Mixture Of Products Research Articles

Understanding the uneven phase distribution and multi-step reaction mechanism of carbonated γ-C2S-based foam concrete

γ-C2S has been attracting much attention as the role of exclusive or primary binder to fabricate carbonated materials due to its high carbonation reactivity. However, the very limited hydration reactivity of γ-C2S makes it difficult in the production of casting-formed materials such as foam concrete, and this is exacerbated by the presence of bursting-prone foams in the mixture. Given the highly cementitious property of Portland cement (PC), 10wt.% of PC was added to γ-C2S-based foam concrete (CFC) as the supplemented binder to maintain its cellular structure while providing demoulding strength. The compressive strength of the CFC (600 kg/m3), carbonated for 2 hours at ambient conditions, impressively peaks at 4.49 MPa, comparable to that of autoclaved aerated concrete with the same density grade, and is three times higher than the standard strength of foam concrete. This is partly attributed to the more uniform air-void size distribution formed by the enrichment of cement hydration products on the void-wall. Furthermore, the presence of cement hydration products positively promotes the dissolution of calcium ions from γ-C2S, forming a mixture of calcium and silicon products. This paper aims to understand the carbonation mechanisms of composite CFC, and also provide guidance for further realizing the reaction process associated with multiple carbonatable phases.

Chiral Organic Salt Supported Pd Nanoparticles as Selective Heterogeneous Catalysts of Hydrogenation Reactions

AbstractIn this study, we report the synthesis of a new type of chiral crystalline organic porous salt CF2 derived from the ionic reaction between tetrakis(4‐sulfophenyl)methane (TSPM) and the tetra‐(S)‐prolylamide of tetrakis(4‐aminophenyl)methane, (S)‐TPPM, and its ability to stabilize 2 nm palladium nanoparticles to give a novel, nonpyrophoric, chiral, catalytic material Pd@CF2. The preparation of the catalyst was very simple and conducted in water. The heterogeneous catalytic performance of Pd@CF2 was tested in hydrogen reductions of olefins and substituted nitroaromatic compounds using Pd/C as a comparison to determine the specific features of the novel catalyst. Although both types of catalysts exhibited similar catalytic activity in case of reductions of diphenylacetylene and nitrobenzene, Pd@CF2 predominantly promoted the reduction of p‐nitrobenzaldehyde to p‐aminobenzyl alcohol whereas Pd/C gave p‐toluidine. The reduction of p‐dinitrobenzene led to predominant formation of p‐nitrophenylhydroxylamine if promoted by the novel catalyst and to a mixture of products if promoted by Pd/C. In addition, the introduction of p‐alkoxy groups onto nitrobenzenes slowed down the reduction with Pd@CF2 but had no influence on Pd/C activity. A hypothesis ascribing these observations to dissimilar equilibrium distributions of nitro and polar groups within the organic framework and the palladium metal surface is proposed to rationalize the selectivity of the novel catalytic material.

Reaction kinetics and product evolution of hydrolysis in copper-chlorine thermochemical cycle for hydrogen production

By-products of the hydrolysis reaction in the copper-chlorine thermochemical cycle for hydrogen production are key to the final thermal and hydrogen efficiency. The current study focuses on the influences of reaction time, temperature, and steam partial pressure on the hydrolysis reaction and by-product formation mechanism via experimental and multiple analytical methods. The result demonstrates that the hydrolysis reaction of CuCl2 and steam converts to CuCl and Cu2OCl2, with a high conversion of 97%, while the Cu2OCl2 and CuCl2-CuO product mixtures exhibit interconversion capabilities. The increase of temperature increases the CuCl product content, while the decrease of steam partial pressure increases the by-product CuCl2. Particle morphology and reaction thermodynamics are analyzed for main and by-products formation. Finally, the homogeneous reaction model and shrinking core model are used and compared for the activation energy of the formation of Cu2OCl2 for the hydrolysis reaction and the effect of by-products.

