
Abil E AlievUniversity College London | UCL · Department of Chemistry
Abil E Aliev
PhD
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354
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Introduction
Abil E Aliev currently works at the Department of Chemistry, University College London.
Additional affiliations
December 1993 - present
Publications
Publications (354)
Here we report the first biocatalytic asymmetric synthesis of alkyl fluorides via reduction of α-fluoroenones and α-fluoroenoates using ene reductase enzymes. The reduction of a wide range of (Z) or (E)-α-fluoroenones was shown to proceed in high yield and selectivity using ene reductases, with the different alkene geometries leading to opposite en...
The conformational preferences of N‐((6‐methylpyridin‐2‐yl)carbamothioyl)benzamide were studied in solution, the gas phase and the solid state via a combination of NMR, density functional theory (DFT) and single crystal X‐ray techniques. This acyl thiourea derivative can adopt two classes of low energy conformation, each stabilized by a different 6...
Reversible cysteine modification has been found to be a useful tool for a plethora of applications such as selective enzymatic inhibition, activity-based protein profiling and/or cargo release from a protein or a material. However, only a limited number of reagents display reliable dynamic/reversible thiol modification and, in most cases, many of t...
Semiconducting polymer nanoparticles (SPN), formulated from organic semiconducting polymers and lipids, show promise as exogenous contrast agents for photoacoustic imaging (PAI). To fully realise the potential of this class of nanoparticles for imaging and therapeutic applications, a broad range of active targeting strategies, where ligands specifi...
In this work, two multi-enzyme catalysed processes to access a 1,3,4-substituted tetrahydroisoquinoline (THIQ), using either purified enzymes or lyophilised whole-cell catalysts, are presented.
Correction for ‘Use of pyridazinediones as extracellular cleavable linkers through reversible cysteine conjugation’ by Calise Bahou et al. , Chem. Commun. , 2019, 55 , 14829–14832, https://doi.org/10.1039/C9CC08362F.
The prebiotic origin of catalyst-controlled peptide synthesis is fundamental to understanding the emergence of life. Building on our recent discovery that thiols catalyze the ligation of amino acids, amides, and peptides with amidonitriles in neutral water, we demonstrate the outcome of ligation depends on pH and that high pKa primary thiols are th...
Herein we report a fundamental discovery on the use of tris(dialkylamino)phosphine reagents for peptide and protein modification. We discovered that C-terminal thiophosphonium species, which are uniquely stable, could be selectively and rapidly generated from their disulfide counterparts. In sharp and direct contrast, internal thiophosphonium speci...
The spontaneous dissolution of 2D polytriazine imide (PTI) carbon nitrides diverges dramatically with the inherent insolubility of other 2D materials such as graphene. Here, the mechanism of dissolution and underlying factors which govern PTI solubility are probed, uncovering a complex and adaptable system. At high concentrations, multi-layered spe...
This solid-state NMR report summarises the subject and results of 247 articles and original papers published in 2019. In addition to the published reviews, the two major sections in this report consider various methodological developments and a broad range of applications. The presented classification of papers into different sections and subsectio...
As one of the first semi-synthetic plastics produced industrially, cellulose acetate (CA)-based artefacts represent valued items in museum collections and archives which, however, present stability issues. High temperature and relative humidity conditions have long been known to promote changes in CA properties, for instance, due to the deacetylati...
The palladium‐catalysed sp³ C−H arylation of a selection of saturated amine scaffolds was investigated using substituted picolinamide directing groups. On the bornylamine scaffold, highly selective monoarylation takes place using unsubstituted picolinamide or 3‐methylpicolinamide, whereas a double C−H arylation occurs with other substituents presen...
The palladium-catalysed sp<sup>3</sup> C-H arylation of a selection of saturated amine scaffolds was investigated using substituted picolinamide directing groups. On the bornylamine scaffold, highly selective monoarylation takes place using unsubstituted picolinamide or 3-methylpicolinamide, whereas a double C-H arylation occurs with other substitu...
Four new conjugated microporous polymers (CMPs) were synthesised by Buchwald-Hartwig cross-coupling reaction of tri- and tetra- functionalised precursors to yield materials with tuneable surface area and pore size distribution. This approach yielded LPCMP1–4, CMPs with significantly higher Brunauer–Emmett–Teller (BET) surface area (more than five t...
