Isomerization Process Research Articles

Double‐Bond Isomerization of Rapeseed Oil Methyl Esters in a Continuous Flow Reactor Efficiently Catalyzed by H‐Mordenite

AbstractUnsaturated fatty acids are attractive alternatives to fossil‐based materials as a source of hydrocarbons, but potential applications are limited by the preset chain length of 16–20 carbon atoms. However, if the double bond can be randomly moved along the chain, subsequent bond‐breaking operations such as ethenolysis or oxidative cleavage will give rise to products with chain lengths ranging from 2 to 18 carbon atoms. A process for the double bond isomerization of rapeseed oil methyl esters in a flow‐through reactor using zeolites as the catalyst is herein disclosed. Using H‐mordenite as the catalyst at a flow of 0.125 mL min−1 at 290 °C, near equilibrium isomerization is reached with up to 49% recovery of linear monomeric products after 5 h and up to 44% after 48 h. The main side products are oligomers (3%–15%) and skeletal isomerization products (10%–23%).Practical applications: With a suitable follow‐up modification addressing the double bond (metathesis, ozonolysis, oxidative cleavage), the product mixtures of double‐bond positional isomers can be used in the production of short‐chain base chemicals. In repetitive combination with metathesis catalysis, biofuels with customized chain length distributions can be generated.

Hybrid Bicyclo[1.1.0]butanes [(R4Si3)CH2] and [(R4Si2Ge)CH2] (R = SiMetBu2): Synthesis and Thermal Isomerization to Alkyl-Substituted Cyclopropenes [R3Si3]CH2R and [R3Si2Ge]CH2R

Hybrid bicyclo[1.1.0]butanes comprised of different group 14 elements, namely, 1,2,3-trisilabicyclo[1.1.0]butane and 1,3-disila-2-germabicyclo[1.1.0]butane, were readily prepared by the reductive dichlorination of 1,3-dichlorocyclobutane precursors. Both compounds feature exceptionally short bridging Si–Si bonds and practically planar geometry around the bridging Si atoms, thus representing a novel structural motif in the chemistry of the heavy analogues of bicyclo[1.1.0]butanes. These peculiar structures were explained by the steric interaction between the substituents at the bridging and bridgehead positions. Thermolysis of the title bicyclo[1.1.0]butanes in toluene at 130 °C resulted in their isomerization to the alkyl-substituted cyclopropene analogues. The mechanism of this isomerization was revealed in detail on the basis of deuterium-labeled experiments, kinetic investigations, trapping experiments, and computational studies to establish the nature of the key intermediate of the whole isomerization process.

CALCULATION OF PROPANE THERMAL CRACKING PROCESS PARAMETERS

Thermal and one many thermocatalytic processes high temperature conditions is going This consider taking raw material first tubular in ovens certain temperature up to is heated. Some in processes the same as the tubular furnace at the time replace the reactor is doing In the oven placed serpentine of pipes beginning part raw material it heats up. Next in pipes cracking process goes. Raw material whom individual of hydrocarbons use when done unconverted raw material live reaction environment to give too favorable. Catalytic isomerization process of 50-65% isopentane from normal pentane is taken. 1-2% gas during the process hydrocarbons too doesn't buy N- pentanm non-isomerizable the part live again to the reactor when returned of isopentane to normal pentane according to it reaches 97-98%. According to the prepared model, the final indicator of the output of the target products (propylene + ethylene) and the output of these components relative to the total filling of the reactor were taken as optimality criteria during the process study. The essence of the recirculation method is that the mixture of reacting and non-reacting products enters the separator system after the reactor. Here they are separated from each other, and then the unreacted part is mixed with fresh raw materials and fed back into the reactor. In our case, only unreacted propane and ethane are given to recirculation, not all of the output products from the reactor. Because only they are converted into the intended products - propylene and ethane - by primary reactions. if a part of the devices included in the complex is not taken into account in the mathematical modeling and optimization of the process, the obtained value of the optimality criterion will be wrong. This can change the optimal value of the optimality criterion. In the complex systems of the mentioned processes, the separating node is one of the main conditions. A recirculation system usually consists of reactors, separators and other associated units. An inversely related process is carried out with a continuous output of reaction products between the steps and the input of the unreacted part of the previous raw material at each subsequent step. It seems clear that process optimization considering recirculation and kinetics simultaneously is usually not sufficient. To obtain realistic results, it is necessary to use the above equations together with the equations of the processes taking place in the separator.In this work, the results of the study of the preparation of the theoretical regularities of the adsorption-separation junctions of recirculated chemical-technological complexes and their practical use are shown. During the mathematical modeling, along with other nodes of the complex, the main attention was paid to the adsorption node and additions to German results in practice. Keywords: propane, cracking, n-pentane, isopentane, methane, hydrogen, hydrocarbon.