Tandem microplastic degradation and hydrogen production by hierarchical carbon nitride-supported single-atom iron catalysts

Microplastic pollution, an emerging environmental issue, poses significant threats to aquatic ecosystems and human health. In tackling microplastic pollution and advancing green hydrogen production, this study reveals a tandem catalytic microplastic degradation-hydrogen evolution reaction (MPD-HER) process using hierarchical porous carbon nitride-supported single-atom iron catalysts (FeSA-hCN). Through hydrothermal-assisted Fenton-like reactions, we accomplish near-total ultrahigh-molecular-weight-polyethylene degradation into C3-C20 organics with 64% selectivity of carboxylic acid under neutral pH, a leap beyond current capabilities in efficiency, selectivity, eco-friendliness, and stability over six cycles. The system demonstrates versatility by degrading various daily-use plastics across different aquatic settings. The mixture of FeSA-hCN and plastic degradation products further achieves a hydrogen evolution of 42 μmol h‒1 under illumination, outperforming most existing plastic photoreforming methods. This tandem MPD-HER process not only provides a scalable and economically feasible strategy to combat plastic pollution but also contributes to the hydrogen economy, with far-reaching implications for global sustainability initiatives.

Synergistic Nanoscale Mn3O4-CoO-Co Heterojunctions for Boosting the Selectivity in Hydrogenation of Nitrostyrenes and Nitroarenes.

Metal-metal oxide interface catalysts are in high demand for advanced catalytic applications due to their multi-component active sites, which facilitate synergistic cooperation where a single component alone cannot effectively promote the desired reaction. Demonstrated herein graphene oxide-supported nanoscale Mn3O4-CoO-Co as highly efficient catalysts for hydrogenation of nitro styrenes/nitro arenes to amino styrenes/arenes under mild reaction conditions (0.5 MPa and 100 °C in 1:1 THF/water). Charge relocalization at the Co-CoO-Mn3O4 heterojunction interfaces, primarily driven by Mn3O4, significantly improves reaction selectivity. Replacing Mn3O4 with MnO or using other supported bimetallic CoMnOx catalysts decreases selectivity, leading to the formation of a mixture of products. The catalyst demonstrated remarkable selectivity in converting nitro groups to amines, even in the presence of highly reactive functional groups such as C=C, O-C=O, C=O, C≡N, chalcones, and halides. It also exhibited high yields, multiple reusability, and a broad substrate scope. This study demonstrates how Mn3O4, in synergy with CoO-Co, fine-tunes selectivity, paving the way for the development of advanced metal-metal oxide interface catalysts to enhance both selectivity and efficiency in organic transformations.

Toward Sustainable Chemical Synthesis: Metathesis of Sunflower-Derived Ethyl Esters and Evaluation of the Surfactant Potential of the Product Mixtures

Toward Sustainable Chemical Synthesis: Metathesis of Sunflower-Derived Ethyl Esters and Evaluation of the Surfactant Potential of the Product Mixtures

Pentaethylphenol (Not 2,6-di-tert-butyl-4-ethylphenol) verified as the primary product of guaiacol ethanol alkylation reaction

Guaiacol ethanol alkylation (GEA), a model reaction of lignin solvolysis, has been intensively investigated. However, the product identification with gas chromatograph-mass spectrometer (GC-MS) was wrong due to the defect of the GC-MS databases. In this work, the main product was isolated with a flash chromatography technique and analyzed with 1H NMR and was identified as ethyl fully substituted phenol (or pentaethylphenol), which is contrary to the reported 2,6-di-tert-butyl-4-ethylphenol in previous literature. The NMR analysis of the entire product mixture further confirms that the product only contains ethyl substituted molecules, with no existence of isopropyl or tert-butyl substituted products. The byproducts, including ethyl partially substituted phenols, i.e., tetraethylphenol and triethylphenol, ethyl partially substituted guaiacol, 2-ethoxyphenol, and pentaethylbenzene, were also speculated based on the MS spectra. These findings rectify a long-standing error in product identification and may offer critical insights for mechanism investigations.

