior to the assault. This work extends the research on nonpharmacological effects of alcohol into a novel domain of blame attribution toward rape victims. In two studies, participants in lab settings (Study 1; N = 184) and online (Study 2; N = 421) were primed with alcohol or neutral beverage advertisements as part of a purportedly separate ad-rating task and then were presented with a vignette depicting an acquaintance rape where the characters consumed beer or soda. Participants subsequently completed a questionnaire assessing victim blame and perpetrator blame. Across both studies, participants blamed the victim most when they were exposed to both contextual (story) and noncontextual (ads) alcohol cues; this effect was especially prominent in males in Study 1. Findings for perpetrator blame were inconsistent across studies. Implications of nonpharmacological effects of alcohol on blame attribution toward rape victims are discussed in the context of courtroom situations and bystander intervention.

What Drives Racial Attitudes in Elementary School Children: Skin Tone, Facial Physiognomy, or Both?

This work examines whether racial attitudes-when measured by both explicit and implicit measures- are driven primarily by skin tone, facial physiognomy, or both in 5 to 12-year-old children. Participants evaluated faces varying in skin tone (from dark to light) and facial physiognomy (from Afrocentric to Eurocentric). In an explicit task, children rated how much they liked each face. In an implicit task, participants completed a child-friendly version of the Affect Misattribution Procedure, where they rated a Chinese character as "good" or "bad" following a racial prime. Results suggest that pro-White attitudes (especially those measured by the explicit task) are driven by both factors, vary by perceivers' race, and are present in both White and non-White children, though skin tone exerts a larger influence than other features, at least in explicit evaluations. Our results also raise the possibility that pro-White biases might be more internalized by non-White children in the American South.

Stereoselective synthesis of unnatural α-amino acid derivatives through photoredox catalysis.

A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids. The developed protocol allows the use of ubiquitous carboxylic acids as radical precursors without prior derivatization. The protocol utilizes near-stoichiometric amounts of the imine and the acid radical precursor in combination with a catalytic amount of an organic acridinium-based photocatalyst. Alternative mechanisms for the developed transformation are discussed and corroborated by experimental and computational studies.

Catalyst-free regioselective acetylation of primary hydroxy groups in partially protected and unprotected thioglycosides with acetic acid.

Highly regioselective acetylation of primary hydroxy groups in thioglycoside derivatives with gluco- and galacto-configurations was achieved by treatment with aqueous or anhydrous acetic acid (60-100% AcOH) at elevated temperatures (80-118 °C), avoiding complex, costly and time-consuming manipulations with protective groups. Acetylation of both 4,6-O-benzylidene acetals and the corresponding diols as well as the unprotected tetraol with AcOH was shown to lead selectively to formation of 6-O-acetyl derivatives. For example, the treatment of phenyl 1-thio-ß-d-glucopyranoside with anhydrous AcOH at 80 °C for 24 h gave the corresponding 6-O-acetylated derivative in 47% yield (71% based on the reacted starting material) and unreacted starting tetraol in 34% yield, which can easily be recovered by silica gel chromatography and reused in further acetylation.

Kinetic and theoretical comprehension of diverse rate laws and reactivity gaps in Coriolus hirsutus laccase-catalyzed oxidation of acido and cyclometalated Ru(II) complexes.

The reactivity of the acido Ru(II) complexes cis-[RuCl(2)(LL)(2)], [RuCO(3)(LL)(2)], cis-[RuCO(3)-(bquin)(2)] (LL = 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen); bquin = 2,2'-biquinoline) and cyclometalated Ru(II) derivatives of 2-phenylpyridine and 4-(2-tolyl)pyridine [Ru(o-C(6)H(4)-2-py)(phen)(2)]PF(6) (1), [Ru(o-C(6)H(3)-p-R-2-py)(bpy)(MeCN)(2)]PF(6) (2), and [Ru(o-C(6)H(3)-p-R-2-py)(phen)(MeCN)(2)]PF(6) (3) (R = H (a), Me (b)) toward laccase from Coriolus hirsutus has been investigated by conventional UV-vis spectroscopy at pH 3-7 and 25 degrees C. The acido and cyclometalated complexes are readily oxidized into the corresponding Ru(III) species, but the two types of complexes differ substantially in reactivity and obey different rate laws. The acido complexes are oxidized more slowly and the second-order kinetics, first-order in laccase and Ru(II), holds with the rate constants around 5 x 10(4) M(-1) s(-1) at pH 4.5 and 25 degrees C. The cyclometalated complexes 1-3 react much faster and the hyperbolic Michaelis-Menten kinetics holds. However, it is not due to formation of an enzyme-substrate complex but rather because of the ping-pong mechanism of catalysis, viz. E(ox) + Ru(II) --> E(red) + Ru(III) (k(1)); E(red) + 1/4O(2) --> E(ox) (k(2)), with the rate constants k(1) in the range (2-9) x 10(7) M(-1) s(-1) under the same conditions. The huge values of k(1) move the enzymatic oxidation toward a kinetic regime when the dioxygen half-reaction becomes the rate-limiting step. Cyclometalated compounds 1-3 can therefore be used for routine estimation of k(2), that is, the rate constant for reoxidation for laccases by dioxygen. The mechanism proposed was confirmed by the direct stopped-flow measurements of the k(2) rate constant (8.1 x 10(5) M(-1) s(-1) at 26 degrees C) and supported by the theoretical modeling of interaction between the bpy analogue of 1 and Coriolus hirsutes laccase using Monte Carlo simulations.