A dual-functional chemosensor based on acylhydrazone derivative for rapid detection of Zn(II) and Mg(II): Spectral properties, recognition mechanism and application studies

In this work, an acylhydrazone derivative (QN62) was developed via the one-step condensation of 6-hydroxy-2-naphthoic hydrazide with quinoline-8-carboxaldehyde. The structure of the QN62 compound was characterized by 1H NMR, 13C NMR, HR-MS (ESI), and X-ray crystallography. As a dual-functional turn-on fluorescence chemosensor, QN62 exhibited rapid recognition for Zn2+ in DMSO-H2O (4:1, v/v) and Mg2+ in ethanol-H2O (9:1, v/v). The enhancement in fluorescence detection was associated with the coordination reaction between QN62 and the target ions, which promoted intramolecular charge transfer and prevented the CN isomerization process. Simultaneously, a rapid color change from colorless to yellowish-green or yellow under UV light (365 nm) was easily visible to the naked eye. Under optimal conditions, the limit of detection and limit of quantification were 32.3 nM and 97.8 nM for Zn2+ and 16.1 nM and 48.9 nM for Mg2+, respectively. The recognition mechanism was reasonably speculated based on analysis of the Job’s plot, HR-MS, 1H NMR, and density functional theoretical calculations. Utilizing silica-gel plates fabricated from the QN62 chemosensor, the visual and rapid identification of Zn2+ and Mg2+ was successfully achieved, which could provide a convenient approach for on-site detection in environmental fields. The QN62 chemosensor could also quantify trace amounts of Zn2+ and Mg2+ in water samples. Furthermore, the cell imaging experiments indicated that QN62 could effectively sense intracellular Zn2+ and Mg2+, providing potential applications in biological systems.

Structure, spectroscopic signatures, and formation of hydroxy-azirine: a potential interstellar prebiotic molecule

ABSTRACT Hydroxy-azirine (C2H3NO) is a -OH derivative of azirine (C2H3N), molecule that has been the subject of several unfruitful searches in space. Hydroxy-azirine is an isomer of the detected prebiotic species methyl isocyanate, CH3NCO, and glycolonitrile, HOCH2CN, as well as the yet undetected imine acetaldehyde, NHCHCHO. However, the lack of preliminary spectroscopic data on hydroxy-azirine has prevented its astronomical search. The aim of this study is to provide high-level theoretical spectroscopic signatures of the most stable hydroxy-azirine isomers to enable their eventual interstellar search. A total of 12 isomers have been characterized for hydroxy-azirine and their isomerization processes have been analysed at the CCSD(T)-F12/cc-pVTZ-F12 level. The most stable structures are 3-hydroxy-2H-azirine (I) and 2-hydroxy-2H-azirine (II) in their syn- and anti-configurations, which are suggested as the most relevant candidates for laboratory and interstellar detection. To ease their identification by means of rotational spectroscopy, we report a set of the required spectroscopic parameters using state-of-the-art composite and coupled-cluster approaches. For astronomical purposes, we provide a complete line list for I-syn and I-antihydroxy-azirine up to 50 GHz, which takes the hyperfine structure into account, and will be essential to hunt for these interstellar candidates experimentally. In addition, anharmonic vibrational frequencies and intensities are reported to predict a trustworthy vibrational spectra and to estimate the vibrational partition function. Finally, we analyse the possibility of formation of hydroxy-azirine from the reaction of azirine with the hydroxyl radical in the gas-phase and on the surface of ices, finding for the latter a feasible formation route under interstellar conditions.