In vitro assessment of acute airway effects from real-life mixtures of ozone-initiated oxidation products of limonene and printer exhaust

In indoor air the reaction of ozone (O3) with terpenes may lead to the formation of irritating gas-phase products which may induce acute airway effects (i.e. sudden, short-term changes or symptoms related to the respiratory system). We aimed to perform an in vitro study on possible health effects of products from the O3-initiated reaction of limonene with printer exhaust, representing real-life mixtures in offices. Human bronchial epithelial cells were exposed for 1 hour (h) to limonene and O3, combined with printer exhaust. The resulting concentrations represented 34% and 6% of the generated initial concentrations of limonene (400 µg/m³) and O3 (417 µg/cm³), respectively, which were in range of high end realistic indoor concentrations. We observed that the reaction of limonene with O3 generated an increase of ultrafine particles within 1 h, with a significant increase of secondary reaction products 4-oxopentanal and 3-isopropenyl-6-oxo-heptanal at high end indoor air levels. Simultaneous printing activity caused the additional release of micron-sized particles and a further increase in reaction products. Relevant cellular endpoints to evaluate the possible induction of acute airway effects were measured. However, none of the test atmospheres representing office air was observed to induce these effects.

Nickel-Catalyzed C-C Activation of Vinylcyclobutane with Visible Light: Scope, Mechanism, and Application to Chemically Recyclable Polyolefins.

N-heterocyclic carbene (NHC)-supported nickel complexes were investigated for the oxidative ring-opening of vinylcyclobutane (VCB) and photocatalytic activity. Addition of VCB to in situ generated [(NHC)Ni(0)] compounds furnished (NHC)Ni(VCB)2 that underwent oxidative addition and conversion to the corresponding Ni(II) alkyl, allyl-metallacycles. The (NHC)Ni(C6H10) metallacycles were isolated, characterized, and exhibited high thermal and chemical stability. Irradiation with visible light at ambient temperature produced a mixture of ethylene and 4-vinylcyclohexene and 1,5-cyclooctadiene, cycloaddition dimers of butadiene, arising from formal retro-[2 + 2] cycloaddition. A mixture of hexadiene products arising from β-H elimination from the metallacycle was also observed. Free ethylene also underwent a secondary reaction to form cyclopropane products through formal [2 + 1] cycloaddition. A series of sterically and electronically modified NHC ligands was evaluated to establish the structure-activity relationship governing the rate of photocatalytic conversion of VCB and the resulting product distribution. Isotopic labeling experiments, resting state analysis, and independent synthesis of a range of nickel bis(olefin) complexes provided insight into the mechanism of the reaction and origins of the organic product mixture. (NHC)Ni-catalysis was also applied toward the retro-[2 + 2] depolymerization of (1,n'-divinyl)-oligocyclobutane to butadiene dimers.

Structured Triacylglycerol with Optimal Arachidonic Acid and Docosahexaenoic Acid Content for Infant Formula Development: A Bio-Accessibility Study.

Polyunsaturated fatty acids (PUFAs), especially arachidonic acid (ARA) and docosahexaenoic acid (DHA), are extremely important fatty acids for brain development in the fetus and early childhood. Premature infants face challenges obtaining these two fatty acids from their mothers. It has been reported that supplementation with triacylglycerols (TAGs) with an ARA:DHA (w/w) ratio of 2:1 may be optimal for preterm infants, as presented in commercial formulas such as Formulaid™. This study explored methods to produce TAGs with a 2:1 ratio (ARA:DHA), particularly at the more bioavailable sn-2 position of the glycerol backbone. Blending and enzymatic acidolysis of microalgae oil (rich in DHA) and ARA-rich oil yielded products with the desired ARA:DHA ratio, enhancing sn-2 composition compared to Formulaid™ (1.6 for blending and 2.3 for acidolysis versus 0.9 in Formulaid™). Optimal acidolysis conditions were 45 °C, a 1:3 substrate molar ratio, 10% Candida antarctica lipase, and 4 h. The process was reproducible, and scalable, and the lipase could be reused. In vitro digestion showed that 75.5% of the final product mixture was bio-accessible, comprising 19.1% monoacylglycerols, ~50% free fatty acids, 14.6% TAGs, and 10.1% diacylglycerols, indicating better bio-accessibility than precursor oils.