The monocyclic 1,4‐benzoquinone, HU‐331, the direct oxidation product of cannabidiol, inhibits the catalytic activity of topoisomerase II but without inducing DNA strand breaks or generating free radicals, and unlike many fused‐ring quinones exhibits minimal cardiotoxicity. Thus, monocyclic quinones have potential as anticancer agents, and investig...
Herein we report a retro-Michael deconjugation pathway of thiol-pyridazinedione linked protein bioconjugates to provide a novel cleavable linker technology. We demonstrate that the novel pyridazinedione linker does not suffer from...
Ene-reductases (ERs) of the Old Yellow Enzyme family catalyse asymmetric reduction of activated alkenes providing chiral products. They have become an important method in the synthetic chemists' toolbox offering a sustainable alternative to metal-catalysed asymmetric reduction. Development of new biocatalytic alkene reduction routes, however needs...
Molecular balances are unique tools, which are used for the experimental measurements of the strength of weak noncovalent interactions. However, even a carefully designed balance can often show several different noncovalent interactions making it difficult to selectively characterise the one of interest. In this Review, molecular balances previousl...
A comparison of chlorido-gallium functionalized alkoxides as precursors for aerosol-assisted chemical vapor deposition (AACVD) was carried out. Variable-temperature (VT)-NMR studies were used to probe the fluxional behavior of these alkoxides in solution, and hence their utility as precursors. The synthesis involved the initial isolation of the dim...
Herein, various molecular balances used for comparing the strengths of intramolecular noncovalent interactions are reviewed. Our overview indicates that considerable quantitative insight into the strength of noncovalent interactions can be gained through the careful design of molecular balances. Many exciting opportunities certainly exist for the d...
The development of processes to tune the properties of materials is essential for the progression of next-generation technologies for catalysis, optoelectronics and sustainability including energy harvesting and conversion. Layered carbon nitrides have been identified as of significant interest across these fields of application. However, most carb...
[This corrects the article DOI: 10.1021/acsomega.8b02122.].
Because of its electrically conducting properties combined with excellent thermal stability and transparency throughout the visible spectrum, tin oxide (SnO2) is extremely attractive as a transparent conducting material for applications in low-emission window coatings and solar cells, as well as in lithium-ion batteries and gas sensors. It is also...
Spent coffee grounds (SCG) are a potentially sustainable source of C16-C18 triglycerides. This study investigates known solvent extraction technologies with a wide range of solvents for lipid extraction from SCGs, and determines the effect of solvent selection and process temperature on the extraction efficiency and composition of the obtained oil....
A range of novel β-nitroacetamides with an alkenyl- or alkynyl tether were synthesized using the deprotonative or conjugate addition nitro-Mannich reaction. They were subjected to radical denitration-cyclisation with a 10 equivalent excess of tributyltin hydride, catalytic AIBN in refluxing benzene to explore the structural and electronic requireme...
In this paper we outline how dihalohydration reactions of propargylic alcohols can be used to access a wide variety of useful halogenated building blocks. A novel procedure for dibromohydration of alkynes has been developed, and a selection of dichloro and dibromo diols and cyclic ethers were synthesized. The dihalohydration of homo‐propargylic alc...
A correlation between taste masking, assessed using a taste sensor system, and inclusion complex formation, assessed using NMR and molecular docking studies, has been identified for ranitidine HCl and (2-hydroxypropyl)-β-cyclodextrin.
The relative strength of noncovalent interactions between a thioether sulfur atom and various π systems in designed top pan molecular balances was determined by NMR measurements. Compared to its oxygen counterpart, the sulfur atom displays a remarkable ability to interact with almost equal facility over the entire range of π systems studied, with t...
Two different axial symmetries of the 119Sn chemical shift anisotropy (CSA) in tin dioxide with the asymmetry parameter (η) of 0 and 0.27 were reported previously based on the analysis of MAS NMR spectra. By analyzing the static powder pattern, we show that the 119Sn CSA is axially symmetric. A nearly axial symmetry and the principal axis system of...
The relative strength of noncovalent interactions between a thioether sulfur atom and various π systems in designed top pan molecular balances was determined by NMR measurements. Compared to its oxygen counterpart, the sulfur atom displays a remarkable ability to interact with almost equal facility over the entire range of π systems studied, with t...
The combustion of mercury (II) thiocyanate to form "Pharaoh's serpents" is a spectacular reaction first described nearly two centuries ago. The large volume of distinctive yellow branches that grow from a tiny quantity of flaming reactants makes this an enchanting demonstration, often used to depict the magic of chemistry. In recent years several v...
