Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 21.375
Filtrar
1.
Food Chem ; 398: 133858, 2023 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-35964569

RESUMO

This work investigated the isomerization of galactose to tagatose, a low caloric rare sugar, using arginine as a catalyst. Galactose (5 % w/v) and arginine (0.10 mol/mol-galactose) in water were treated at 90-120 °C. The results showed that as the temperature and time increased, galactose was continuously consumed. Rare sugars namely tagatose, talose, and sorbose were formed with the highest yield of 16.8, 2.7, and 3.3 %, respectively at 120 °C, 20 min. High temperature and short time conditions resulted in lower Maillard reaction extent. The arginine concentrations at 0.05, 0.10, and 0.15 mol/mol-galactose resulted in a slight increase in tagatose yield while an increase of the initial galactose concentration from 5 to 20 % resulted in a decrease in tagatose yield, although the tagatose concentration increased. The highest tagatose productivity of 278 g/(L⋅h) was obtained using galactose of 20 % w/v and arginine of 0.10 mol/mol-galactose at 120 °C and 4 min.


Assuntos
Arginina , Galactose , Hexoses , Isomerismo
2.
Molecules ; 27(21)2022 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-36364066

RESUMO

The influence of solvents on intramolecular interactions in 5- or 6-substituted nitro and amino derivatives of six tautomeric forms of uracil was investigated. For this purpose, the density functional theory (B97-D3/aug-cc-pVDZ) calculations were performed in ten environments (1 > ε > 109) using the polarizable continuum model (PCM) of solvation. The substituents were characterized by electronic (charge of the substituent active region, cSAR) and geometric parameters. Intramolecular interactions between non-covalently bonded atoms were investigated using the theory of atoms in molecules (AIM) and the non-covalent interaction index (NCI) method, which allowed discussion of possible interactions between the substituents and N/NH endocyclic as well as =O/-OH exocyclic groups. The nitro group was more electron-withdrawing in the 5 than in the 6 position, while the opposite effect was observed in the case of electron donation of the amino group. These properties of both groups were enhanced in polar solvents; the enhancement depended on the ortho interactions. Substitution or solvation did not change tautomeric preferences of uracil significantly. However, the formation of a strong NO∙∙∙HO intramolecular hydrogen bond in the 5-NO2 derivative stabilized the dienol tautomer from +17.9 (unsubstituted) to +5.4 kcal/mol (substituted, energy relative to the most stable diketo tautomer).


Assuntos
Elétrons , Uracila , Uracila/química , Isomerismo , Ligação de Hidrogênio , Solventes
3.
MAbs ; 14(1): 2143006, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36377085

RESUMO

Deamidation of asparagine (Asn) and isomerization of aspartic acid (Asp) residues are among the most commonly observed spontaneous post-translational modifications (PTMs) in proteins. Understanding and predicting a protein sequence's propensity for such PTMs can help expedite protein therapeutic discovery and development. In this study, we used proton-affinity calculations with semi-empirical quantum mechanics and microsecond long equilibrium molecular dynamics simulations to investigate mechanistic roles of structural conformation and chemical environment in dictating spontaneous degradation of Asn and Asp residues in 131 clinical-stage therapeutic antibodies. Backbone secondary structure, side-chain rotamer conformation and solvent accessibility were found to be key molecular indicators of Asp isomerization and Asn deamidation. Comparative analysis of backbone dihedral angles along with N-H proton affinity calculations provides a mechanistic explanation for the strong influence of the identity of the n + 1 residue on the rate of Asn/Asp degradation. With these findings, we propose a minimalistic physics-based classification model that can be leveraged to predict deamidation and isomerization propensity of proteins.