Investigation of Ultrafast Configurational Photoisomerization of Bilirubin Using Femtosecond Stimulated Raman Spectroscopy

Phototherapy is an efficient and safe way to reduce high levels of free 4Z,15Z-bilirubin (ZZ-BR) in the serum of newborns. The success of BR phototherapy lies in photoinduced configurational and structural isomerization processes that form excretable isomers. However, the physical picture of photoinduced photoisomerization of ZZ-BR is still unclear. Here, we strategically implement tunable femtosecond stimulated Raman spectroscopy and several time-resolved electronic spectroscopies, assisted by quantum chemical calculations, to dissect the detailed primary configurational isomerization dynamics of free ZZ-BR in organic solvents. The results of this study demonstrate that upon photoexcitation, ultrafast configurational isomerization proceeds by a volume-conserving "hula twist", followed by intramolecular hydrogen-bond distortion and large-scale rotation of the two dipyrrinone halves of the ZZ-BR isomer in a few picoseconds. After that, most of the population recovers back to ZZ-BR, and a very small amount is converted into stable BR isomers via structural isomerization.

Diarylethene Isomerization by Using Triplet-Triplet Annihilation Photon Upconversion.

Green-to-blue triplet-triplet annihilation photon upconversion with the well-studied upconversion pair 9,10-diphenylanthracene (DPA)/platinum octaethylporphyrin (PtOEP) was used to reversibly drive the photoisomerization of diarylethene (DAE) photoswitches by using visible light. By carefully selecting the kinetic and spectral properties of the molecular system as well as the experimental geometry, a single green light source can be used to selectively trigger both the ring-opening and the ring-closing reactions, whilst also inducing fluorescence from the colored closed isomer that can be used as a readout to monitor the isomerization process in situ. The upconversion solution and the DAE solution are kept physically separated, allowing them to be characterized both concomitantly and individually without further separation processes. The ring-closing reaction using upconverted photons was quantified and compared to the efficiency of direct isomerization with ultraviolet light.

Solvent-Controlled Photoswitching of Azobenzene: An Excited State Shuttle.

Light controlled excited state trans-cis isomerization process is a key to the development of conversion of light energy to mechanical motion at the molecular level. Considerable efforts have been made in tuning the isomerization process with electron donor and acceptor substituents by altering the excited state reaction coordinate. Here, we report a two novel push-pull series of para-diethylamino (DEA) and diphenylamino (DPA) substituted (E)-4'-((4-(diethylamino)phenyl)diazenyl)-N,N-diphenyl-[1,1'-biphenyl]-4-amine (1) and (E)-4'-((4-(diphenylamino)phenyl)diazenyl)-N,N-diphenyl-[1,1'-biphenyl]-4-amine (2). Compound 1 and 2 undergoes both photochemical and photophysical excited state deactivation pathways which can be controlled by varying the solvent polarity. These structural motifs of 1 and 2 would undergo torsional motions upon excitation to exhibit either trans → cis photoisomerization or to form a twisted intramolecular charge transfer state and both the process originates from the same excited state and competes with each other. Thus, alternations in the surrounding environment such as solvent polarity, solution viscosity, and protonation were employed to understand the preferential excited state deactivation pathway and thereby these systems could be employed as a new class of azobenzene-based luminescent photochromic molecules. For instance, in nonpolar solvent, toluene photoisomerization is preferred over TICT, but polar solvent, ethanol preferentially stabilizes the TICT state by virtue of N-C rotation which renders the energy barrier unfavourable for photoisomerization. The photostationary state of 1 in toluene is predominantly the Z isomer, whereas in ethanol E isomer is nearly two-fold higher than the Z isomer. These feature sets up a new approach towards the construction of multinary molecular switches and subsequent development in diverse fields.

