Curcumin-derivatives as fluorescence-electrochemical dual probe for ultrasensitive detections of picric acid in aqueous media.

We are reporting the two curcumin derivatives, ferrocenyl curcumin (Fc-cur) and 4-nitro-benzylidene curcumin (NBC), as a probe through dual modalities, i.e., fluorescence and electrochemical methods, for the detection of nitro-analytes, such as picric acid (PA). The probes exhibited aggregation-induced enhanced emission (AIEE), and the addition of picric acid (PA) demonstrated good and specific fluorimetric identification of PA in the aggregated state. By using density functional theory (DFT), the mechanism of picric acid's (PA) interactions with the probes was further investigated. DFT studies shows evidence of charge transfer from curcumin derivatives probe to picric acid resulting into the formation of an adduct. The reduction of trinitrophenol (PA) to 2, 4, 6-trinitrosophenol was investigated utilizing a probe-modified glassy carbon electrode (GCE) with a good detection limit of 9.63 ± 0.001 pM and 41.01 ± 0.002 pM, respectively, for Fc-cur@GCE and NBC@GCE, taking into account the redox behavior of the probe. The applicability of the designed sensor has been utilized for real-time application in the estimation of picric acid in several water samples collected from the different source.

Thermodynamic and optical properties of HCOOH(H2O)n and HCOOH(NH3)(H2O)(n-1) clusters at various temperatures and pressures: a computational study.

Density functional theory has been used to compute the gas-phase geometries, binding energies, ZPE-corrected binding energies, BSSE-corrected binding energies, binding enthalpies, and binding free energies of HCOOH(H2O)n and HCOOH(NH3)(H2O)(n-1) clusters with n = 1-8, 10, 12, 14, 16, 18, and 20. Enthalpies and free energies are calculated for a range of atmospherically relevant temperatures (T) and pressures (P) (from T = 298.15 K, P = 1013.25 hPa to T = 216.65 K, P = 226.32 hPa). The optical properties of those clusters have been studied at the CAM-B3LYP/aug-cc-pVDZ level of theory.

Chemically induced crosslinked enhanced emission of carbon polymer dots discerning healthy and cancer cells through pH-dependent tunable photoluminescence.

Chemically induced crosslinked enhanced emission (CEE) of urea and citric acid-derived carbon polymer dot (CPD) nanoparticles is established here with a rare zero linker approach, i.e. without the use of any separate crosslinkers. Such chemical CEE like any chemical reaction was achieved through amide bond formation using carbodiimide chemistry, pointing towards the feasibility of developing a general methodology for their formation through engineering the nanoparticle surface functionality. Exhaustive characterization was done to pinpoint the structure, morphology, and photophysics of the CPDs and concurrently eliminate the possibility of the involvement and interference by molecular fluorophores for the unique optical tuning of the CPDs. The structure-photophysics relation was further restated through theoretical studies involving density functional theory (DFT) that correlated significantly well with the experimental findings. Most interestingly, the CPDs revealed pH responsiveness due to the formation or hydrolysis of amide bonds with acid or base, respectively, which was manifested through a spectacular change in fluorescence emission visible to the naked eye through UV illumination. This distinct pH-dependent photoluminescence properties of CPDs opens up an enormous opportunity for interesting applications, including discriminating normal and cancerous cells, which we demonstrate herein as a proof of concept through in vitro imaging.

Absorption of Volatile Organic Compounds Toluene and Acetaldehyde in Choline Chloride-Based Deep Eutectic Solvents.

Unrestricted emission of volatile organic compounds (VOCs)─a threat to human health and the environment─can be controlled to a large extent by the capturing mechanism. Few recent experimental studies explored the efficacy of the deep eutectic solvent (DES), a designer solvent with some fascinating properties, as a VOC-capturing medium. Through the partition coefficient measurement, it was found that the choline chloride-based DESs exhibit excellent VOC-capturing potencies. However, a molecular picture of the above absorption process is still lacking. Here, we study the molecular mechanism of the absorption of two commonly occurring VOCs, toluene and acetaldehyde, in two different choline chloride-based DESs with varying donor molecules, urea, and levulinic acid via the molecular dynamics simulation technique. Strong absorption of the VOCs is observed in both the DESs. The free energy profile for the absorption process has been explored using the umbrella sampling method. The VOCs are preferentially solvated near the liquid/vapor interface. The simulated partition coefficients for the VOCs from the vapor to the liquid phase show good agreement with the experimental results. Detailed analyses of the spatial and orientational structure of the VOCs and different components of DESs are performed to elucidate the interaction among them. The above analyses have indicated that DES is a better VOC-capturing medium compared to a room-temperature ionic liquid, which is more extensively studied in the literature.