Assuntos
Asparagina , Prótons , Isomerismo , Asparagina/química , Ácido Aspártico/química , Estrutura Secundária de Proteína
4.
Int J Mol Sci ; 23(21)2022 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-36361928

RESUMO

This paper proposes a tandem mass spectrometry (MS/MS) approach in isomer recognition by playing in the "energetic dimension" of the experiment. The chromatographic set up (HPLC) was tuned to minimize the run time, without requiring high efficiency or resolution between the isomers. Then, the MS/MS properties were explored to solve the signal assignment by performing a series of energy resolved experiments in order to optimize the parameters, and by applying an interesting post-processing data elaboration tool (LEDA). The reliability of the new approach was evaluated, determining the accuracy and precision of the quantitative results through analysis of the isomer mixture solutions. Next, the proposed method was applied in a chemical stability study of human plasma samples through the simultaneous addition of a pair of isomers. In the studied case, only one of the isomers suffered of enzymatic hydrolysis; therefore, the influence of the stable isomer on the degradation rate of the other was verified. In order to monitor this process correctly, it must be possible to distinguish each isomer present in the sample, quantify it, and plot its degradation profile. The reported results demonstrated the effectiveness of the LEDA algorithm in separating the isomers, without chromatographic resolution, and monitoring their behavior in human plasma samples.


Assuntos
Algoritmos , Espectrometria de Massas em Tandem , Humanos , Cromatografia Líquida de Alta Pressão/métodos , Espectrometria de Massas em Tandem/métodos , Reprodutibilidade dos Testes , Isomerismo
5.
Int J Mol Sci ; 23(21)2022 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-36362136

RESUMO

When working on the synthesis of substituted cyclodextrins (CDs), the main challenge remains the analysis of the reaction media content. Our objective in this study was to fully characterise a complex isomers mixture of Lipidyl-ßCDs (LipßCD) obtained with a degree of substitution 1 (DS = 1) from a one-step synthesis pathway. The benefit of tandem mass spectrometry (MS/MS) and ion mobility separation hyphenated with mass spectrometry (IM-MS) was investigated. The MS/MS fragment ion's relative intensities were analysed by principal component analysis (PCA) to discriminate isomers. The arrival time distribution (ATD) of each isomer was recorded using a travelling wave ion mobility (TWIM) cell allowing the determination of their respective experimental collision cross section (CCSexp). The comparison with the predicted theoretical CCS (CCSth) obtained from theoretical calculations propose a regioisomer assignment according to the ßCD hydroxyl position (2, 3, or 6) involved in the reaction. These results were validated by extensive NMR structural analyses of pure isomers combined with molecular dynamics simulations. This innovative approach seems to be a promising tool to elucidate complex isomer mixtures such as substituted cyclodextrin derivatives.


Assuntos
Ciclodextrinas , Espectrometria de Massas em Tandem , Espectrometria de Massas em Tandem/métodos , Espectrometria de Mobilidade Iônica/métodos , Modelos Moleculares , Isomerismo
6.
J Comput Aided Mol Des ; 36(11): 805-824, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-36319876

RESUMO

Accurate calculation of relative tautomer energies in different environments is a prerequisite to many parameters of relevance in drug discovery. This work provides a thorough benchmark of the semiempirical methods AM1, PM3 and GFN2-xTB, the force-field OPLS4, Hartree-Fock and HF-3c, the density functionals PBEh-3c, B97-3c, r2SCAN-3c, PBE, PBE0, TPSS, r2SCAN, ω-B97X-V, M06-2X, B3LYP, B2PLYP, and second-order perturbation theory MP2 versus the gold-standard coupled-cluster DLPNO-CCSD(T) using the def2-QZVPP basis set. The outperforming method identified is M06-2X, whereas r2SCAN-3c is the best-perfoming one in the set of cost-optimized methods. Application of the two methods on a challenging subset from the SAMPL2 challenge provides evidence that deviations from experiment are caused by deficiencies of current continuum solvation methods.


Assuntos
Descoberta de Drogas , Isomerismo
7.
J Chem Phys ; 157(18): 184305, 2022 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-36379780

RESUMO

To assign cis and trans isomers of m-tolyl isocyanate (mTI) and p-phenylene diisocyanate (pPDI) in the electronic excitation transition, we measured the time-of-flight mass-selected resonant ionization spectra of jet-cooled phenyl isocyanate (PI), mTI, and pPDI in the region of the 275 nm first ππ* absorption system. In the excitation spectra of jet-cooled mTI and pPDI, cis- and trans-rotational isomers appeared as doublets. Isomers were assigned by analyzing the methyl-group internal rotation for mTI and by applying low-frequency bending vibrations to the mutual exclusion rule between the one- and two-photon spectra for pPDI. The electronic spectra of the three molecules observed in the jet were assigned to the transition to the first ππ* and third singlet excited states with the aid of time-dependent (TD)-B3LYP/aug-cc-pVDZ and TD-CAM-B3LYP/aug-cc-pVDZ calculations. The 0 - 0 band of PI was observed at 36 354 cm-1, those of the cis and trans isomers of mTI at 36 018 and 35 853 cm-1, respectively, and those of the cis and trans isomers of pPDI at 34 437 and 34 383 cm-1, respectively. All vibronic bands were diffuse, probably because of internal conversion to two singlet nπ* states. For mTI, based on changes in the barrier height of methyl-group internal rotation upon excitation, the Hammett-σm of PI was determined to be -0.12.