Catalytic Performance and Kinetic Modeling of n-Butane Isomerization over Metal Bearing Silicotungstic Acid Supported on Mesoporous KIT-6

In this study, mesoporous KIT-6 support was synthesized hydrothermally. Its structure was improved by impregnation with phosphotungstic acid (HPW), silicotungstic acid (HSiW), and some metals such as Pt, Pd, and Ce. This work converts mesoporous KIT-6 into a bifunctional catalyst containing acid and metal sites. The structures of the synthesized catalysts were characterized by various analyses such as XRD, XRF, FTIR, SEM, EDS, BET, NH3-TPD, and TGA. Furthermore, the catalytic performances of heteropoly acids (HPW and HSiW) and KIT-6 modified samples were investigated in an n-butane isomerization process. Impregnation of HSiW on mesoporous support resulted in higher initial n-butane conversion and isobutane selectivity and improved catalyst stability compared to the unsupported sample. The introduction of 0.5 wt % platinum on the 60%HSiW/KIT-6 led to the highest n-butane conversion (72%) and isobutane yield (56.8%) at 250 °C and weight hourly space velocity (WHSV) of 0.15 h–1, at the beginning of the reaction. The 0.5%Pt/60%HSiW/KIT-6 sample was the most stable catalyst against deactivation compared to other modified samples. Its conversion and its selectivity to isobutane reached 51.8 and 73.8%, respectively, after 7 h of reaction. Also, the influence of different process variables such as reaction temperature, WHSV, and carrier gas on the catalyst activity (n-butane conversion, isobutane selectivity, and yield) was investigated. In addition, the classical bifunctional model was used to describe the kinetic behavior of 0.5%Pt/60%HSiW/KIT-6 in the isomerization reaction. This model inhibits the hydrogen and n-butane pressure effects on the reaction rate and agrees with the ideal bifunctional metal–acid mechanism. The activation energy for this model was found to be 29.64 kJ mol–1. The classical bifunctional model provided a reasonable fit for the experimental data and allowed to specify the kinetic parameters.

An ab initio study on the stability of isolated phosphaalkene synthons.

Using ab initio methods and flexible basis sets, we examined the electronic, geometric, and thermodynamic stabilities of selected phosphaalkene synthons matching the (PCR2)- formula (R = H, CH3, C6H5, C6F5, and Mes). All isolated synthons considered were found to be electronically stable and susceptible to neither fragmentation nor isomerization processes. The structures corresponding to the most stable isomers of the studied phosphaalkene synthons contain a PC double-bond (whose presence was confirmed by natural bond orbital occupancies of σ(P-C) and π(P-C) approaching 2 electrons) and two R substituents connected to the carbon atom in either (PCR2)- (for R = H, CH3, C6H5, and Mes) or (PCF-R-R)- (for R = C6F5) manner. Vertical electron detachment energies (spanning the 0.924-3.118 eV range) characterizing the phosphaalkene synthons were predicted and discussed.

Kinetic Modeling of Light Naphtha Hydroisomerization in an Industrial Universal Oil Products Penex™ Unit

Recently, the isomerization of light naphtha has been increasingly significant in assisting refiners in meeting sternness specifications for gasoline. Isomerization process provides refiners with the advantage of reducing sulfur, olefin, and benzene in the gasoline basin without significantly victimizing the octane. The mathematical modeling of a chemical reaction is a critical tool due to it can used to optimize the experimental data to estimate the optimum operating conditions for industrial reactors. This paper describes light naphtha isomerization reactions over a Pt/Al₂O₃-Cl catalyst at the Al-Dura Oil Refinery (Baghdad, Iraq) using a newly developed universal mathematical model. The proposed kinetic model involves 117 isomerization reactions and 90 cracking reactions to describe 52 real components graded from methane to n-octane. A Genetic Algorithm stochastic optimization technique applied in MATLAB R2020a software was employed to estimate the optimal set of kinetic parameters. The calculated activation energies for hydrocracking reactions was found to be higher than the other reactions because of hydrocracking reactions occur at higher range of temperatures. By benchmarking between the experimental and theoretical results for all 117 data sets, the mean absolute error was obtained to be 0.00360 for all 52 components. Also, a positive effect of increasing reaction temperatures was recognized on enhancing the research octane number (RON).