Hair treatment products containing pigeon pea oil as chemical properties and anti-oxidant activity

The comparing small type (T9) and big type (ICP 7035), which were extracted by hexane maceration, this study looks at the properties of pigeon pea oil in hair treatment products. It finds that the percentage yield of big seed (ICP 7035) oil is higher than that of small seed (T9) oil, at 9.64 ± 0.10 and 9.32 ± 0.08, respectively. A study on the chemical properties of the oil revealed values for saponification, acidity, iodine, and peroxide. In all trials, T9 outperformed ICP 7035 in terms of test results, demonstrating the presence of fatty acids in the molecular components of triglycerides. Compared to ICP 7035, T9 had a lower molecule weight and a lower saturation level, making it less susceptible to oxidative lipid disorder and the tendency to deplete oil. The flavonoid content of T9 is higher than that of ICP 7035, equal to 27.76 ± 0.65 mg GAE g-1 extract and 25.90 ± 0.69 mg GAE g-1 extract, respectively. The flavonoid content of T9 is higher than that of ICP 7035, equal to 20.67 ± 0.58 mg QE g-1 extract and 18.76 ± 0.65 mg QE g-1 extract, respectively. The DPPH test showed that T9 was a stronger antioxidant than ICP 7035, with amounts of 0.26 ± 0.04 mg g-1 of extract and 0.35 ± 0.05 mg g-1, respectively. The development of hair care products revealed that a mixture containing the optimal dosage of T9 effectively ensured smooth hair lines and prevented microorganism contamination in all recipes. GRAPHICAL ABSTRACT HIGHLIGHTS Pigeon Pea Oil in Hair Care Products Comparison of T9 and ICP 7035 oil properties. ICP 7035 yield was higher than T9 yield. Chemical properties of oil included saponification, acidity, iodine, and peroxide. T9 oil had better phenolics, flavonoids, and DPPH values than ICP 7035. T9-rich mixtures in hair care products ensure smooth hair lines and prevent microorganism contamination.

Revealing the Role of Solvent in anti-Oxypalladation-Triggered Regiocontrolled Domino Reactions for the Synthesis of Benzazepine- and Tetrahydroquinoline-Containing Scaffolds: A Combined Computational and Experimental Study.

Palladium-catalyzed regiocontrolled intramolecular oxypalladation-initiated cascades of multifunctional internal alkyne bearing an N-tosyl tether deliver functionalized benzazepine as an exclusive product via 6-endo-dig pathway in 1,4-dioxane solvent and tetrahydroquinoline scaffold as a major product via the 5-exo-dig pathway in the DMSO solvent. The role of the solvent in controlling the regioselectivity is still unknown which can be a major hurdle for further reaction development. Moreover, the reaction in DMSO suffered from having a mixture of products, and no exclusive formation of tetrahydroquinoline was achieved. Herein, we report a concerted computational and experimental study, revealing the role of the solvent in controlling the reaction outcome. DFT study revealed that the formation of the σ-vinylpalladium intermediate is reversible for the 5-exo-dig pathway while it is irreversible for the 6-endo-dig mechanism in 1,4-dioxane and consequently, the 5-exo-dig pathway is difficult to proceed. In contrast, both the 5-exo-dig and 6-endo-dig pathways are irreversible in DMSO. We predicted an exclusive formation of isobenzofuranone-fused chromane via the 5-exo-dig pathway when the N-tosyl tether is replaced by the O-tether in the internal alkyne in DMSO. The experimental study confirms the theoretical hypothesis and provides a highly chemo-divergent approach for the synthesis of biologically significant chromane with a large substrate scope and up to 95% yield at room temperature.