Synthetic utility of biomimicking vanadium bromoperoxidase and n-tetrabutylammonium tribromide (TBATB) in organic synthesis.

Nature has established a broad spectrum of methods to introduce halogen atoms in organic compounds. Recent developments have revealed that haloperoxidases are one of the major sources responsible for incorporating bromines to produce bromoorganics in nature. Pioneering studies of numerous researchers have unravelled the details of haloperoxidases, mainly vanadium dependent enzyme bromo- and iodo-peroxidases, including reaction mechanism, kinetics and especially biomimicking studies. In this review, we initially have described the scope of biomimicking vanadium bromoperoxidase in producing the bromonium ion and its further utilisation in conducting oxidative bromination or cleavage of various organic molecules. Moreover, by biomicmicking, the synthesis of OATB and the synthetic utility of various organic ammonium tribromides (OATBs) have been discussed. Among such OATBs, n-tetrabutylammonium tribromide (TBATB) has been explored for bromination of organic molecules as well as in the facile removal of several protecting groups and as a potential catalyst in various synthetic transformations. This review attempts to compile a myriad of reactions concerning the catalytic activity of vanadium bromoperoxidases and the usefulness of various OATBs, particularly with special emphasis on TBATB in various organic transformations.

Thermodynamic properties of forming methanol-water and ethanol-water clusters at various temperatures and pressures and implications for atmospheric chemistry: A DFT study.

The gas-phase geometries, binding energies, enthalpies, and free energies of methanol-(water)n and ethanol-(water)n clusters containing n=1-10,20,30,40, and 50 water molecules have been calculated using density functional theory. The binding energies are calculated at 0 K. The enthalpies are calculated at a temperature of 298.15 K and pressure of 1013.25 hPa (1 atm). The free energies are calculated at a wide range of temperature (T) and pressure (P) (from T = 298.15 K, P = 1013.25 hPa to T = 216.65 K, P = 226.32 hPa). The results show that the free energy of the formation of a specific cluster from its free molecules is negative (i.e., favorable) only below some critical temperature and pressure, which depends on the cluster's size. One of the most common volatile organic compounds (VOCs) in the troposphere is methanol, ethanol, and atmospheric aerosols containing methanol and ethanol. The Rayleigh scattering properties of methanol-water and ethanol-water clusters have been investigated. The scattering intensities were computed at static (∞ nm) and different wavelengths (700, 600, 500, and 400 nm) of naturally polarized light. Rayleigh scattering intensities increase about 9%-10% at 400 nm compared to the static limit (∞ nm) for both methanol-water and ethanol-water clusters.

Cyanomethyl Ether as an Orthogonal Participating Group for Stereoselective Synthesis of 1,2-trans-ß-O-Glycosides.

Stereoselective formation of glycosidic linkages has been the prime focus for contemporary carbohydrate chemistry. Herein, we report cyanomethyl (CNMe) ether as an efficient and effective participating orthogonal protecting group for the stereoselective synthesis of 1,2-trans-ß-O-glycosides. The participating group facilitated good to high ß-selective glycosylation with a broad range of electron-rich and electron-deficient glycosyl acceptors. Detailed experimental and theoretical studies reveal the involvement of CNMe ether in the formation of a six-membered imine-type cyclic intermediate for the observed stereoselectivity. Rapid incorporation and selective removal of the CNMe ether group in the presence of benzyl ether and isopropylidene acetal protection have also been reported here. The nitrile group provided an opportunity for the glycodiversification through further derivatizations.

A dielectric and spectrophotometric study of the tautomerization of 2-hydroxypyridine and 2-mercaptopyridine in water.

The basic ionization (pk 1) and acidic ionization (pk 2) constants and equilibrium constant (K T) of 2HPy and 2MPy were determined. The pk 1(s) of their N- and X-methyl derivatives (X = O, S) were also determined. The equilibrium constant of 2MPy is approximately 60 times greater than its oxygen analog, 2HPy. The micro-ionization constants of the functional groups, -NH (pk A and pk C) and -XH (pk B and pk D), were determined to provide further insights into the ionization equilibria of these N-heteroaromatic XH compounds (2HPy and 2MPy). The relaxation time of water (τ) in aqueous solutions of 2HPy and 2MPy are collectively used with the K T values to determine the forward (k f) and backward (k b) rate constants of tautomerization. Subsequently, the k f and k b are used to provide the rationale for the K T and τ values.