Intimate relationship between C-I reductive elimination, aryl scrambling and isomerization processes in Au(III) complexes.

19F NMR monitoring shows that heating trans-[AuIIIRf2I2]- solutions (Rf = C6F3Cl2-3,5) leads to formation of cis-[AuRf2I2]-, [AuRf3I]- and [AuRfI3]-via kinetic competition between isomerization and Rf/I scrambling. The system evolution is driven by the easy Rf-I reductive elimination from [AuRfI3]- (forming also [AuI2]-), which is faster than any of the Rf-Rf couplings from the coexisting species, hindering the commonly desired and thermodynamically preferred C-C coupling. A kinetic model where I- dissociation triggers both isomerization and transmetalation steps is proposed, which fits well the experimental data. DFT calculations support that the lower bond strength of AuIII-I compared to other halides produces a pathway switch that makes C-I coupling kinetically preferred. Consequently, it is better avoided in reactions looking for C-C coupling.

Ti3C2 MXenes-based catalysts for the process of α-pinene isomerization.

In this study, the catalytic performance of Ti3C2 MXene materials in the reaction of α-pinene isomerization was demonstrated. The influence of etching agents (HF, HF/H2SO4, and HF/HCl; weight ratios of mixed acids: 1 : 3, 1 : 4, and 1 : 5) on removing Al atoms from MAX phase, creation of an accordion-like structure typical for MXenes and catalytic activity of the produced samples have been revealed. The MXene HF obtained by MAX phase HF treatment exhibited the highest activity (conversion of α-pinene 74.65 mol%), while materials produced with the mixed acids (HF/H2SO4 and HF/HCl) showed a significant reduction in the conversion of α-pinene (on average about 28-fold). However, these last samples displayed an increase of about 10 mol% in the selectivity to the most desirable product-camphene. The high activity of MXene HF is a result of a high concentration of acid sites (11.62 mmol g-1) - the concentration of acid sites in the samples obtained by MAX phase mixed acids treatment was about 2.5-5.5 times smaller. This work proposes possible mechanisms for the α-pinene isomerization reaction on the MXene HF and on the MXene HF/H2SO4X : Y and MXene HF/HCl X : Y in connection with their structure.

A biphenyl thiosemicarbazide based fluorogenic chemosensor for selective recognition of Cd2+: application in cell bioimaging.

A diversified biphenyl thiosemicarbazide based chemosensor (HBMC) has been fabricated and reported for the specific detection of Cd2+ in a MeOH : H2O (4 : 1) solution. We observed a chromogenic change from colorless to light yellow colour, and it showed a "turn-on" fluorogenic change from non fluorescent to blooming cyan colour. In fluorometric titration a sharp "turn-on" emission for Cd2+ was observed with a ∼16 fold increase in fluorescence intensity value at 496 nm by incremental addition of Cd2+ ions in the MeOH : H2O (4 : 1) solution. The reversibility of the chemosensor (HBMC) was confirmed by a sequential addition of the EDTA solution. Again the binding stoichiometry of HBMC with Cd2+ was found to be 2 : 1, as confirmed by Job's plot analysis and HRMS spectra of the HBMC-Cd2+ complex. The mechanism for Cd2+ sensing in MeOH : H2O (4 : 1) is based upon the inhibition of CN isomerization and ESIPT process and simultaneously turning on the CHEF (chelation enhanced fluorescence) process. The limit of detection for Cd2+ was found to be in the order of 10-8 (M), which implies that HBMC is an efficient probe to detect Cd2+ at the microscopic level. A reusability study was performed and on-sight detection of cadmium ions by the chemosensor (HBMC) was established by dip-stick experiment. In vitro detection of Cd2+ in human breast cancer cells (MDA-MB-231) by HBMC discloses its cell permeability and biocompatible nature. Computational studies (DFT and TDDFT) with the probe HBMC and HBMC-Cd2+ complex were also performed.

