Rate Of Isomerization Research Articles

Copper-Catalyzed Chemoselective Asymmetric Hydrogenation of C=O Bonds of Exocyclic α,β-Unsaturated Pentanones.

A highly chemoselective earth-abundant transition metal copper catalyzed asymmetric hydrogenation of C=O bonds of exocyclic α, β-unsaturated pentanones was realized using H2. The desired products were obtained with up to 99% yield and 96% ee (enantiomeric excess) (99% ee, after recrystallization). The corresponding chiral exocyclic allylic pentanol products can be converted into several bioactive molecules. The hydrogenation mechanism was investigated via deuterium-labelling experiments and control experiments, which indicate that the keto-enol isomerization rate of the substrate is faster than that of the hydrogenation and also show that the Cu-H complex can only catalyze chemoselectively the asymmetric reduction of the carbonyl group. Computational results indicate that the multiple attractive dispersion interactions (MADI effect) between the catalyst with bulky substituents and substrate play important roles which stabilize the transition states and reduce the generation of by-products.

Copper‐Catalyzed Chemoselective Asymmetric Hydrogenation of C=O Bonds of Exocyclic α,β‐Unsaturated Pentanones

AbstractA highly chemoselective earth‐abundant transition metal copper catalyzed asymmetric hydrogenation of C=O bonds of exocyclic α,β‐unsaturated pentanones was realized using H2. The desired products were obtained with up to 99 % yield and 96 % ee (enantiomeric excess) (99 % ee, after recrystallization). The corresponding chiral exocyclic allylic pentanol products can be converted into several bioactive molecules. The hydrogenation mechanism was investigated via deuterium‐labelling experiments and control experiments, which indicate that the keto‐enol isomerization rate of the substrate is faster than that of the hydrogenation and also show that the Cu−H complex can only catalyze chemoselectively the asymmetric reduction of the carbonyl group. Computational results indicate that the multiple attractive dispersion interactions (MADI effect) between the catalyst with bulky substituents and substrate play important roles which stabilize the transition states and reduce the generation of by‐products.

Selective control of donor-acceptor Stenhouse adduct populations with non-selective stimuli

Selective control of donor-acceptor Stenhouse adduct populations with non-selective stimuli

Membrane Order Effect on the Photoresponse of an Organic Transducer.

Non-genetic photostimulation, which allows for control over cellular activity via the use of cell-targeting phototransducers, is widely used nowadays to study and modulate/restore biological functions. This approach relies on non-covalent interactions between the phototransducer and the cell membrane, thus implying that cell conditions and membrane status can dictate the effectiveness of the method. For instance, although immortalized cell lines are traditionally used in photostimulation experiments, it has been demonstrated that the number of passages they undergo is correlated to the worsening of cell conditions. In principle, this could impact cell responsivity against exogenous stressors, including photostimulation. However, these aspects have usually been neglected in previous experiments. In this work, we investigated whether cell passages could affect membrane properties (such as polarity and fluidity). We applied optical spectroscopy and electrophysiological measurements in two different biological models: (i) an epithelial immortalized cell line (HEK-293T cells) and (ii) liposomes. Different numbers of cell passages were compared to a different morphology in the liposome membrane. We demonstrated that cell membranes show a significant decrease in ordered domains upon increasing the passage number. Furthermore, we observed that cell responsivity against external stressors is markedly different between aged and non-aged cells. Firstly, we noted that the thermal-disordering effect that is usually observed in membranes is more evident in aged cells than in non-aged ones. We then set up a photostimulation experiment by using a membrane-targeted azobenzene as a phototransducer (Ziapin2). As an example of a functional consequence of such a condition, we showed that the rate of isomerization of an intramembrane molecular transducer is significantly impaired in aged cells. The reduction in the photoisomerization rate translates in cells with a sustained reduction of the Ziapin2-related hyperpolarization of the membrane potential and an overall increase in the molecule fluorescence. Overall, our results suggest that membrane stimulation strongly depends on membrane order, highlighting the importance of cell passage during the characterization of the stimulation tools. This study can shine light on the correlation between aging and the development of diseases driven by membrane degradation as well as on the different cell responsivities against external stressors, such as temperature and photostimulation.