Assuntos
Isocianatos , Teoria Quântica , Isomerismo , Eletrônica
8.
Int J Mol Sci ; 23(21)2022 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-36362367

RESUMO

Details on the unexpected formation of two new (dimethylamino)methyl corrole isomers from the reaction of 5,10,15-tris(pentafluorophenyl)corrolatogallium(III) with sarcosine and paraformaldehyde are presented. Semi-empirical calculations on possible mechanism pathways seem to indicate that the new compounds are probably formed through a Mannich-type reaction. The extension of the protocol to the free-base 5,10,15-tris(pentafluorophenyl)corrole afforded an unexpected new seven-membered ring corrole derivative, confirming the peculiar behavior of corroles towards known reactions when compared to the well-behaved porphyrin counterparts.


Assuntos
Porfirinas , Sarcosina , Porfirinas/química , Isomerismo
9.
Molecules ; 27(20)2022 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-36296572

RESUMO

The utilization of 6,6-dimethyl-3-((trimethylsilyl)oxy)cyclohex-2-en-1-one made from an unsymmetrical 4,4-dimethylcyclohexane-1,3-dione in iridium-catalyzed allylic enolization involving keto-enol isomerization is accomplished under mild conditions. The chemoselectivity, regioselectivity, and enantioselectivity are facilitated by the quaternary carbon and adjusting the reaction conditions. This method provides the substituted 2-(but-3-en-2-yl)-3-hydroxy-6,6-dimethylcyclohex-2-en-1-ones in good to high yields with high level of chemo-, regio-, and enantioselectivities. The chiral carbon-fluorine bond formation is induced by an adjacent chiral carbon center of the allylated 3-hydroxy-6,6-dimethylcyclohex-2-en-1-one, as well.


Assuntos
Flúor , Irídio , Irídio/química , Estereoisomerismo , Catálise , Isomerismo , Carbono
10.
Molecules ; 27(20)2022 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-36296608

RESUMO

This work presents a literature review on the biological activity of S-carvone, geraniol and derivatives of these compounds, which are formed in the process of isomerization (during the process of geraniol isomerization, oxidation products of this compound are also obtained). Moreover, this work presents preliminary microbiological tests of creams with the addition of these biologically active compounds: S-carvone, geraniol, carvacrol (an S-carvone isomerization product), nerol (a geraniol isomerization product), linalool (a geraniol isomerization product) and citral (a geraniol oxidation product). Because the post-reaction mixture obtained after the S-carvone isomerization has a relatively simple composition, it was also added to creams and tested without isolating pure compounds. This may be a cheaper alternative to creams prepared with the addition of pure compounds. The mixture obtained after the geraniol isomerization process has a very complex composition; therefore, only compounds with the lowest molecular weight and are easily commercially available were selected for studies. The content of the tested compounds in the creams ranged from 0.5 to 3 wet%. The following microorganisms were selected for microbiological tests: the Gram-negative bacterium Escherichia coli K12, the Gram-positive bacterium Staphylococcus epidermidis, and the fungi Candida albicans, Trichophyton rubrum, Aspergillus niger, and Penicillium chrysogenum. A content of 3% carvacrol, nerol, geraniol and citral inhibited the growth of E. coli, and attenuated the growth of C. albicans and T. rubrum. On the other hand, 3% carvacrol and citral only poorly attenuated the growth of the mould fungi P. chrysogenum and A. niger.