Theoretical studies of hydrogen abstraction from H2X and CH3XH (X = O, S) by trichloromethyl radicals.

We have theoretically investigated the hydrogen abstraction reactions of H2O, H2S, CH3OH, and CH3SH by the CCl3 radical, which is of interest in atmospheric chemistry research. In this study, mechanistic and kinetic analyses for the title reactions have been performed at the W1 and the CCSD(T)/cc-pVTZ//M06-2X/cc-pVTZ level. Standard Gibbs free energies for all reaction channels at the W1 level with ZPE corrections were also calculated. Intrinsic Reaction Coordinate (IRC) calculations were performed to verify the connectivity of all the transition states with the reactants and products. All rate coefficients are computed by conventional transition state theory (CTST) with the zero-curvature tunneling (ZCT) and also Wigner's tunneling (W) correction in the temperature range from 200 K to 2000 K. The rate coefficients for each reaction channel are also evaluated by canonical variational transition state theory (CVT) with the small-curvature tunneling correction method (SCT) in the same temperature range. Three-parameter Arrhenius expressions have been obtained by fitting to the computed rate coefficients of all abstraction channels between 200 and 2000 K. The branching ratios for these reactions have been determined. This study provides the first theoretical and kinetic determination of the CCl3 rate coefficient for reactions with H2O, H2S, CH3OH, and CH3SH over a large temperature range.

Rapid synthesis of polysubstituted phenanthridines from simple aliphatic/aromatic nitriles and iodo arenes via Pd(ii) catalyzed domino C-C/C-C/C-N bond formation.

An efficient and straightforward method has been developed for the synthesis of polysubstituted phenanthridines from simple aryl iodides and alkyl/aryl nitriles via the palladium-catalyzed nucleophilic addition of aryl iodides to nitriles followed by cascade formation of C-C and C-N bonds viz. in situ generated imine directed sequential two fold C-H activation.

Bonding and spectroscopic analyses of N2O-CS2 and N2O-OCS heterodimer complexes and their atmospheric consequences.

Different isomers of the valence isoelectronic pairs of the heterodimers N2O-SCS and N2O-OCS were investigated using MP2 and CCSD(T) methods with the aug-cc-pVXZ (X = D, T) basis set with anharmonic frequency calculations. Interaction energies of both the heterodimers were estimated at the CBS limit and for CCSD(T)/aug-cc-pVTZ. One isomer was located for the N2O-SCS heterodimer. In the case of the N2O-OCS heterodimer, three planar slipped-parallel isomers were characterized. There was no significant change in electron density at the bond critical points (BCPs) of various intra-bonds but the presence of inter-bonds with a weak electron density at the BCPs in the complexes was found as per the results from the quantum theory of atoms in molecules (QTAIM) analysis. The interorbital interactions of the monomer in the heterodimers are discussed herein in terms of the natural bond orbital (NBO) charge transfer. Symmetry-adapted perturbation analysis was performed for all the isomers. In the case of the stable complex of N2O-SCS, induction dominated over the dispersion energy. Among the N2O-OCS isomers, the dispersion effect predominates for the most stable isomer, while for the other two isomers, the induction effect is dominant. Frequency calculations for these complexes showed a number of interactions induced by the low frequency modes in the far IR region. The atmospheric implications are also discussed for these complexes.

Primary Amide Directed Regioselective ortho-C-H-Arylation of (Aryl)Acetamides.

An efficient and regioselective palladium(II)-catalyzed primary acetamide assisted ortho arylation of arylacetamide has been discovered. This is the first report where functionalizable primary acetamide (-CH2CONH2) is used as a directing group for C(sp2)-H activation/cross-coupling reactions, circumventing the extra steps of installation and subsequent removal of the directing groups. The synthetic utility of this transformation is demonstrated through the scale-up synthesis. In addition, the primary acetamide can be manipulated into synthetically important derivatives such as nitriles and carboxylic acids.

A theoretical investigation of the energetics and spectroscopic properties of the gas-phase linear proton-bound cation-molecule complexes, XCH(+)-N2 (X = O, S).