One-pot conversion of glucose to 5-hydroxymethylfurfural under aqueous conditions using acid/base bifunctional mesoporous silica catalyst

One-pot conversion of carbohydrate-derived biomass compounds to 5-hydroxymethylfurfural (HMF) using an environmentally green solvent such as water is meritorious, yet challenging, which requires the strategic design of catalysts. We prepare an ordered bifunctional organocatalyst (MS-AB) containing 3-aminopropylacetic acid grafted within the silica nanocage that converts glucose-to-HMF, exhibiting the highest HMF yield (60 wt.%/85.7 mol%) in water and under microwave conditions. Moreover, the calculated activation energies (150–170 °C) for glucose isomerization to fructose, vis-à-vis dehydration to HMF were 59.06 and 138.05 kJ mol−1, respectively which can even be comparable with the metal-catalyzed reactions. Further evidence was shown from the rate constant values, indicating fructose dehydration is faster (rate constant: k2: 1.92 x 10−2 to 1.13 x 10−1 min−1) than glucose isomerization (rate constant: k1: 2.5 to 5.3 x 10−3 min−1). Considering the advantages associated with MS-AB, the results might showcase the potential of organocatalyst for sustainable utilization of lignocellulosic biomass to platform chemicals.

Fast Isomerization Before Isomerization‐Hydroformylation: Probing the Neglected Period with A Novel Microfluidic Device

AbstractBy combining the concept of flash chemistry and radial synthesis, a novel microreactor (Flashstop reactor) was designed to study isomerization process of hydroformylation by a Rh/tetraphosphite catalyst in a time scale of seconds. It was found that in the initial 313 seconds, 60–99 % of 1‐octene was isomerized to 2‐ and 3‐octenes before the formation of aldehydes. Within this period, two different types of isomerization reactions were observed. It was proposed that a monohydride complex without CO ligand accounts for the ultrafast isomerization in the initial 30 seconds. The isomerization rate with such monohydride species was calculated much faster than that with the well‐known H(CO)Rh(P−P) species. Both experimental and DFT computational studies were carried out to support this assumption. Fast transformations early on in catalytic cycles have been rarely studied due to the lack of proper tools. We believe that the Flashstop reactor is a powerful tool for analysis of kinetics in gas‐liquid biphasic reactions within a time scale of seconds to minutes.

Fast Isomerization Before Isomerization-Hydroformylation: Probing the Neglected Period with A Novel Microfluidic Device.

By combining the concept of flash chemistry and radial synthesis, a novel microreactor (Flashstop reactor) was designed to study isomerization process of hydroformylation by a Rh/tetraphosphite catalyst in a time scale of seconds. It was found that in the initial 313 seconds, 60~99% of 1-octene was isomerized to 2- and 3-octenes before the formation of aldehydes. Within this period, two different types of isomerization reactions were observed. It was proposed that a monohydride complex without CO ligand accounts for the ultrafast isomerization in the initial 30 seconds. The isomerization rate with such monohydride species was calculated much faster than that with the well-known H(CO)Rh(P-P) species. Both experimental and DFT computational studies were carried out to support this assumption. Fast transformations early on in catalytic cycles have been rarely studied due to the lack of proper tools. We believe that the Flashstop reactor is a powerful tool for analysis of kinetics in gas-liquid biphasic reactions within a time scale of seconds to minutes.

Synthesis and anticancer profile of novel FTY720 analogues with azobenzene frameworks

A short synthetic route towards novel cytotoxic FTY720 analogues bearing a variously substituted azobenzene unit was developed. The target compounds were constructed either via a Wittig olefination or Mills reaction as the key processes. Preliminary biological screening revealed the antiproliferative activity of several newly synthesised derivatives against Jurkat, HeLa and HCT-116 cells to be quite promising, comparable or higher than the potency of cisplatin (Brinkmann et al., 2010) [1]. The structure-activity relationship showed that a loss of the alkyl side chain on the azobenzene core or its substitution with hydroxymethyl moiety seem to be detrimental for the resulting cytotoxic profile in this series of derivatives. To probe the photochromic properties of the final derivatives, the reversible E/Z isomerisation and thermal relaxation rate were determined.