Alumina-supported multi-metal catalyst for e-waste management for reclamation of valuable products

ABSTRACT Electronic and electrical waste (e-waste) has increased exponentially due to the humungous growth in the information technology and communication sector. Many multi-metal catalysts are developed by researchers for electronic waste plastic conversion into fuel products and recovery of valuable metals. In the present study, an Alumina-supported catalyst powder with selected transition metals metal oxides was prepared to improve the yield of hydrocarbon liquids. FESEM with energy-dispersive spectroscopy, XRD and laser diffraction particle size analysis were used to characterise catalysts. The shredded e-waste chips to catalyst weight ratio was maintained from 2:1 to 10:1 and studied. The experiments were conducted with a reaction temperature range from 300°C to 500°C. The produced fuel density was 0.88 kg/L, with 0.75 liquid fuel conversion and 71.7% overall liquid fuel yield. The light gas percentage was 4–6%. NMR analysis, bomb calorimetric study and gas chromatography-mass spectroscopy of liquid fuel analysis suggest carbon chain compounds of C3–C20 hydrocarbon, indicating a mixture of petrol and diesel-like liquid products. The catalyst can be tuned to improve liquid fuel conversion. The liquid fuel product is promising for fuel use, however, upgrading treatments are needed to meet standard product specifications.

Optimization design and interface characteristics research of high damping NiTi - Nickel-Aluminum Bronze functional gradient composite coating additively manufactured by high-speed laser-directed energy deposition

The near-equatomic NiTi shape memory alloy demonstrates exceptional damping performance due to its distinctive low-temperature self-cooperative martensitic internal friction. This study successfully fabricated NiTi-NAB (Nickel-Aluminium bronze shape memory alloy) functionally graded composite coatings with excellent metallurgical bonding between layers on Q235 steel substrates by designing an appropriate interlayer structure and employing the high-speed laser-directed energy deposition (LDED). Through comprehensive evaluation of the composite coating's performance and the numerical simulations of heat transfer within the molten pool, we elucidated the impact of process parameter levels on the microstructure and phase transformation characteristics of the NiTi alloy coating (NTC). The phase composition and phase interface characteristics of the NTC surface and bonding interface were analyzed using an electron probe microanalyzer and transmission electron microscopy, while dynamic thermomechanical analysis was employed to evaluate the damping performance of the NTC. The results indicate that an optimal parameter combination area still exists within the NTC-LDED process parameter window, even with equal laser energy density. Insufficient parameter levels can lead to an increase of micro-defects within the NTC, consequently causing a deterioration in both the cohesion and deformation resistance of the coating. Excessively high parameter levels can lead to significant element loss and residual stress, which in turn contributes to an increase in microcracks within the coating. A considerable quantity of reaction product mixture phases was formed at the interface between NTC and NAB, tending to align coherently with the NAB phase interface. The NTC, prepared with optimal process parameters, exhibits exceptional damping performance with a damping ratio of 0.498 at internal friction equilibrium, rendering it highly promising for applications in surface erosion protection for fluid machinery.

Elusive Arylalkylcarbenes in Solution and in Crystals: Facile 1,2-R (R = H, Ph) Migrations of 1,2,2-Triphenylethylidene.

Highly reactive arylalkylcarbenes generated in solution by photolysis of their aryldiazoalkane precursors tend to undergo competing inter- and intramolecular reactions to yield a complex mixture of products. Having previously shown the use of crystals to effectively control the reactivity of arylalkylcarbenes to afford high yields of a single product, it was of interest to investigate whether the crystalline environment could also enable spectroscopic detection of these intermediates en route to the photoproduct. Using 1,2,2-triphenyldiazoethane (3) as a model substrate to probe the effect of alternative reaction trajectories that yield triphenylethylene (5) by competing 1,2-H shift or 1,2-Ph migration, we report selectivities consistent with reaction from a spin-equilibrated carbene 4 in solution, while reactions in crystals primarily afford alkene 5 via a lattice-controlled 1,2-H shift. Attempts to detect 1,2,2-triphenylethylidene 4 in crystals by nanosecond laser-flash photolysis or by triplet-triplet fluorescence at 77 K were unsuccessful, indicating that arylalkylcarbenes possessing α-H substituents undergo facile 1,2-H shifts both in solution and in the solid state. However, related tert-butylphenylmethylene with no α-H substituents could be observed by triplet-triplet fluorescence at 77 K in glassy matrices.