Isomerization and reaction process of N2O4(H2O) n.

Liquid propellant N2O4 is prone to absorb H2O to form an N2O4(H2O) n system during long-term storage, ultimately generating HNO3, HNO2, and other substances capable of corroding the storage tank, which will adversely affect the performance of weapons and equipment. In this work, the reaction process of the N2O4(H2O) n system is simulated using density functional theory, and the potential energy surface, the geometric configurations of the molecules, the charge distribution, and the bond parameters of the reaction course at n = 0-3 are analyzed. The results show that the potential energy of the system is lower and the structure is more stable when the H2O in the N2O4(H2O) n system is distributed on the same side. When n = 1 or 2, the reaction profiles are similar, and the systems are partly ionic, although still mainly covalently bonded. When n = 3, the charge on the trans-ONONO2 group and the ON-ONO2 bond length change abruptly to -0.503 a.u. and 2.57 Å, respectively, at which point the system is dominated by ionic bonds. At n = 2, a proton-transfer phenomenon occurs in the reaction course, with partial reverse charge-transfer from NO3 - to NO+, making the ON-ONO2 bond less susceptible to cleavage, further verifying that N2O4(H2O) n tends to afford the products directly in one step as H2O accumulates in the system.

Palladium-catalyzed generation of CO from formic acid for alkoxycarbonylation of internal alkenes involves a PTSA-assisted NH-Pd mechanism: a DFT mechanistic study.

DFT calculations have been performed to find the mechanism of the alkyloxycarbonylation of an internal alkene with HCOOH catalyzed by a palladium complex with P,N hemilabile ligands. Four different cycles have been explored in detail, and a plausible catalytic cycle involves the decomposition of HCOOH/HCOOMe to CO, internal alkene isomerization, terminal alkene insertion, CO migratory insertion and methanolysis. It is shown that decomposition and isomerization processes involve a cooperative P,N hemilabile ligand and Pd(0) (NH-Pd) rather than the Pd(II) hydride (Pd-H) mechanism. Intriguingly, the simultaneous presence of PTSA acts as a hydrogen shuttle (H-shuttle), assisting CO generation and methanolysis. With such a mechanism, the rate-determining transition state corresponds to internal alkene isomerization, which is consistent with the experimental observation that isomerization was the slow step in this process. The back-bonding between palladium and olefin and rapid hydrogen transfer in the presence of a PTSA H-shuttle are responsible for the moderate barriers. In addition, a careful study of the solvent effect indicates that polar solvents, which are capable of hydrogen bonding, can promote the catalytic reactions. Mechanistic insights gained by this theoretical study have not only rationalized the experimental observations well but also have implications for new reaction development.

Sequential annulation and isomerisation reaction of 3-acylmethylidene oxindoles with Huisgen zwitterions and synthesis of 5-(3-oxindolyl)oxazoles.

Herein, we report a facile synthesis of 5-(3-oxindolyl)oxazole derivatives via a sequential annulation and isomerisation reaction of 3-acylmethylidene oxindoles with in situ generated Huisgen zwitterions (HZs) from PPh3 and azodicarboxylates. This reaction exhibits good functional group tolerance with 30 examples of structurally diverse products prepared with moderate to good efficiencies (up to 88% yield), thus providing a generally applicable route to the biologically important 5-(3-indolyl)oxazole structural motifs. Key to the success of this sequential one-pot strategy is the utilization of DBU as a base to promote the isomerisation process of the corresponding intermediate annulation products.

A new family of luminescent [Pt(pbt)2(C6F5)L]n+ (n = 1, 0) complexes: synthesis, optical and cytotoxic studies.