Combined calorimetric, spectroscopic and microscopic investigation on the inclusion complex from cyclocurcumin and sulfobutylether-β-cyclodextrin in aqueous solution and Kinetics of thermal cis-trans isomerization

The complexation reaction between cyclocurcumin (CyCur), a natural curcuminoid with bioactive effects, and sulfobutylether-β-cyclodextrin (SBE-βCD), one of the more versatile and tolerate β-cyclodextrin derivates, was investigated in aqueous solution at 298 K. The UV–vis spectral changes of CyCur in the presence of SBE-βCD indicate the formation of the host-guest inclusion complex according to a 1:1 stoichiometry. The binding constant (Kb) determined by applying the Benesi-Hildebrand model was comparable to the value obtained by Isothermal Titration Calorimetry (ITC) measurements. Moreover, the thermodynamic parameters of the SBE-βCD/CyCur interactions demonstrate that the complexation process is enthalpically driven. Interestingly, microscopy analysis highlights the tendency of cyclocurcumin to aggregate into spherical fluorescent structures able to change their aspect and morphology in the presence of SBE-βCD. Finally, the thermal cis-trans isomerization rates of CyCur in the temperature range 294–314 K and the energetic parameters calculated by Arrhenius and Eyring plots were spectroscopically determined in SBE-βCD aqueous solution.

Photoisomerization of linear merocyanines in salt solutions

AbstractThe trans‐cis isomerization in the excited state of linear merocyanine L‐Mero4 and phenyl substituted linear merocyanine P‐L‐Mero4 in salt solution and in ionic liquid was investigated using frequency upconversion measurements. Strontium chloride and cesium iodide were added to solvent dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) to vary the ionic strength. The time‐resolved fluorescence curves of merocyanines displayed multiple exponential decay behavior. The second temporal component with time constant τ2 ≈ 2.8 (11) ps of L‐Mero4 (P‐L‐Mero4) in DMSO was assigned to the duration to reach the isomerization equilibrium between the trans and the twisted conformers. The τ2 increased at higher salt concentrations and was explained by the attachment of salt ions on the polar excited merocyanines decelerating the isomerization rate. The rotational correlation time constants obtained from the anisotropy decay of fluorescence were 360 and 240 ps in neat DMSO for L‐Mero4 and P‐L‐Mero4, respectively, and they increased to 790 and 450 ps in the most concentrated SrCl2. Using Perrin relation, we estimated the increase in the rotating volume at [SrCl2] = 536 mM, revealing ≈15 SrCl2 molecules surrounding L‐Mero4 and 7 SrCl2 on P‐L‐Mero4. The experimental data indicated that the ion–molecule interaction was stronger with SrCl2 and on L‐Mero4 than on P‐L‐Mero4.

Olefin Metathesis under Spatial Confinement and Continuous Flow: Investigation of Isomeric Side Reactions with a Grubbs–Hoveyda Type Catalyst

AbstractA 2nd‐generation Grubbs–Hoveyda type catalyst was immobilized inside mesoporous silica and used in the ring‐closing metathesis (RCM) of an α,ω‐diene to a large macro(mono)cycle. The goal was to investigate the relationship between substrate concentration, reaction time, and overall experiment time on the rate of isomerization under spatial (mesopore space) confinement with continuous‐flow microreactors. RCM reactions are commonly monitored by 1H NMR analysis, however, elucidation of reaction mixtures yielding large rings with a difference of only a single carbon atom remains difficult, because NMR signals are sometimes indistinguishable. In this work, an analytical platform with on‐line separation and detection of UV‐active substrate as well as (side) products by high‐performance liquid chromatography and a UV/Vis‐diode array detector (DAD) plus mass spectrometry served as enabling technology to quantify yield and selectivity under the respective reaction conditions. Using this setup, competitive reaction equilibria and isomerization reactions, in particular, could be resolved. Identification and quantification of relevant compounds of the reaction scheme under spatial confinement became possible despite chemical similarity. Kinetic data revealed that isomerization increases with higher substrate concentrations (up to 250 mM) and longer reaction times (from 1.2 to 18.6 min), but shows a distinct decline for prolonged overall experiment times (up to ∼250 min).

