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Topological investigations of excess heat capacities of ternary mixtures containing chlorotoluenes and cyclic amides

Excess heat capacities, (CPE)123 of 1-methylpyrrolidin-2-one (1) + pyrrolidin-2-one (2) + o- or m- or pchlorotoluene (3) ternary and CPE of 1-methylpyrrolidin-2-one (1) + pyrrolidin-2-one (2) binary mixtures have been determined at 293.15, 298.15, 303.15 K and 0.1 MPa using micro differential scanning calorimeter. The results were discussed in terms of Graph (which deals with the topology of the constituent molecules) and Flory’s theories. The results suggested that CPE and (CPE)123 values determined by Graph theory compared well with experimental values. Thermodynamics is the cornerstone for many scientific and engineering disciplines including physics, chemistry, chemical engineering, petroleum engineering and material science. It provides the basis for the design and optimization of new sustainable processes and the development of advance materials and products.

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Pyrroline – Wikipedia,
1-Pyrroline | C4H7N – PubChem

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Chemical and computational methods for the characterization of covalent reactive groups for the prospective design of irreversible inhibitors

Interest in drugs that covalently modify their target is driven by the desire for enhanced efficacy that can result from the silencing of enzymatic activity until protein resynthesis can occur, along with the potential for increased selectivity by targeting uniquely positioned nucleophilic residues in the protein. However, covalent approaches carry additional risk for toxicities or hypersensitivity reactions that can result from covalent modification of unintended targets. Here we describe methods for measuring the reactivity of covalent reactive groups (CRGs) with a biologically relevant nucleophile, glutathione (GSH), along with kinetic data for a broad array of electrophiles. We also describe a computational method for predicting electrophilic reactivity, which taken together can be applied to the prospective design of thiol-reactive covalent inhibitors.

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Pyrroline – Wikipedia,
1-Pyrroline | C4H7N – PubChem

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A road map for prioritizing warheads for cysteine targeting covalent inhibitors

Targeted covalent inhibitors have become an integral part of a number of therapeutic protocols and are the subject of intense research. The mechanism of action of these compounds involves the formation of a covalent bond with protein nucleophiles, mostly cysteines. Given the abundance of cysteines in the proteome, the specificity of the covalent inhibitors is of utmost importance and requires careful optimization of the applied warheads. In most of the cysteine targeting covalent inhibitor programs the design strategy involves incorporating Michael acceptors into a ligand that is already known to bind non-covalently. In contrast, we suggest that the reactive warhead itself should be tailored to the reactivity of the specific cysteine being targeted, and we describe a strategy to achieve this goal. Here, we have extended and systematically explored the available organic chemistry toolbox and characterized a large number of warheads representing different chemistries. We demonstrate that in addition to the common Michael addition, there are other nucleophilic addition, addition-elimination, nucleophilic substitution and oxidation reactions suitable for specific covalent protein modification. Importantly, we reveal that warheads for these chemistries impact the reactivity and specificity of covalent fragments at both protein and proteome levels. By integrating surrogate reactivity and selectivity models and subsequent protein assays, we define a road map to help enable new or largely unexplored covalent chemistries for the optimization of cysteine targeting inhibitors.

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Pyrroline – Wikipedia,
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2,2′-Pyrromethene-5<1H>-one, its 1- and 1′-mono- and 1,1′-dimethyl homologues; Synthesis, thermal and photochemical reactivity

2,2′-Pyrromethene-5<1H>-one, together with the 1- and 1′-monomethyl and 1,1′-dimethyl homologues are prepared in high yield. 2,2′-Pyrromethene-5<1H>-one (1) and its 1′-methyl homologue (2) are obtained in the Z form and the 1-methyl (3) and 1,1′-dimethyl homologue (4) in the E form.All four systems photoisomerize upon irradiation with light (lambda > 360 nm> (Fig. 1).Separation of the photoisomeric mixtures provides the geometrical isomers that cannot be obtained via the thermal synthesis.The photoisomers do not isomerize thermally in refluxing methanol.Upon addition of sodium carbonate in methanol the photoisomers are converted back to theoriginal isomers, demonstrating that Z-(1), Z-(2), E-(3) and E-(4) are thermodynamically more stable than E-(1), E-(2), Z-(3) and Z-(4), respectively.The presence of the 1-methyl group in 2,2′-pyrromethene-5<1H>-one systems is reflected in the thermodynamics and the photochemistry of these molecules.

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Pyrroline – Wikipedia,
1-Pyrroline | C4H7N – PubChem

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PHOTOCYCLISATION OF KETO-LACTAMS. A NEW SYNTHESIS OF FUNCTIONALIZED 1-AZA-BICYCLO(X.Y.0.)ALKANES

A series of 1-azabicyclo(x.y.0)alkanes has been synthesized using an intramolecular photoreduction.The methodology consists of a regioselective abstraction of a hydrogen alpha to the nitrogen of an amide by the triplet T1(n, ?*) of a carbonyl derivative.

