A comprehensive theoretical study was conducted on the thermal Curtius rearrangement of N,N-dimethylcarbamoyl azide in its syn and anti conformations, examining both concerted and stepwise pathways in the gas phase and various solvents. The syn conformer is consistently more stable than the anti conformer by 7.99-10.05 kcal mol-1 and rearranges via a single transition state along a concerted, exergonic pathway to form N,N-dimethylamino isocyanate. The anti conformer undergoes a two-step conversion through an intermediate, with an endergonic first step followed by an exergonic second step. In the gas phase, the concerted pathway dominates, proceeding 101-104 times faster than the stepwise mechanism, while in highly polar solvents the stepwise pathway becomes favored due to solvent effects on relative rates, with NBO analyses providing a rationale for the solvent-dependent rate variations. Potential energy profiles were analyzed at the B3LYP/6-311++G(2d,d,p) level within the electron localization function framework, combined with bonding evolution theory and Thom's catastrophe theory. The concerted pathway proceeds through eight structural stability domains (syn-DMCA:8-CF†TSC†F†E CC†-0:DMAI + N2), whereas the stepwise pathway involves five and eight domains in its first and second steps (anti-DMCA:5-C†CF†C†TS-0:NI + N2 and NI:8-FC†TSFEFCC†-0:DMAI), highlighting the role of the nitrene intermediate. Topological and electronic analyses reveal pronounced asynchronicity in both the concerted mechanism and the second step of the stepwise pathway.

The degradation mechanism of aflatoxin B1 using some reactive oxygen and nitrogen species of plasma-activated water have been investigated theoretically at the M06-2X/aug-cc-pVTZ//M06-2X/6-31G(d) level. Diffusion rate coefficient for all studied reactions was calculated to be ∼109 M-1 s-1 and related activation energy was about 18-19 kJ mol-1. The most favorable pathways of degradation were addition the vinyl bond of terminal furan ring. The apparent rate coefficients triggered by •OH, ozone, •O2-, •NO, and NO3- at 298.15 K were 109, 104, 10-8, 10-7, and 10-41 M-1 s-1, implying that •OH and ozone play efficient role in the degradation while the effect of •O2-, •NO, and NO3- species can be ignored. Overall activation energies associated with the apparent rate coefficients for addition of •OH and ozone to the vinyl bond of terminal furan ring were 17.02 and 18.96 kJ mol-1, while corresponding branching ratios were 82.8 % and 86.28 %, respectively. Ecotoxicity and mutagenicity of major degradation adducts have been estimated using the quantitative structure activity relationships methodologies. Aflatoxin B1 as mutagenic compound does not show acute and chronic toxicity to earthworm and aquatic organisms but was toxic for rats. Mutagenicity of the most abundant oxidation products was negative while the toxicity of them was less than AFB1.

The objective of the present study is to develop a novel nanocomposite platform for drug delivery, and photothermal therapy. Molybdenum disulfide (MoS2) nanosheet, as one of the most stable transitional metal dichalcogenides, indicates unique structure, thermal, and optical properties. In this work, MFC nanocomposite was synthesized from MoS2 nanosheets, iron oxide (Fe3O4) nanoparticles, and copper monosulfide (CuS) nanoparticles. Then structural, morphology, and optical properties of the nanocomposite were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), fourier transform infrared (FTIR), and ultraviolet-visible (UV-Vis) spectroscopies. After that, a photothermal experiment was done for the MFC nanocomposite with different concentrations (50, 100, 150, 200, and 400 ppm). Photothermal experiments indicated that nanocomposite with the concentration of 400 ppm have produced the highest photothermal heat (58.3 ℃ ) after 10 min near infrared (NIR) laser irradiation. Then, a doxorubicin (DOX) drug was loaded into the nanocomposite. It was further studied for in-vitro DOX release with, and without laser irradiation. Results indicated that in the presence of NIR laser irradiation (1 W/cm2), the optimized DOX/MFC nanocomposite show a controlled drug release of 63.5