The structural features, spectroscopic properties, and interaction energies of the linear proton-bound complexes of OCH(+) and its sulfur analog SCH(+) with N2 were investigated using the high-level ab initio methods MP2 and CCSD(T) as well as density functional theory with the aug-cc-pVXZ (X = D, T) basis sets. The rotational constants along with the vibrational frequencies of the cation-molecule complexes are reported here. A comparison of the interaction energies of the OCH(+)-N2 and SCH(+)-N2 complexes with those of the OCH(+)-CO and OCH(+)-OC complexes was also performed. The energies of all the complexes were determined at the complete basis set (CBS) limit. CS shows higher proton affinity at the C site than CO does, so the complex OCH(+)-N2 is relatively strongly bound and has a higher interaction energy than the SCH(+)-N2 complex. Symmetry-adapted perturbation theory (SAPT) was used to decompose the total interaction energies of the complexes into the attractive electrostatic interaction energy (E elst), induction energy (E ind), dispersion energy (E disp), and repulsive exchange energy (E exch). We found that the ratio of E ind to E disp is large for these linear proton-bound complexes, meaning that inductive effects are favored in these complexes. The bonding characteristics of the linear complexes were elucidated using natural bond orbital (NBO) theory. NBO analysis showed that the attractive interaction is caused by NBO charge transfer from the lone pair on N to the σ*(C-H) antibonding orbital in XCH(+)-N2 (X = O, S). The quantum theory of atoms in molecules (QTAIM) was used to analyze the strengths of the various bonds within and between the cation and molecule in each of these proton-bound complexes in terms of the electron density at bond critical points (BCP). Graphical Abstract Linear proton-bound complexes of OCH(+)-N2 and SCH(+)-N2. In these complexes, inductive effect is favored over dispersive effect. The attractive interaction is the NBO charge transfer from N-lone pair of N2 to CH σ* antibonding orbital of XCH(+) (X = O, S).

Bonding and spectroscopic properties of complexes of SO2-O2 and SO2-N2 and its atmospheric consequences.

van der Waals complexes of sulfur dioxide (SO2) with oxygen (O2) and nitrogen (N2) have been investigated by using MP2 and aug-cc-pVXZ (X = D, T) basis set. Two minimum structures with symmetry C1 and Cs have been located at the intermolecular potential energy surface (IPES) of the complex of SO2-O2. Stacked Cs structure of SO2-O2 is found to have greater stability than C1 structure. In the case of SO2-N2, one minimum structure with Cs symmetry has been characterized. In this study, CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ and interaction energy calculation at complete basis set (CBS) limit has been employed for better energetic description. The natural bond orbital (NBO) calculation demonstrates the bonding in terms of charge transfer from X-atom lone pair of X2 (X = O or N) to the antibonding SO orbital of SO2. The strength of various intra and inter bonds in the complexes were calculated in terms of electron density at bond critical points (BCP) using quantum theory of atoms in molecules (QTAIM). Frequency calculations for these complexes show a number of interactions induced by low frequency modes in the far IR region. Symmetry adapted calculation were also computed for the complexes and is established that the ratio of dispersion to induction effect is large for the most stable conformers. The atmospheric implications are also discussed for these complexes.

Reaction of chlorine radical with tetrahydrofuran: a theoretical investigation on mechanism and reactivity in gas phase.

Reaction of chlorine (Cl) radical with heterocyclic saturated ether, tetrahydrofuran has been studied. The detailed reactivity and mechanism of this reaction is analyzed using hybrid density functional theory (DFT), B3LYP and BB1K methods, and aug-cc-pVTZ basis set. To explore the mechanism of the reaction of tetrahydrofuran with Cl radical, four possible sites of hydrogen atom (H) abstraction pathways in tetrahydrofuran were analyzed. The barrier height and rate constants are calculated for the four H-abstraction channels. The BB1K calculated rate constant for α-axial H-abstraction is comparable with the experimentally determined rate constant. It reflects that α-axial H-abstraction is the main degradation pathway of tetrahydrofuran with Cl radical. DFT-based reactivity descriptors are also calculated and these values describe α-axial H-abstraction as the main reaction channel.

Production of a slit skimmer for use in cold supersonic molecular beams.

Cold molecular beams generated by skimming pulsed supersonic gas expansions normally employ conical skimmers. The use of slit shaped skimmers instead of conical skimmers can afford significant signal enhancements. At this time, however, slit shaped skimmers are not available commercially. We describe a straightforward method for producing functional slit skimmers.