Cavity-catalyzed hydrogen transfer dynamics in an entangled molecular ensemble under vibrational strong coupling.

Microcavities have been shown to influence the reactivity of molecular ensembles by strong coupling of molecular vibrations to quantized cavity modes. In quantum mechanical treatments of such scenarios, frequently idealized models with single molecules and scaled, effective molecule-cavity interactions or alternatively ensemble models with simplified model Hamiltonians are used. In this work, we go beyond these models by applying an ensemble variant of the Pauli-Fierz Hamiltonian for vibro-polaritonic chemistry and numerically solve the underlying time-dependent Schrödinger equation to study the cavity-induced quantum dynamics in an ensemble of thioacetylacetone (TAA) molecules undergoing hydrogen transfer under vibrational strong coupling (VSC) conditions. Beginning with a single molecule coupled to a single cavity mode, we show that the cavity indeed enforces hydrogen transfer from an enol to an enethiol configuration with transfer rates significantly increasing with light-matter interaction strength. This positive effect of the cavity on reaction rates is different from several other systems studied so far, where a retarding effect of the cavity on rates was found. It is argued that the cavity "catalyzes" the reaction by transfer of virtual photons to the molecule. The same concept applies to ensembles with up to N = 20 TAA molecules coupled to a single cavity mode, where an additional, significant, ensemble-induced collective isomerization rate enhancement is found. The latter is traced back to complex entanglement dynamics of the ensemble, which we quantify by means of von Neumann-entropies. A non-trivial dependence of the dynamics on ensemble size is found, clearly beyond scaled single-molecule models, which we interpret as transition from a multi-mode Rabi to a system-bath-type regime as N increases.

Product distribution, kinetics, and aerosol formation from the OH oxidation of dimethyl sulfide under different RO2 regimes

Abstract. The atmospheric oxidation of dimethyl sulfide (DMS) represents a major natural source of atmospheric sulfate aerosols. However, there remain large uncertainties in our understanding of the underlying chemistry that governs the product distribution and sulfate yield from DMS oxidation. Here, chamber experiments were conducted to simulate gas-phase OH-initiated oxidation of DMS under a range of reaction conditions. Most importantly, the bimolecular lifetime (τbi) of the peroxy radical CH3SCH2OO was varied over several orders of magnitude, enabling the examination of the role of peroxy radical isomerization reactions on product formation. An array of analytical instruments was used to measure nearly all sulfur-containing species in the reaction mixture, and results were compared with a near-explicit chemical mechanism. When relative humidity was low, “sulfur closure” was achieved under both high-NO (τbi<0.1 s) and low-NO (τbi>10 s) conditions, though product distributions were substantially different in the two cases. Under high-NO conditions, approximately half the product sulfur was in the particle phase, as methane sulfonic acid (MSA) and sulfate, with most of the remainder as SO2 (which in the atmosphere would eventually oxidize to sulfate or be lost to deposition). Under low-NO conditions, hydroperoxymethyl thioformate (HPMTF, HOOCH2SCHO), formed from CH3SCH2OO isomerization, dominates the sulfur budget over the course of the experiment, suppressing or delaying the formation of SO2 and particulate matter. The isomerization rate constant of CH3SCH2OO at 295 K is found to be 0.13±0.03 s−1, in broad agreement with other recent laboratory measurements. The rate constants for the OH oxidation of key first-generation oxidation products (HPMTF and methyl thioformate, MTF) were also determined (kOH+HPMTF=2.1×10-11 cm3 molec.−1 s−1, kOH+MTF=1.35×10-11 cm3 molec.−1 s−1). Product measurements agree reasonably well with mechanistic predictions in terms of total sulfur distribution and concentrations of most individual species, though the mechanism overpredicts sulfate and underpredicts MSA under high-NO conditions. Lastly, results from high-relative-humidity conditions suggest efficient heterogenous loss of at least some gas-phase products.