The effect of external field on the oxidative degradation of AFB1 by plasma activated water was at the M06-2X/aug-cc-pVTZ//M06-2X/6-31G(d) level. For both ·OH addition and ozonolysis of vinyl bond of the terminal furan ring, bimolecular rate coefficients increase with increasing of external field. An increase in the external field leads to an increase in solvent viscosity and, consequently, a decrease in the diffusion rate coefficients. These two opposing effects ultimately result in a decrease in the apparent rate coefficients for ·OH addition and an increase for ozonolysis under the external field. The activation energy for ·OH addition process decreases from 17.02 to 12.17 in the presence of an external field 0.0004 a.u., while the pre-exponential factor decreases by about 12 times. In the ozonolysis process, the activation energy decreases from 10.37 to 10.31, and the pre-exponential factor increases by about 1.26 times. For the degradation of AFB1 by ·OH and ozone in the presence of an external field of 0.0004 a.u., the temperature dependence of the apparent rate coefficients within the range 298.15–320 K is given by lnk = (–1463.8/T) + 27.063 and lnk = (–1240.8/T) + 14.208. It can be concluded that AFB1 degradation is highly diffusion-controlled, with the external field exerting a negative impact on the process.

MoS₂ nanoflakes are emerging as a promising material for photothermal therapy due to their high absorption in the NIR region, large specific surface area, biocompatibility, efficient photothermal conversion, and ability to be functionalized for targeted therapy. In this paper, MoS₂ nanoflakes were incorporated to Fe3O4 nanoparticles, gold nanorod (GNR), and copper sulfide (CuS) (MCG nanocomposite) to investigate chemo-photothermal therapy in this nanocomposite. The structural and optical properties of the MCG nanocomposite were characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), Zeta potential, Dynamic Light Scattering (DLS), Fourier transform infrared (FTIR), and Ultraviolet-visible (UV-Vis) spectroscopies. The photothermal results of samples indicated that MCG nanocomposite produced higher photothermal heat than each individual sample alone (808 nm NIR laser irradiation at a power density of 1 W/cm2 after 10 min). Under NIR laser irradiation, the release of DOX was greatly accelerated at pH = 5.5 as compared to pH = 7.4. So, this nanocomposite can be used as dual responsive systems, with DOX release controllable through pH and NIR irradiation. Finally, MTT assays experiment showed that, using NIR irradiation, the relative viabilities of HeLa cells decreased when the concentration of drug increased. Hence MCG nanocomposite could be a potent system for targeted drug delivery and synergistic chemo-photothermal cancer therapy.

Atmospheric oxidation of the p-chloroaniline-OH center dot adduct [C6H4ClNH2-OH](center dot) (AD-C2) by (3)Sigma(-)(g) O-2 and internal isomerization processes of peroxy radical [C6H4ClNH2-OH](center dot)-O-2 are theoretically investigated at the M06-2X/aug-cc-pVTZ and CBS-QB3//M06-2X/aug-cc-pVTZ level of theories. Potential energy surfaces (PESs) for the most efficient pathways indicated that the oxidation process begins via the complexation of individual reactants in syn mode forming PRCy-iOO-syn (y = 2,5) in an exothermic and endogenic step. The syn mode addition is favored over the anti one due to the formation of internal hydrogen bond between the hydroxyl and peroxy groups. Formation of new C5-OO bond in PRCy-iOO-syn complex is an unimolecular process which is exothermic and exoergic. This pathway is predominated over other internal conversions due to the presence of stronger intramolecular hydrogen bond. Cyclization of the produced [C6H4ClNH2-OH](center dot)-O-2 peroxy radical AD-C2-5OO-syn into the bicyclic peroxy radical AD-C2-5,6OO-syn is the last step which is strongly endothermic and endogenic. The rate coefficients are calculated by means of the RRKM theory over the temperature range 250-350 K and at a pressure range of 0.1 bar to the high-pressure limit. The RRKM rate coefficients at the M06-2X/aug-ccpVTZ level for the first bimolecular and last unimolecular steps are in order of 10(-16) cm(3) molecule(-1) s(-1) and 10(-7) s(-1), respectively, while the obtained rate coefficients at the CBS-QB3//M06-2X/aug-cc-pVTZ are overe-stimated about two order of magnitude.