Given the widely recognized bioactivity of 2-arylbenzothiazoles against tumor cells, we have designed a new family of luminescent heteroleptic pentafluorophenyl-bis(2-phenylbenzothiazolyl) PtIV derivatives, fac-[Pt(pbt)2(C6F5)L]n+ (n = 1, 0) [L = 4-Mepy 1, 4-pyridylbenzothiazole (pybt) 2, 4,4'-bipyridine (4,4'-bpy) 3, 1,2-bis-(4-pyridyl)ethylene (bpe) 4 (E/Z ratio: 90/10), 1,4-bis-(pyridyl)butadiyne (bpyb) 5, trifluoroacetate (-OCOCF3) 6] and a dinuclear complex [{Pt(pbt)2(C6F5)}2(μ-bpyb)](PF6)27, in which the trans ligand to the metalated C-(pbt) was varied to modify the optical properties and lipophilicity. Their photophysical properties were systematically studied through experimental and theoretical investigations, which were strongly dependent on the identity of the N-bonded ligand. Thus, complexes 1, 3 and 6 display, in different media, emission from the triplet excited states of primarily intraligand 3ILCT nature localized on the pbt ligand, while the emissions of 2, 5 and 7 were ascribed to a mixture of close 3IL'(N donor)/3ILCT(pbt) excited states, as supported by lifetime measurements and theoretical calculations. Irradiation of the initial E/Z mixture of 4 (15 min) led to a steady state composed of roughly 1 : 1.15 (E : Z) and this complex was not emissive at room temperature due to an enhanced intramolecular E to Z isomerization process of the 1,2-bis-(4-pyridyl)ethylene ligand. Complexes 1-3 and 6 showed excellent quantum yields for the generation of singlet oxygen in aerated MeCN solution with the values of ϕ(1O2) ranging from 0.66 to 0.86 using phenalenone as a reference. Cationic complexes 1-3 exhibited remarkable efficacy in the nanomolar range against A549 (lung carcinoma) and HeLa (cervix carcinoma) cell lines with notable selectivity relative to the non-tumorigenic BEAS-2B (bronchial epithelium) cells. In the A549 cell line, the neutral complex 6 showed low cytotoxicity (IC50: 29.40 μM) and high photocytotoxicity (IC50: 5.75) when cells were irradiated with blue light for 15 min. These complexes do not show evidence of DNA interaction.

Catalytic isomerization of glucose to fructose over organic ligands: a DFT study.

Isomerization processes between glucose and fructose catalyzed by four different organic ligands are investigated with quantum chemistry methods in this study. These organic ligands are the carboxylic pendant group, sulfonic pendant group, amino pendant group, and 1H-imidazole ligand. After guessing and verifying a variety of elementary reactions, transition states and energy barriers that are relevant to the optimum pathways have been confirmed. The effective barriers under the catalysis of the carboxylic pendant group, sulfonic pendant group, amino pendant group, and 1H-imidazole ligand are 97.5kJmol-1, 134.7kJmol-1, 146.7kJmol-1, and 167.7kJmol-1, respectively. Then, based on the conclusions of the non-solvation model, the effective barriers in solvents are briefly investigated. The implicit model predicts that solvents bring little improvement or setback to catalyzed reaction models. The explicit model shows that the proton transfer with the participant of water molecules can improve the catalytic performance of Lewis bases in these reactions. The detailed reaction mechanism combing and reliable reaction templates provided in this work will be useful for catalysis designs for glucose transformation to fructose. This work used the computational level of ωB97M-D3BJ/def2-SVP and the software package of ORCA 4.2. For solvent effects, energies of the gas phase were corrected by the combination of C-PCM and SMD.

One-Pot Tandem Nickel-Catalyzed α-Vinyl Aldol Reaction and Cycloaddition Approach to [1,2,3]Triazolo[1,5-a]quinolines.

A one-pot tandem approach to [1,2,3]triazolo[1,5-a]quinolines was developed from (E)-β-chlorovinyl ketones and 2-azidoaryl carbonyls using a sequence of α-vinyl aldol and azide-alkyne cycloaddition reactions. In particular, the intramolecular azide-alkyne cycloaddition of allenol intermediates was readily promoted by a synergistic action of NEt3 and nickel catalysts. Given that the [1,2,3]triazolo[1,5-a]quinolines are useful synthetic precursors to α-diazoimines through ring-chain isomerization process, the subsequent denitrogenative transformations should provide ready access to valuable heterocyclic compounds.