The diagenetic continuum of steroid hydrocarbon transformation from early diagenesis into the oil window

Steroids and their derivatives are ubiquitous in the sedimentary rock record, where they are widely applied as biological or geochemical markers to determine organic facies as well as thermal maturation of bitumen and oils covering the diagenetic to catagenetic stages. The diagenetic continuum from early diagenesis into catagenesis of steroids has not been extensively studied despite the importance of these reactions in influencing the successive continuum of late diagenetic transformations.This study utilizes a stratigraphically constrained transect of 9 wells from the Upper Cretaceous Second White Specks and Belle Fourche formations of south-central Alberta, Canada ranging in thermal maturity from 0.2 %VRE to 0.8 %VRE. Biomarkers were examined from 69 samples from 8 wells and thermal maturity was determined from 87 samples from 9 wells using HAWK programmed pyrolysis analysis. Relative and absolute abundances of regular sterane, diasterene, diasterane, monoaromatic steroid, and triaromatic steroid biomarkers and changes in the proportions of steroid compound classes were determined and evaluated for thermal maturity. Additionally, isomerization ratios within each of the compound classes were examined with increasing thermal maturation.Rearranged diasterenes initially dominate the steroidal hydrocarbons, followed by diasteranes in the late diagenetic and catagenetic stages and at peak oil maturity (0.8 %VRE) diasteranes were most abundant. The relative abundance of a steroid is initially controlled by its rate of production or isomerization from a biological precursor, but at higher thermal maturities selective catagenetic destruction alters the relative abundance of steroid classes, with aromatic steroids and regular steranes being degraded or expelled earliest. Thermal maturity parameters based on the isomerization of regular steranes, and the aromatization of monoaromatic steroids are effective thermal maturity indicators in specific but overlapping ranges beginning at 0.2 %VRE. This work represents a novel examination of a natural thermal maturity transect and helps to consolidate our understanding and application of the diagenetic transformations of steroid compounds.

Molecular Twisting Affects the Solid-State Photochemical Reactions of Unsaturated Ketones and the Photomechanical Effects of Molecular Crystals.

Three groups of chalcone derivatives and their analogues involving halogen atoms (X=F, Cl, Br) have been synthesized. Firstly, the nearly planar acyclic chalcone derivatives were inclined to undergo photo-induced stereospecific [2+2] cycloaddition, which triggered the crystals to exhibit macroscopic motions of bending or cracking. In particular, the single-crystal-to-single-crystal transformation happened upon UV irradiation of the crystals, which was helpful for the understanding photomechanical effects. Cyclic 3,4-dihydronaphthalene-based chalcone analogues possess a more twisted conformation, and they tend to undergo trans-cis isomerization. No photomechanical effect was observed for the crystals of the cyclic chalcone analogues due to the lower isomerization rate. The twist degree of chroman-based molecules was in between of the first two, [2+2] cycloaddition and trans-cis isomerization simultaneously took place in crystals. Photo-induced bending and twisting were observed for the crystals of chroman-based chalcone analogues. Therefore, the differences in molecular dihedral angles in α,β-unsaturated ketones were responsible for their photochemical characters and in turn to tune the photomechanical effects. In this work, a bridge between the molecular structures and solid-state photochemical reactions triggered photomechanical crystals is built.

Preparation and photo-responsive behavior of azobenzene decorated PEG single crystal

In this work, we prepared the azobenzene decorated PEG single crystal for the first time. The azobenzene terminated PEG was prepared by the nucleophilic substitution reaction between the tosylate ended PEG and 4-hydroxy-4′-methoxy azobenzene. Uniform square-shaped crystals were obtained by a self-seeding approach. Due to the relatively large size of azobenzene, the azobenzene groups could only exist in the surface layer of the lamella crystals. The photo-responsive behavior of the azobenzene was studied by using UV–vis spectra. The photo-induced trans-cis isomerization of azobenzene could take place very well. The trans-cis isomerization rate was even similar with that in solution, which proved that the azobenzene groups attached on the single crystal had relatively loose surroundings.