An innovative and comprehensive theoretical investigation was conducted to examine the thermal Curtius rearrangement of malonyl azide in its syn-syn and syn-anti conformations, taking into account both the concerted and stepwise pathways. This study covered analyses performed in gaseous environments and a range of solvents. In both the gas phase and different solvents, the syn-syn conformation of malonyl azide proves to be more stable than the syn-anti conformation with a stability difference ranging from 4.15 to 4.99 kcal mol-1. It undergoes an exergonic concerted process with a single transition state, leading to the formation of syn-2-isocyanatoacetyl azide. Furthermore, syn-2-isocyanatoacetyl azide can be converted into methylene diisocyanate via a concerted pathway. In contrast, the rearrangement of the syn-anti conformation involves two transition states and an intermediate. The initial step is endergonic, followed by an exergonic subsequent step. The calculated Delta G values for the conversion of syn-syn-MA to syn-ICA and syn-ICA to MDI in the gas phase, determined at the CBS-QB3 level of theory, are -62.91 and -64.67 kcal mol-1, respectively. Meanwhile, the Gibbs free energies for the first and second steps of the rearrangement of syn-anti conformation are 10.51 and -77.98 kcal mol-1, respectively. Theoretical results indicate the dominance of the concerted pathway, surpassing the stepwise mechanism by roughly 104-106 and 104 times in both the gas phase and various solvents, respectively. Analyzing the electron localization function using the B3LYP/6-311++G(2d,d,p) level of theory unveils the catastrophe sequences for syn-syn malonyl azide and syn-2-isocyanatoacetyl azide structures, denoted as 8-CF dagger C dagger TSF dagger C dagger C dagger C and 9-CF dagger C dagger TSFC dagger FC dagger C-0, respectively. The Curtius rearrangement of the syn-syn malonyl azide conformer commences with the transformation of two valence bonding disynaptic attractors, where V1,2(N2,N3) merges into a single disynaptic attractor. This is followed by the division of the non-bonding monosynaptic attractor V(N1) into two non-bonding monosynaptic attractors. Subsequently, the N1-N2 bond breaks, eliminating a nitrogen molecule and altering the topological signature of C1-N1. This transformation leads to the consolidation of the pair of non-bonding monosynaptic attractors V1,2(N1) into a single non-bonding monosynaptic attractor V(N1). Then, the C1-C2 bond breaks, resulting in the formation of pseudo-radical centers on the C1 and C2 atoms. Following this, a transformation in the topological signature of C1-N1 occurs, leading to the elimination of pseudo-radical centers on the C1 atom and the formation of a C2-N1 bond. The results of ELF calculations indicate that the Curtius rearrangement of syn-ICA follows a method similar to that of syn-syn. The results indicate that the reaction follows a concerted mechanism but is highly asynchronous, with absolute asynchronicity indices of 0.801 and 0.763 for the Curtius rearrangement of syn-syn-MA and syn-ICA, respectively.

Hercynite magnetic nanoparticles were produced through the co-precipitation of ferrous and aluminum cations. The surface of hercynite was respectively coated with silica, 2,4,6-trichloro-1,3,5-triazine, and 1H-pyrazole-3,5-dicarboxylic acid to provide a suitable substrate for Pd(II) loading, furnishing Pd@Her-TCT-PDA. Subsequently, the introduced Pd(II) was reduced to Pd(0) using NaBH4. FT-IR, EDS, XRD, TGA, TEM and SEM images were the characteristic methods to prove the success of catalyst synthesis. The SEM image illustrated the particles with a nanosize of 25-50 nm and TEM image confirmed the presence of Pd nanoparticles with sizes lower than 2 nm. EDS elemental analysis of the catalyst proved the existence of Pd, Fe, and Al atoms along with the C, O, N, and Si atoms belong to the heterocyclic moieties. VSM analysis clarified a considerable drop in the magnetic properties of the hercynite core of the final catalyst due to its modified surface. TGA curve demonstrated that Pd@Her-TCT-PDA contains 20% organic content, attributed to the anchored heterocyclic ligands. Finally, Pd@Her-TCT-PDA was employed along with NaBH4 as a catalytic system to reduce completely the nitro group of aromatic compounds to their corresponding amines. The recyclability tests showed low drop in the catalytic activity of Pd@Her-TCT-PDA after third run with negligible leaching of Pd NPs.

Aza-Diels-Alder cycloaddition reaction is a critical synthetic method for the production of bioactive tetrahydroquinolines. To this aim, an imine obtained from the reaction of an aniline derivative and a carbonyl compound is cyclized with an alkene in the presence of a catalyst. In this research, some tetrahydroquinoline compounds are synthesized through aza-Diels-Alder reaction in the presence of a prepared Ce(III) immobilized on the functionalized halloysite (Ce/Hal-TCT-IDA) as a catalyst. Ce/Hal-TCT-IDA was prepared by incorporation of aminopropyl silane on the halloysite surface, followed by treatment with 2,4,6-trichloro-1,3,5-triazine (TCT) and iminodiacetic acid (IDA), and loading cerium nitrate. Then, it was characterized and analyzed by different analytical methods, indicating the amorphous agglomerated grains (20-60 nm), containing 0.00196 mmol g-1 Ce(III) ions. The catalytic activity and reusability of Ce/Hal-TCT-IDA were studied in this research.