Assuntos
Monoterpenos , Terpenos , Monoterpenos/farmacologia , Terpenos/farmacologia , Isomerismo , Escherichia coli , Aspergillus niger
11.
Nat Commun ; 13(1): 6420, 2022 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-36307413

RESUMO

Orange Carotenoid protein (OCP) is the only known photoreceptor which uses carotenoid for its activation. It is found exclusively in cyanobacteria, where it functions to control light-harvesting of the photosynthetic machinery. However, the photochemical reactions and structural dynamics of this unique photosensing process are not yet resolved. We present time-resolved crystal structures at second-to-minute delays under bright illumination, capturing the early photoproduct and structures of the subsequent reaction intermediates. The first stable photoproduct shows concerted isomerization of C9'-C8' and C7'-C6' single bonds in the bicycle-pedal (s-BP) manner and structural changes in the N-terminal domain with minute timescale kinetics. These are followed by a thermally-driven recovery of the s-BP isomer to the dark state carotenoid configuration. Structural changes propagate to the C-terminal domain, resulting, at later time, in the H-bond rupture of the carotenoid keto group with protein residues. Solution FTIR and UV/Vis spectroscopy support the single bond isomerization of the carotenoid in the s-BP manner and subsequent thermal structural reactions as the basis of OCP photoreception.


Assuntos
Proteínas de Bactérias , Ciclismo , Isomerismo , Proteínas de Bactérias/metabolismo , Carotenoides/metabolismo , Luz
12.
Phys Chem Chem Phys ; 24(41): 25182-25190, 2022 Oct 27.
Artigo em Inglês | MEDLINE | ID: mdl-36250320

RESUMO

Oxidation of the nucleobases is of great concern for the stability of DNA strands and is considered as a source of mutagenesis and cancer. However, precise spectroscopy data, in particular in their electronic excited states are scarce if not missing. We here report an original way to produce isomer-selected radical cations of DNA bases, exemplified in the case of cytosine, through the photodissociation of cold cytosine-silver (C-Ag+) complex. IR-UV dip spectroscopy of C-Ag+ features fingerprint bands for the two keto-amino cytosine tautomers. UV photodissociation (UVPD) of the isomer-selected C-Ag+ complexes produces the cytosine radical cation (C˙+) without isomerization. IR-UV cryogenic ion spectroscopy of C˙+ allows for the unambiguous structural assignment of the two keto-amino isomers of C˙+. UVPD spectroscopy of the isomer-selected C˙+ species is recorded at a unique spectral resolution. These benchmark spectroscopic data of the electronic excited states of C˙+ are used to assess the quantum chemistry calculations performed at the TD-DFT, CASSCF/CASPT2 and CASSCF/MRCI-F12 levels.


Assuntos
Citosina , DNA , Citosina/química , Isomerismo , Análise Espectral , Cátions/química , DNA/química
13.
J Agric Food Chem ; 70(43): 13959-13968, 2022 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-36264233

RESUMO

The development of a suitable immobilization strategy to improve the performance of immobilized glucose isomerase for the isomerization of glucose to fructose is crucial to promoting the industrial production of high-fructose syrup. In this work, a novel recyclable upper critical solution temperature (UCST)-type mVBA-b-P(AAm-co-AN)@glucose isomerase biocatalyst (PVAA@GI) was prepared, and the immobilized glucose isomerase could capture the glucose substrate through the affinity of 4-vinylbenzeneboronic acid (4-VBA) and the glucose substrate, which led to the enhanced substrate affinity and catalytic efficiency of the PVAA@GI. The biocatalyst exhibited excellent stability in pH, thermal, storage, and recycling compared to the free enzyme. The mVBA-b-P(AAm-co-AN)@glucose isomerase biocatalyst displayed reversibly soluble-insoluble characteristics with temperature change, which was in the soluble state during the enzyme reaction process but could be recovered in an insoluble form by lowering the temperature after the reaction. The highest fructose production rate reached 62.79%, which would have potential application in the industrial production of high-fructose syrup.