Temperature-controlled, solvent-free centrifugal spinning may be used as a means of rapid production of amorphous solid dispersions in the form of drug-loaded sucrose microfibers. However, due to the high content of amorphous sucrose in the formulations, such microfibers may be highly hygroscopic and unstable on storage. In this study, we explore b...
The use of biomass-sourced chemical feedstocks creates a conflict over land use between food and fuel/chemical production. Such conflict could be reduced by making use of the annual 1.3 Pg food waste resource. Oleic acid is available from seed oils such as pumpkin, grape, avocado and mango. Its esterification with diols 1,3-propanediol, resorcinol...
Two new palladium-catalysed reactions have been developed for the synthesis of stable 4-substituted benzooxaborinin-1-ols. A palladium-catalysed cyclisation of ortho-alkenylbenzene boronic acids can be used to access 4-chlorobenzooxaborinin-1-ols via a Wacker-type oxidation and chlorination. Alternatively, ortho-alkynylbenzene boronic acids undergo...
The use of biomass-sourced chemical feedstocks creates a conflict over land use between food and fuel/chemical production. Such conflict could be reduced by making use of the annual 1.3 Pg food waste resource. Oleic acid is available from seed oils such as pumpkin, grape, avocado and mango. Its esterification with diols 1,3-propanediol, resorcinol...
Aim:
To establish if a distinct urinary metabolic profile could be identified in Bangladeshi hepatitis-B hepatocellular carcinoma (HCC) patients compared to cirrhosis patients and controls.
Methods:
Urine samples from 42 Bangladeshi patients with HCC (39 patients with hepatitis-B HCC), 47 with cirrhosis on a background of hepatitis B, 46 with ch...
Previously published structures of the potent title toxin are falsified.
Vorapaxar is a first-in-class PAR-1 antagonistic drug based on the ent-himbacine scaffold. Detailed in this article are enantioselective and racemic routes to various novel vorapaxar analogues. Biological testing revealed these compounds to have moderate to excellent potencies against PAR-1 with the most potent analogue demonstrating an IC50 of 27...
Based on detailed analysis of newly acquired NMR data, we show that the previously revised structure of tagetitoxin is incorrect. A new structure of tagetitoxin is proposed which is consistent with the NMR and MS data.
Compounds that comprise the erythrina alkaloid class of natural products are based on a tetracyclic spiroamine framework and exhibit a range of biological activities on the central nervous system. Herein, we report a new and efficient total synthesis of this multiple-ring system based on an intramolecular acylal cyclisation (IAC) approach. Using th...
The Abraham solute hydrogen bond acidity parameter A can be derived both from physical methods, A(Gen) and NMR experiments, A(NMR) and results for a large number of hydroxylic solutes show that the two methods agreed very well. However for halophenols the values of A(NMR) were not consistent with the A(Gen) values. The values of A(NMR) suggest that...
In this paper we describe the use of a chiral aldehyde derived from lactate esters for determining the enantiopurity of primary amines, via the formation of diastereomeric imines. The method was shown to be suitable for reproducibly determining the enantiopurity of a diverse set of chiral amines. Both enantiomers of the aldehyde can be prepared in...
A comparative study by NMR using designed top pan molecular balances demonstrates that the noncovalent interaction of a hydroxyl group with π-deficient pyrazine and quinoxaline units involves a lone pair•••heteroarene interaction which is much stronger and essentially solvent independent when measured relative to the classical π-facial hydrogen bon...
Amides of benzo-fused cyclic amines can undergo a ring-opening reaction with TfOH. In benzene, the intermediate carbocation is trapped by phenylation. However, the cinnamamide of 2-phenyl-1,2-dihydroindole with TfOH in CHCl3 undergoes a novel cascade reaction to form a tetrahydro-azadibenzazulene-11-one.
A comparative study using NMR spectroscopy and designed top-pan molecular balances demonstrates that the noncovalent interaction of a hydroxy group with π-deficient pyrazine and quinoxaline units involves a lone pair-heteroarene interaction which is much stronger and solvent independent when measured relative to the classical π-facial hydrogen bond...
Photolyses at 254 nm of phenylalanine (Phe) in aqueous solutions, were carried out in the presence of oxidized carbon nanotubes modified by the reaction with SO2 (mNTO). Kinetics of the photolyses were followed by UV spectrophotometry at 220 nm and the products were characterized by HPLC, XPS and 13C-SSNMR. The ratio of the initial rates of photoly...