High-resolution infrared spectrum of the nu1 Ba nd of eta5-C5H5NiNO.

Gas-phase rotational constants and distortion constants have been determined for the nu1 (v=1) excited vibrational state of cyclopentadienylnickel nitrosyl (C5H5NiNO) using a high-resolution Fourier transform spectrometer system at Kitt Peak, Arizona. The rotationally resolved lines have been measured for the C-H symmetric stretch vibration (nu1=3110 cm(-1)). In the present analysis, over 150 lines have been assigned and fitted using a rigid-rotor Hamiltonian with centrifugal distortion. The vibrational band center, excited-state rotational constants, and distortion constants derived from the measured spectrum for this prolate symmetric-top molecule are nuo=3110.4129(4) cm(-1), A'=0.14328(8) cm(-1), B'=C'=0.041285(1) cm(-1), DJ'=0.078(1) kHz, DJK'=2.23(4) kHz, and DK'=-2.63(2) kHz, respectively. Several different combination differences, with a common upper state, were calculated for different K stacks for the observed spectra, and the consistency of the lower state rotational constants obtained provided further support for the current assignment. The ground-state rotational constant (B'') derived from this combination differences analysis agrees with the previously obtained Fourier transform microwave value to within 0.15%. However, ground-state rotational constants, A'' and B'', have been fixed in the present analysis to avoid correlation effects and to get more accurate results. The new measured parameters are compared with the previously obtained results from Fourier transform microwave and infrared spectroscopy measurements. The C-H vibration stretching frequency and rotational constants were calculated using density functional theory calculations, and these were quite helpful in resolving ambiguities in the fitting procedure and for initial assignments of measured lines.

Determination of structural parameters for ferrocenecarboxaldehyde using Fourier transform microwave spectroscopy.

Gas-phase structural parameters for ferrocenecarboxaldehyde have been determined using Fourier transform microwave spectroscopy. Rotational transitions due to a-, b-, and c-type dipole moments were measured. Eighteen rotational constants were determined by fitting the measured transitions of various isotopomers using a rigid rotor Hamiltonian with centrifugal distortion constants. Least-squares fit and Kraitchman analyses have been used to determine the gas-phase structural parameters and the atomic coordinates of the molecule using the rotational constants for various isotopomers. Structural parameters determined from the least-squares fit are the Fe-C bond lengths to the cyclopentadienyl rings, r(Fe-C)=2.047(4) A, and the distance between the carbon atoms of the cyclopentadienyl rings, r(C-C)=1.430(2) A and r(C1-C1')=1.46(1) A of ring carbon and aldehyde carbon atom. Structural parameters were also obtained using density-functional theory calculations, and these were quite helpful in resolving ambiguities in the structural fit analysis, and providing some fixed parameters for the structural analysis. The results of the least squares and the calculations indicate that the carbon atoms of the Cp groups for ferrocenecarboxaldehyde are in an eclipsed conformation in the ground vibrational state.

The gas phase structure of ethynylferrocene using microwave spectroscopy.

Gas phase structural parameters for ethynylferrocene have been determined using microwave spectroscopy. Rotational transitions due to a- and b-type dipole moments were measured. Twenty four rotational constants have been determined by fitting the measured transitions of various isotopomers using a rigid rotor Hamiltonian with centrifugal distortion constants. Least-squares fits to determine structural parameters and Kraitchman analyses have been used to determine the gas phase structural parameters and the atomic coordinates from the rotational constants. The distance between the Fe atom and the C atoms of the cyclopentadienyl rings is r(Fe-C1) = 2.049(5) A, and the distance between the carbon atoms of the cyclopentadienyl ring is r(C-C) = 1.432(2) A. The ethynyl group is bent away from the Fe atom and out of the plane of the carbon atoms in the adjacent cyclopentadienyl ring by 2.75(6) degrees. Structural parameters were also obtained from DFT calculations and Kraitchman analyses, and the results are compared. Analysis of fit results for 13C isotopic substitution data indicates that the carbon atoms of the two cyclopentadienyl rings are in an eclipsed conformation in the ground vibrational state. Trends in microwave experimental values for the distance from the Fe atom to the center of the cyclopentadienyl ring for a series of substituted ferrocenes have been analyzed. This analysis provides an estimate of the gas phase distance from the Fe atom to the centers of the cyclopentadienyl rings for ferrocene of 1.65(1) A.