Bioproducts of Pseudomonas chlororaphis Suppress DMI Fungicide-Induced CsCYP51A and CsCYP51B Gene Expression in Colletotrichum siamense and Generate Synergistic Effects with Metconazole and Propiconazole.

Mixtures of fungicides with different modes of action are commonly used as disease and resistance management tools, but little is known of mixtures of natural and synthetic products. In this study, mixtures of metabolites from the rhizobacterium Pseudomonas chlororaphis strain ASF009 formulated as Howler EVO with below-label rates (50 µg/ml) of conventional sterol demethylation inhibitor (DMI) fungicides were investigated for control of anthracnose of cherry (Prunus avium) caused by Colletotrichum siamense. Howler mixed with metconazole or propiconazole synergistically reduced disease severity through lesion growth. Real-time PCR showed that difenoconazole, flutriafol, metconazole, and propiconazole induced the expression of DMI target genes CsCYP51A and CsCYP51B in C. siamense. The addition of Howler completely suppressed the DMI fungicide-induced expression of both CYP51 genes. We hypothesize that the downregulation of DMI fungicide-induced expression of the DMI target genes may, at least in part, explain the synergism observed in detached fruit assays.

Heteroleptic Magnesium n-Butyl on a Chemically Non-innocent 2-Anilidomethylpyridine Ligand Leading to Diverse Magnesium Hydrides.

Molecular magnesium hydrides and hydride-rich clusters are of significant interest for applications ranging from catalysis and small molecule activation to hydrogen storage. Here, we investigate the 2-anilidomethylpyridine framework NNL as an ancillary support for magnesium organometallics with a special emphasis on hydrides. The proligand NNLH (N-[2,6-bis(1-methylethyl)phenyl]-α,6-diphenyl-2-pyridinemethanamine) gives [(NNL)Mg(nBu)(thf)] (1) by nbutane elimination from Mg(nBu)2(thf)n. A stronger donor such as DMAP replaces the THF from 1 to give [(NNL)Mg(nBu)(dmap)] (2). Both are air-sensitive, and 1 is adventitiously oxidized into [(NNL)Mg(μ-OnBu)]2 (32). The homoleptic [(NNL)2Mg] (8) is made from 1 and a second equiv of NNLH. 1's terminal nBu group is selectively protonated by HN(SiMe3)2 to give [(NNL)MgHMDS] (4; HMDS = N(SiMe3)2), whereas Ph3SiOH partially protonates the backbone anilide as well to give a mixture of [(NNL)Mg(OSiPh3)(thf)] (5) and free NNLH. Like HN(SiMe3)2, aprotic MeOTf also reacts by selectively abstracting the nBu group from 1 to give [(NNL)Mg(μ:κ2-O,O'-OTf)(thf)]2 (62). Interestingly, screening the common synthetic routes for magnesium hydrides leads to diverse outcomes upon varying the Mg precursors and hydride sources. 1 and PhSiH3 give the hydride cluster [{(NNL)2Mg2(μ-H)}2(μ-H)4Mg] (7), whereas 2 and PhSiH3 give the molecular complex [(NNLde)Mg(dmap)2] (9) with a dearomatized pyridyl backbone. 1 and HBpin (pinacolborane) give a product mixture, from which a different hydride cluster [(NNL)2Mg2(μ-H)}2(μ:κ2-O,O'-O2C2Me4)] (10) is identified, showing a rare instance of complete deborylation of a HBpin molecule. 1 and HBcat (catecholborane) also give a product mixture, one of which is the borylated ligand [(NNL)Bcat] (11). HBpin with 4 as the Mg precursor takes the ligand borylation route more selectively to give [(NNL)Bpin] (12). Last, 1 reacts with iPrNH2BH3 to give [(NNL)Mg{NH(iPr)BH3}] (13), which shows a slow and fractional conversion into the dinuclear mixed hydrido amidoborane [(NNL)2Mg2(μ-H){(μ-NH(iPr)BH3}] (14) by partial β-hydride elimination. In comparison, [(NNL)Mg(iPrNHBH3)(dmap)] (15) arising from the DMAP-bound 2 and iPrNH2BH3 is stable toward such elimination.