Atmospheric oxidation mechanism of predominant catechol-OH adduct [C6H6O2 OH]* (AD2) by oxygen molecule in its triplet electronic ground state and isomerization processes of catechol peroxy radicals [C6H6O2 OH]* O2 into bicyclic peroxy radicals have been studied at the M06-2X/aug-cc-pVTZ level in conjugation with the RRKM theory. The first step begins via the complexation of [C6H6O2 OH]* with oxygen molecule and formation of two pre-reactive van der Waals complexes in syn and anti modes. Syn mode addition of O2 is more favorable over the anti mode due to the formation of intramolecular hydrogen bond. Kinetically and thermodynamically, addition of O2 at the C5 position in syn mode, namely peroxy radical AD25OO-syn, is the most efficient process with bimolecular RRKM rate coefficient 2.80x10 16 cm3 molecule 1 s 1 at ambient conditions. Isomerization (cyclization) of peroxy radical AD2-5OOsyn into bicyclic peroxy radicals via the formation of OO bridge are strongly endothermic and nonspontaneous processes with high activation energies. Ring closure into the bicyclic peroxy radical AD2-5,6OO-syn is the most favorable process with unimolecular RRKM rate coefficient 1.41x10 8 s 1 at ambient conditions.

Density functional theory (DFT) calculations at the M06-2X/def2-TZVP level have been employed to investigate the atmospheric oxidation mechanism of anthracene (ANT) initiated by HO center dot. Direct hydrogen atom abstraction from the ANT using HO center dot takes place hardly at ambient conditions while addition of HO center dot to the C1, C2, and C4 sites are thermodynamically and kinetically more advantageous. The addition reactions are controlled by the aromaticity and the kinetic trends were justified by resonance stabilization energies. The rate constants were calculated by using the Rice-Ramsperger-Kassel-Marcus (RRKM) and canonical transition state theory (CTST) methods in conjugation with zero curvature tunneling (ZCT). The overall RRKM-bimolecular rate constant at ambient conditions is 6.72 x 10(-12) cm(3) molecule(-1) s(-1), is negatively dependent on the temperature and can be expressed as k(250-350)(1bar) = 3.92 x 10(-14) exp(1534.9/T). Contribution of the AD-C4 path in the overall reaction is about T70-80%, implying that the dependence of overall rate constant on pressure can be ignored. The kinetic data exhibit that the ANT is degraded during its long-range transport in the atmosphere and cannot be classified as persistent organic pollutants.

The atmospheric degradation of chlorotrifluoroethylene (CTFE) by OH˙ was investigated using density functional theory (DFT). The potential energy surfaces were also defined in terms of single-point energies derived from the linked cluster CCSD(T) theory. With an energy barrier of -2.62 to -0.99 kcal mol-1 using the M06-2x method, the negative temperature dependence was determined. The OH˙ attack on Cα and Cβ atoms (labeled pathways R1 and R2, respectively) shows that reaction R2 is 4.22 and 4.42 kcal mol-1, respectively, more exothermic and exergonic than reaction R1. The main pathway should be the addition of OH˙ to the β-carbon, resulting in ˙CClF-CF2OH species. At 298 K, the calculated rate constant was 9.87 × 10-13 cm3 molecule-1 s-1. The TST and RRKM calculations of rate constants and branching ratios were performed at P = 1 bar and in the fall-off pressure regime over the temperature range of 250-400 K. The formation of HF and ˙CClF-CFO species via the 1,2-HF loss process is the most predominant pathway both kinetically and thermodynamically. With increasing temperature and decreasing pressure, the regioselectivity of unimolecular processes of energized adducts [CTFE-OH]˙ gradually decreases. Pressures greater than 10-4 bar are often adequate for assuring saturation of the estimated unimolecular rates when compared to the RRKM rates (in high-pressure limit). Subsequent reactions involve the addition of O2 to the [CTFE-OH]˙ adducts at the α-position of the OH group. The [CTFE-OH-O2]˙ peroxy radical primarily reacts with NO and then directly decomposes into NO2 and oxy radicals. "Carbonic chloride fluoride", "carbonyl fluoride", and "2,2-difluoro-2-hydroxyacetyl fluoride" are predicted to be stable products in an oxidative atmosphere.