Assuntos
Aldose-Cetose Isomerases , Frutose , Glucose , Temperatura , Isomerismo , Enzimas Imobilizadas/metabolismo , Aldose-Cetose Isomerases/metabolismo
14.
Phys Chem Chem Phys ; 24(42): 26223-26231, 2022 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-36278932

RESUMO

Rhodopsins form a family of photoreceptor proteins which utilize the retinal chromophore for light energy conversion. Upon light absorption the retinal chromophore undergoes a photoisomerization. This reaction involves a non-radiative relaxation through a conical intersection between the singlet excited state and the ground state. In this work we studied the possible involvement of triplet states in the photoisomerization of retinaloids using the extended multistate (XMS) version of CASPT2. To this end, truncated models of three retinaloids were considered: protonated Schiff base, deprotonated Schiff base and the aldehyde form. The optimized geometries of the reactant, the product and the conical intersection were connected by a linear interpolation of internal coordinates to describe the isomerization. The energetic position of the low-lying singlet and triplet states as well as their spin-orbit coupling matrix elements (SOCME) were calculated along the isomerization profile. The SOCME values peaked in vicinity of the conical intersection for all the retinaloids. Furthermore, the magnitude of SOCME is invariant to the number of double bonds in the model. The SOCME for the protonated Schiff base is negligible (1.5 cm-1) which renders the involvement of the triplet state as improbable. However, the largest SOCME value of 30 cm-1 was found for the aldehyde form, followed by 15 cm-1 for the deprotonated Schiff base.


Assuntos
Rodopsina , Bases de Schiff , Bases de Schiff/química , Isomerismo , Rodopsina/química , Aldeídos
15.
J Am Chem Soc ; 144(43): 19685-19688, 2022 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-36279217

RESUMO

Here, anion photoelectron spectroscopy and first-principles quantum chemistry are used to demonstrate to what degree Au can act as a surrogate for F in UF6 and its anion. Unlike UF6, UAu6 exhibits strong ligand-ligand, i.e., Au-Au, interactions, resulting in three low-lying isomers, two of which are three-dimensional while the third isomer has a ring-like quasi two-dimensional structure. Additionally, all the UAu6 isomers have open-shell electrons, which in nearly all cases are localized on the central U atom. The adiabatic electron affinity and vertical detachment energy are measured to be 3.05 ± 0.05 and 3.28 ± 0.05 eV, respectively, and are in very good agreement with calculations.


Assuntos
Elétrons , Ligantes , Espectroscopia Fotoeletrônica , Ânions/química , Isomerismo
16.
Molecules ; 27(19)2022 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-36234790

RESUMO

Lobeline is an alkaloid derived from the leaves of an Indian tobacco plant (Lobelia inflata), which has been prepared by chemical synthesis. It is classified as a partial nicotinic agonist and has a long history of therapeutic usage ranging from emetic and respiratory stimulant to tobacco smoking cessation agent. The presence of both cis and trans isomers in lobeline is well known, and many studies on the relationship between the structure and pharmacological activity of lobeline and its analogs have been reported. However, it is a remarkable fact that no studies have reported the differences in pharmacological activities between the two isomers. In this article, we found that different degrees of isomerization of lobeline injection have significant differences in respiratory excitatory effects in pentobarbital sodium anesthetized rats. Compared with cis-lobeline injections, the respiratory excitatory effect was significantly reduced by 50.2% after administration of injections which contained 36.9% trans-lobeline. The study on the influencing factors of isomerization between two isomers shown that this isomerization was a one-way isomerism and only converted from cis to trans, where temperature was the catalytic factor and pH was the key factor. This study reports a new discovery. Despite the widespread use of ventilators, first-aid medicines such as nikethamide and lobeline has retired to second line, but as a nonselective antagonist with high affinity for a4b2 and a3b2 nicotinic acetylcholine receptors (nAChRs). In recent years, lobeline has shown great promise as a therapeutic drug for mental addiction and nervous system disorders, such as depression, Alzheimer disease and Parkinson disease. Therefore, we suggest that the differences between two isomers should be concerned in subsequent research papers and applications.


Assuntos
Alcaloides , Lobelia , Niquetamida , Receptores Nicotínicos , Medicamentos para o Sistema Respiratório , Animais , Eméticos , Isomerismo , Lobelia/química , Lobelina/química , Lobelina/farmacologia , Agonistas Nicotínicos/farmacologia , Pentobarbital , Ratos , Receptores Nicotínicos/metabolismo
17.
Molecules ; 27(19)2022 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-36235252

RESUMO

We describe azophenylindane based molecular motors (aphin-switches) which have two different rotamers of trans-configuration and four different rotamers of cis-configuration. The behaviors of these motors were investigated both experimentally and computationally. The conversion of aphin-switch does not yield single isomer but a mixture of these. Although the trans to cis conversion leads to the increase of the system entropy some of the cis-rotamers can directly convert to each other while others should convert via trans-configuration. The motion of aphin-switches resembles the work of a mixing machine with indane group serving as a base and phenol group serving as a beater. The aphin-switches presented herein may provide a basis for promising applications in advanced biological systems or particularly in cases where on demand disordering of molecular packing has value, such as lipid bilayers.