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Pyrroline – Wikipedia,
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Evaluation of aroma components in Chinese southwest tobacco by headspace gas chromatography-mass spectrometry

In this paper, a simple method of headspace analysis (HSA) was applied to determine aroma components in Chinese southwest tobacco. Ninety-seven aroma compounds were extracted from tobacco under optimized experimental conditions. Meanwhile, it took 4 h for traditional method namely simultaneous distillation and extraction (SDE) for analysis, which is time-consuming and a waste of solvent. Compared with simultaneous distillation and extraction, headspace analysis is faster and more convenient in extracting tobacco aroma compounds. Moreover, six aroma compounds were first proposed in the research. The main aromatic components in tobacco detected by headspace can evaluate the tobacco quality and distinguish a specific variety from others. Headspace analysis method was proposed as an easy, rapid and environment-friendly method for the determination of aroma components in tobacco. The proposed method can not only enhance the extracting rate of aromas but meet the demand of qualitative analysis.

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Controlled oxidation of pyrroles: Synthesis of highly functionalized gamma-lactams

The oxidation of pyrroles usually leads to uncontrolled polymerization and decomposition. To overcome this problem, the controlled oxidation of substituted pyrroles with Dess-Martin periodinane is reported. This strategy yields a range of 5-aroyloxypyrrolinones.

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Reduced graphene oxide grafted by the polymer of polybromopyrroles for nanocomposites with superior performance for supercapacitors

An integrated structure has been designed by grafting the polymer of polybromopyrroles (PPBP) onto reduced graphene oxide (RGO) to produce RGO/PPBP nanocomposites with superior electrochemical performance for supercapacitors. The RGO/PPBP nanocomposites are featured with a high nitrogen content (>9 at%), enhanced degree of graphitization, improved specific surface area, abundant micropores, and a tunable hierarchical structure on the basis of sample characterization by XRD, Raman, FT-IR, XPS, SEM, high-resolution TEM, BET, and scanning probe microscopy (SPM) techniques. The grafting of PPBP onto RGO not only suppresses agglomeration and restacking of RGO but also tailors the growth of PPBP on RGO, producing a developed hierarchical structure beneficial for mass/charge transfer. The synergistic effect between RGO and PPBP ensures superior electrochemical performance of RGO/PPBP. In a three-electrode mode, the typical RGO/PPBP electrode presents a galvanostatic capacitance (Cg) of 256 F g-1 at a current density of 10 A g-1, with a capacitance retention of 99.2% after 10000 cycles in 1 mol L-1 H2SO4. More significantly, the typical RGO/PPBP&3Verbar;RGO/PPBP supercapacitor cell exhibits a high Ccell value of 68 F g-1 at 5 A g-1, with a capacitance retention of 91.9% after 10000 cycles. Also, relatively high energy density values of 13.6, 9.4, and 6.7 W h kg-1 with the corresponding power density of 0.5, 2.5, and 10 kW kg-1 are achieved, enabling the tested cell to stay at the high level for carbon-based supercapacitors with an aqueous electrolyte.

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Pyrroline – Wikipedia,
1-Pyrroline | C4H7N – PubChem

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Cycloaddition of nitrile oxides to cyclic and acyclic alpha,beta-unsaturated amides. Frontier orbital interactions and an unexpected steric drift determine regiochemistry

The regiochemistry of the cycloadditions of nitrile oxides to alpha,beta- unsaturated amides is determined by frontier orbital interactions and by a regiochemical drift due to steric effects. Cycloadditions to alpha,beta- unsaturated lactames afford mainly 4-carboxamido-isoxazolines with high regioselectivity. In cycloadditions to acyclic alpha,beta-unsaturated amides the regioselectivity relaxes and finally reverses in the case of N,N- disubstituted derivatives, because of the increasing steric congestion at the amine nitrogen.

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Pyrroline – Wikipedia,
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Synthesis of Five-membered 2-Heteroaryl 2-Heteroaromatic Carboxylates and Attempted Cyclization to Bisheteroaryl[2,3-b:3?2?-d]pyran-2-one

2-Heteroaryl 2-heteroaromatic carboxylates were prepared by reactions of 2-heteroaromatic carbonyl chlorides and 2(5H)-furanone, 2(5H)-thiophenone, and 1-methyl-2(5H)-pyrrolone in triethylamine. The 1H nmr spectra of the esters showed that the electronic effect of both heteroaromatic rings did not cause any sizable shift from each other except for 1-methyl-2-pyrrolyl 1-methyl-2-pyrrolecarboxylate (5c). Attempts to cyclize the esters to heteroaryl-fused pyran-2-ones were unsuccessful. The results may be explained by the most stable conformation of the esters in which two heteroatoms are anti along the C-O bond of the ester group.

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Pyrroline – Wikipedia,
1-Pyrroline | C4H7N – PubChem