A comprehensive theoretical study has been performed for the Schonberg rearrangement of O,O-diphenyl carbonothioate to O,S-diphenyl carbonothioate. The rate constant from the CBS-QB3/Eckart method in diphenyl ether was expressed via two-and three-parameters conventional Arrhenius equations k = 1.34 x 10(13)exp (-21550.4/T) and k = 1.09 x 10(10)T(0.997)exp( -2.1089.7/T) respectively. The topological analyses have been performed at the B3LYP/CBSB7 level to unravel the molecular mechanism of the Schonberg rearrangement. The sequence of turning points was 3-C dagger C-TS-0 and can be described by the following: (a) transformation of V(C-1,O-1) valence basin into two monosynaptic basins V(C-1) and V-3(O-1) accounting for the homolytic breaking of C-1-O-1 bond; (b) merging of monosynaptic basins V(C-1) and V-3(S) into the single disynaptic basin V(C-1,S) accounting for the C-1- to-S coupling of pseudoradical centers; and formation of new C-1 -S bond. The first turning point takes place near the saddle point indicating that activation energy of the Schonberg rearrangement is mainly associated with the breaking of single C - O bond.

Atmospheric oxidative degradation of p-chloroaniline (PCA) initiated by OH' has been studied theoretically at the M06-2X/aug-cc-pVTZ and CBS-QB3//M06-2X/aug-cc-pVTZ levels, coupled with kinetic calculations using the RRKM/ZCT method over the temperature range of 250-350 K. The calculations exhibit that the OH' addition and hydrogen atom abstraction pathways are thermodynamically favorable. RRKM results revealed that the atmospheric oxidation of PCA is dominated by OH addition to the C1 and C2 atoms and hydrogen atom abstraction from amino group. The individual and overall rate coefficients of PCA reaction triggered by OH' at 1 bar are negatively linear dependent on the temperature and their values are consistent with the experimental data. RRKM calculations also show that the transition state theory approximation for estimation of rate coefficients at ambient pressure breaks down and very high pressures are essential to be valid. The atmospheric lifetime at the benchmark CBS-QB3 level is smaller than 2 days.

The heating of O-furfuryl S-methyl xanthate in p-xylene solvent that is known from the literature to yield in parallel S-furfuryl S-methyl dithiocarbonate and furfuryl methyl sulfide via the thione-to-thiol rearrangement and carbon oxysulfide extrusion, respectively, have been studied theoretically. The CBS-QB3 energies in conjugation with the solvation model density and B3LYP/6-311G(2d,d,p) monodeterminantal wave functions have been used to investigate the kinetics of the parallel reaction by means of canonical transition state theory and molecular mechanism of the thione-to-thiol rearrangement by means of topological approaches. According to the supplied kinetic data the considered reactions are assisted strongly by the solvent molecules implying implicit solvent model cannot account properly the effect of solvent media. The cross topological analysis of the thione-to-thiol rearrangement via [1,3]-sigmatropic rearrangement revealed that the electron density flow along the reaction is not concerted and the sequence of catastrophes can be summarized as 4-(EFC)-C-dagger-0. In simple chemical term, chemical events through the reaction are heterolytic breaking of C-O bond, formation of pseudoradical center on the C atom, and creation of a new chemical C-S bond via the C-to-S coupling of pseudoradical centers, respectively.

The complete theoretical study of thermal Curtius rearrangement of syn-syn and syn-anti conformers of oxalyl diazide, in the gas phase and in solution has been established for the first time. The inexplicit solvent effect was taken into account via the self-consistent reaction field (SCRF) method. The gas and solution phases of all optimized geometries of the mentioned conformers associated with the Curtius rearrangement along the concerted and stepwise pathways were reported using the polarized continuum model and non-electrostatic terms from the SMD universal solvation model. The Curtius rearrangement of syn-syn and syn-anti conformers was taken place via concerted and stepwise pathways, respectively. The syn-syn conformer of oxalyl diazide is more stable than the syn-anti conformer in the gas phase and solution, and rearranged to syn-carbonyl azide isocyanate via an exergonic concerted mechanism with a single transition state. Nevertheless, the rearrangement of syn-anti conformer occurred through the two transition states and an intermediate, which the first and second steps are endergonic and exergonic, respectively. Theoretical results point out that the concerted pathway is predominant with 102-106 and 104-105 times faster than the stepwise mechanism in gas phase and solution, respectively. Topological analysis of the electron localization function at the B3LYP/6-311++G (2d,d,p) level of theory indicate that the catastrophe sequence 1-6-C†TSC†F C†C-0 begins with the N4-N5 bond breaking, elimination of nitrogen molecule and increasing of non-bonding monosynaptic attractor on N4 atom, and then changing of topological signature of C2-N4 bond, breaking of C1-C2 bond, and formation of pseudo-radical centers on C1 and C2 atoms. Subsequently, annihilation of pseudo-radical centers on the C1 atom, change of topological signature of C2-N4 and formation of C1-N4 bond were executed. The obtained results of ELF calculations show that the reaction takes place via a concerted mechanism but highly asynchronous process.