Assuntos
Indanos , Bicamadas Lipídicas , Isomerismo , Fenóis
18.
J Am Chem Soc ; 144(41): 18908-18917, 2022 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-36194812

RESUMO

B-N-fused dianthracenylpyrazine derivatives are synthesized to generate new low gap chromophores. Photophysical and electrochemical, crystal packing, and theoretical studies have been performed. Two energetically similar conformers are identified by density functional theory calculations, showing that the core unit adopts a curved saddle-like shape (x-isomer) or a zig-zag conformation (z-isomer). In the solid state, the z-isomer is prevalent according to an X-ray crystal structure of a C6F5-substituted derivative (4-Pf), but variable-temperature nuclear magnetic resonance studies suggest a dynamic behavior in solution. B-N fusion results in a large decrease of the HOMO-LUMO gap and dramatically lowers the LUMO energy compared to the all-carbon analogues. 4-Pf in particular shows significant absorbance at greater than 700 nm while being almost transparent throughout the visible region. After encapsulation in the biodegradable polymer DSPE-mPEG2000, 4-Pf nanoparticles (4-Pf-NPs) exhibit good water solubility, high photostability, and an excellent photothermal conversion efficiency of ∼41.8%. 4-Pf-NPs are evaluated both in vitro and in vivo as photothermal therapeutic agents. These results uncover B-N Lewis pair functionalization of PAHs as a promising strategy toward new NIR-absorbing materials for photothermal applications.


Assuntos
Nanopartículas , Neoplasias , Humanos , Antracenos , Isomerismo , Polímeros/química , Nanopartículas/química , Neoplasias/tratamento farmacológico , Eletrônica , Carbono , Água , Fototerapia
19.
Analyst ; 147(22): 5000-5010, 2022 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-36254743

RESUMO

Phosphoinositides, phosphorylated derivatives of phosphatidylinositols, are essential signaling phospholipids in all mammalian cellular membranes. With three known phosphorylated derivatives of phosphatidylinositols at the 3-, 4-, and 5-positions along the myo-inositol ring, various fatty acyl chain lengths, and varying degrees of unsaturation, numerous isomers can be present. It is challenging for shotgun-MS to accurately identify and characterize phosphoinositides and their isomers using the most readily available precursor ion types. To overcome this challenge, novel gas-phase ion/ion chemistry was used to expand the range of precursor ion-types for subsequent structural characterization of phosphoinositides using shot-gun tandem mass spectrometry. The degree of phosphorylation and fatty acyl sum composition are readily obtained by ion-trap CID of deprotonated phosphoinositides. Carbon-carbon double bond position of the fatty acyl chains can be localized via a charge inversion ion/ion reaction. Utilizing sequential ion/ion reactions and subsequent activation yields product ion information that is of limited utility for phosphorylation site localization. However, the kinetics of dissociation allowed for isomeric differentiation of the position of the phosphate group. Furthermore, employing the same kinetics method, relative quantitative information was gained for the isomeric species.


Assuntos
Fosfatidilinositóis , Espectrometria de Massas em Tandem , Animais , Cinética , Isomerismo , Espectrometria de Massas em Tandem/métodos , Carbono , Mamíferos
20.
J Org Chem ; 87(21): 14078-14092, 2022 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-36223641

RESUMO

The ene-yne metathesis of alkenyl boronates with terminal alkynes is reported. These challenging metatheses were accomplished using a Grubbs catalyst bearing the cyclic alkyl amino carbene (CAAC) ligand, whereas N-heterocyclic carbene (NHC) derived catalysts gave lower yields. Subsequent dienyl isomerization via a cobalt-catalyzed hydrogen atom transfer (HAT) furnished the more substituted dienyl boronate with high EE/EZ ratios. Finally, the resulting dienyl boronate products were successfully used in Suzuki-Miyaura cross-coupling reactions and in a Diels-Alder cycloaddition.


Assuntos
Alcinos , Polienos , Isomerismo , Estrutura Molecular , Reação de Cicloadição
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...