Rebuilding with sand roses: Cold sintering of sand-gypsum mixture for sustainable brick production

In the arid climate of the Sahara Desert, several historical cities dating back to the 16th century were constructed using bricks made from sand roses, a rosette-like rock composed of sand and gypsum. This study proposes the cold sintering of sand – dihydrate gypsum (uncalcined) mixtures as a sustainable approach to develop geomimetic sand roses with satisfactory mechanical performance. The results showed that crucial factors for enhancing the unconfined compressive strength (UCS) of the cold-sintered sand-gypsum mixtures are reducing gypsum size, utilizing cyclic loading, and applying higher pressures. Reducing sand size or introducing lubricant has minimal or negative effects. Cold-sintered sand-gypsum mixtures containing over 30 % micron-sized gypsum, subjected to cyclic pressures of 100 MPa for 15 minutes, can achieve superior UCS values compared to equidimensional concrete bricks. In addition, coating the mixture with calcium carbonate can be a viable approach for protecting against weathering agents. Coating and recycling the sand-gypsum mixture do not compromise the mechanical performance of the bricks. The proposed integration of sustainable materials and manufacturing practices has the potential to reduce costs, energy consumption, and industrial emissions, while promoting a circular economy and resource preservation. The proposed brick is referred to as “sand rose brick.”

Optical Relay Sensing of Cryptochiral Alcohols Displaying α‐, β‐, γ‐ and δ‐Stereocenters or Chirality by Virtue of Isotopic Substitution

AbstractA reaction‐based optical relay sensing strategy that enables accurate determination of the concentration and enantiomeric ratio (er) of challenging chiral alcohols exhibiting stereocenters at the α‐, β‐, γ‐ or even δ‐position or hard‐to‐detect cryptochirality arising from H/D substitution is described. This unmatched application scope is achieved with a conceptually new sensing approach by which the alcohol moiety is replaced with an optimized achiral sulfonamide chromophore to minimize the distance between the covalently attached chiroptical reporter unit and the stereogenic center in the substrate. The result is a remarkably strong, red‐shifted CD induction that increases linearly with the sample er. The CD sensing part of the tandem assay is seamlessly coupled to a redox reaction with a quinone molecule to generate a characteristic UV response that is independent of the enantiopurity of the alcohol and thus allows determination of the total analyte concentration. The robustness and utility of the CD/UV relay are further verified by chromatography‐free asymmetric reaction analysis with small aliquots of crude product mixtures, paving the way toward high‐throughput chiral compound screening workflows which is a highly sought‐after goal in the pharmaceutical industry.

Optical Relay Sensing of Cryptochiral Alcohols Displaying α-, β-, γ- and δ-Stereocenters or Chirality by Virtue of Isotopic Substitution.

A reaction-based optical relay sensing strategy that enables accurate determination of the concentration and enantiomeric ratio (er) of challenging chiral alcohols exhibiting stereocenters at the α-, β-, γ- or even δ-position or hard-to-detect cryptochirality arising from H/D substitution is described. This unmatched application scope is achieved with a conceptually new sensing approach by which the alcohol moiety is replaced with an optimized achiral sulfonamide chromophore to minimize the distance between the covalently attached chiroptical reporter unit and the stereogenic center in the substrate. The result is a remarkably strong, red-shifted CD induction that increases linearly with the sample er. The CD sensing part of the tandem assay is seamlessly coupled to a redox reaction with a quinone molecule to generate a characteristic UV response that is independent of the enantiopurity of the alcohol and thus allows determination of the total analyte concentration. The robustness and utility of the CD/UV relay are further verified by chromatography-free asymmetric reaction analysis with small aliquots of crude product mixtures, paving the way toward high-throughput chiral compound screening workflows which is a highly sought-after goal in the pharmaceutical industry.