Kinetics and molecular mechanism of the Newman–Kwart rearrangement (NKR) of N , N -dimethyl O -arylthiocarbamate into N , N -dimethyl S -arylcarbamate have been investigated theoretically.

Gas phase oxidation of catechol with hydroxyl radical is expected as dominant atmospheric removal process. The mechanism and kinetics of OH.-initiated atmospheric oxidation of catechol was investigated theoretically by employing of M06-2X/aug-cc-pVTZ level of theory at 300 K and 760 Torr by considering of OH. addition and H-atom abstraction reactions. Oxidation of catechol begins with reversible formation of pre-reactive molecular complex and its conversion to products in unimolecular manner. Fall-off pressure expression indicated that canonical transition state theory breaks down to estimate rate constant at 760 Torr. RRKM unimolecular rates were corrected for basis set superposition error and quantum tunneling effects. RRKM bimolecular rates for OH. addition and H-atom abstraction pathways at 300 K and 760 Torr were about 10(-12) cm(3) molecule(-1) s(-1). The RRKM bimolecular rate for oxidation of catechol triggered by OH. at 300 K and 760 Torr was 9.45x10(-12) cm(3) molecule(-1) s(-1) and its temperature dependence over 200-400 K can be expressed by the lnk=(2929.8/T)+(5.82x10(-16)), indicating that reaction rate is negatively dependent on the temperature. H-atom abstraction from the hydroxy group at the C-2 position and addition of OH. onto the C-2 atom are the most favorable processes. Evolution of branching ratios demonstrate that the OH.-initiated oxidation of catechol is not essentially selective process.

The CBS-APNO and CBS-QB3 model chemistries have been used to study the temperature- and pressure-dependent kinetics of degenerate Cope rearrangement of hypostrophene. The rate constants are calculated by means of RRKM theory and corrected by the Wigner tunneling correction. The high- and low-pressure limits of the rate constants reveal that the TST is valid to estimate the rate constant at 1 bar and the reaction in the bimolecular region cannot be observed experimentally. The estimated rate constant and activation energy at 1 bar and 308 K are 10(-2) s(-1) and 89 kJ.mol(-1), respectively, such that the homoaromatic transition structure is stabilized by 85 kJ.mol(-1) because of the interactions between the allyl moieties. Evolution of chemical events along the reaction has been analyzed by the BET together with the NCI and AIM topological approaches at the B3LYP with 6-311G(d,p) basis set. The progress of reaction was monitored by five SSDs and controlled by the succession of catastrophes C-dagger[F](2)(TS)[F-dagger](2)C. The sequential chemical events consist of homolytic rupture of C-C bond and formation of pseudoradical centers on carbon atoms, disappearance of the generated pseudoradical centers, formation of new pseudoradical centers on two carbon, and formation of new C-C single bond through the C- to -C coupling of the generated pseudoradical centers. The NCI and AIM analyses have been performed to study the nature of the interaction in the regions where bond rupture/formation occur.

In this work, without using any linker or chemical modification of graphene oxide, a zinc oxide immobilized graphene oxide-based catalyst was used for the direct aerobic oxidative conversion of alcohols to the nitriles in water. In the first step, graphene oxide was prepared and then zinc ions were electrostatically adsorbed onto the surface of graphene oxide. In the following step, zinc oxide nanoparticles were generated via in-situ growth in presence of NaOH. It was illustrated that graphene oxide layers can control the size of in-situ generated zinc oxide nanoparticles. Various aromatic/aliphatic/heteroaromatic primary alcohols converted to the nitriles in high yields under O2 balloon with ZnO/GO catalyst. This catalyst can be used for 7 successful consecutive runs without significant loss of activity.