A comparative study by NMR spectroscopy using molecular balances indicates that non-covalent functional group interactions with an arene dominate over those with an alkene and a p-facial intramolecular hydrogen bond from a hydroxyl group to an arene is favoured by ~1.2 kJ mol-1. The strongest interaction observed in this study is with the cyano gro...
A comparative study of molecular balances by NMR spectroscopy indicates that noncovalent functional-group interactions with an arene dominate over those with an alkene, and that a π-facial intramolecular hydrogen bond from a hydroxy group to an arene is favored by approximately 1.2 kJ mol−1. The strongest interaction observed in this study was with...
1H-NMR Chemical shifts have been obtained in the solvents deuterochloroform and dimethyl sulfoxide. The differences in chemical shift of an OH or NH group in these two solvents, δ∆ = δ(DMSO) - δ(CDCl3) can be converted into the hydrogen bond acidity, A, of the group, A = 0.0065 + 0.133 δ∆ The NMR A-value, ANMR, can be used as a quantitative assessm...
The regioselective conversion of propargylic alcohols into previously unreported α,α-diiodo-β-hydroxyketones was achieved by treatment with N-iodosuccinimide in the presence of a gold catalyst. The corresponding α,α-dichloro-β-hydroxyketones were obtained by treatment with trichloroisocyanuric acid in the absence of a catalyst. The latter reaction...
The regioselective conversion of propargylic alcohols into previously unreported α,α-diiodo-β-hydroxyketones was achieved by treatment with N-iodosuccinimide in the presence of a gold catalyst. The corresponding α,α-dichloro-β-hydroxyketones were obtained by treatment with trichloroisocyanuric acid in the absence of a catalyst. The latter reaction...
Supplementary Information
N-Cinnamoyl-9-aminoanthracenes cyclise with PPA or triflic acid to form novel 2-azahexacyclo[10.6.6.0(1,5).0(6,11).0(13,18).0(19,24)]tetracosa-6(11),7,9,13,15,17,19(24),20,22-nonaen-3-ones. In contrast, both N-cinnamoyl-N-methyl-9-(2-aminomethyl)anthracene and N-cinnamoyl-9-(2-aminoethyl)anthracene undergo an intramolecular Diels-Alder cycloadditio...
Graphite particles (0.505mm) were oxidized to graphite oxide with KClO3 in a H2SO4/HNO3 mixture. Graphite and graphite oxide particles were modified by reaction with SO2 at 630 degrees C. Thiolysis with sodium dodecane-1-thiolate and aminolysis with dodecane-1-amine of these particles occurred with the insertion of the organic moiety in the carbon...
Solid-state NMR studies of collagen samples of various origin confirm that the amplitude of collagen backbone and sidechain motions increases significantly on increasing the water content. This conclusion is supported by the changes observed in three different NMR observables: (i) the linewidth dependence on the (1) H decoupling frequency; (ii) (13...
We propose a new approach for force field optimisations which aims at reproducing dynamics characteristics using biomolecular MD simulations, in addition to improved prediction of motionally averaged structural properties available from experiment. As the source of experimental data for dynamics fittings, we use (13) C NMR spin-lattice relaxation t...
N-Cinnamoyl-1-naphthylamines undergo a cyclisation reaction with triflic acid to form 4-phenyl-3,4-dihydro-1H-naphth[1,8-bc]azepin-2-ones and 4-phenyl-3,4-dihydro-1H-benzo[h]quinolin-2-ones. However, the N-benzyl analogues also undergo a unique cascade reaction to form novel heptacyclic structures via a 1,2 followed by a 4-addition to the naphthale...
Molecular dynamics characterisations in solids can be carried out selectively using dipolar-dephasing experiments. Here we show that the introduction of a sum of Lorentzian and Gaussian functions greatly improve fittings of the "intensity vs. time" data for protonated carbons in dipolar-dephasing experiments. The Lorentzian term accounts for remote...
The photocycloaddition reaction of thiomaleimides (I) and (XIII) leads to dimers (II) and (XIV)/(XV), resp., in quantitative yields.
Isolated model anion chromophores of the green and cyan fluorescent proteins were generated in an electrospray ion source, and their photodetachment spectra were recorded using photoelectron imaging. Vertical photodetachment energies of 2.85(10) and 4.08(10) eV have been measured for the model green fluorescent protein chromophore anion, correspond...