Layered Double Hydroxides Used in the Construction of Photoisomeric Space for Organic Dye Molecules

AbstractThe application of photoisomerization in the storage of electron energy, molecular actuators, and medical fields has attracted extensive attention. However, the difficult regulation of the photoisomeric process hinders its practical application. Here, we provide organic molecule (acid orange, AO7) with two different nano‐confined spaces by changing the interlayer spacing of layered double hydroxide (LDH). The obtained host‐guest AO7‐LDHs‐1 and AO7‐LDHs‐2 complexes show distinctly different photoisomeric behaviors. When the LDH spacing is 1.66 nm, the relative isomerization rate of AO7 is 34 %, while when the LDH spacing is 1.13 nm, the relative isomerization rate of AO7 is 13 %. This is because the isomerization rate of AO7 molecule can be reasonably controlled by the size of LDH nano‐microenvironment. This work provides a reference for the further study of the effect of nano‐space on the photoisomeric process of organic molecules.

The Dependence of Olefin Hydrogenation and Isomerization Rates on Zirconium Metal–Organic Framework Structure

The Dependence of Olefin Hydrogenation and Isomerization Rates on Zirconium Metal–Organic Framework Structure

Design, Synthesis, and Photo-Responsive Properties of a Collagen Model Peptide Bearing an Azobenzene

Collagen is a vital component of the extracellular matrix in animals. Collagen forms a characteristic triple helical structure and plays a key role in supporting connective tissues and cell adhesion. The ability to control the collagen triple helix structure is useful for medical and conformational studies because the physicochemical properties of the collagen rely on its conformation. Although some photo-controllable collagen model peptides (CMPs) have been reported, satisfactory photo-control has not yet been achieved. To achieve this objective, detailed investigation of the isomerization behavior of the azobenzene moiety in CMPs is required. Herein, two CMPs were attached via an azobenzene linker to control collagen triple helix formation by light irradiation. Azo-(PPG)10 with two (Pro-Pro-Gly)10 CMPs linked via a photo-responsive azobenzene moiety was designed and synthesized. Conformational changes were evaluated by circular dichroism and the cis-to-trans isomerization rate calculated from the absorption of the azobenzene moiety indicated that the collagen triple helix structure was partially disrupted by isomerization of the internal azobenzene.

Excited-state dynamics of all-trans protonated retinal Schiff base in CRABPII-based rhodopsin mimics

The rhodopsin mimic is a chemically synthetized complex with retinyl Schiff base (RSB) formed between protein and the retinal chromophore that can mimic the natural rhodopsin-like protein. The artificial rhodopsin mimic is more stable and designable than the natural protein and hence has wider uses in photon detection devices. The mimic structure RSB, like the case in the actual rhodopsin-like protein, undergoes isomerization and protonation throughout the photoreaction process. As a result, understanding the dynamics of the RSB in the photoreaction process is critical. In this study, the ultrafast transient absorption spectra of three mutants of the cellular retinoic acid-binding protein II-based rhodopsin mimic at acidic environment were recorded, from which the related excited-state dynamics of the all-trans protonated RSB (AT-PRSB) were investigated. The transient fluorescence spectra measurements are used to validate some of the dynamic features. We find that the excited-state dynamics of AT-PRSB in three mutants share a similar pattern that differs significantly from the dynamics of 15-cis PRSB of the rhodopsin mimic in neutral solution. By comparing the dynamics across the three mutants, we discovered that the aromatic residues near the β-ionone ring structure of the retinal may help stabilize the AT-PRSB and hence slow down its isomerization rate. The experimental results provide implications on designing a rhodopsin-like protein with significant infrared fluorescence, which can be particularly useful in the applications in biosensing or bioimaging in deeper tissues.