Chemical Composition of Essential Oil from Pilea microphylla and its Antimicrobial Activity

Chemistry of Natural Compounds -     

Effect of seasonal variation on dust samples of a winter fog affected urban environment of India,South East Asia

Physical and chemical characteristics of leaf dust (LD) samples, collected between 2011 and 2013, of a severely winter fog affected and polluted urban environment (Allahabad, India) of Indo-Gangetic plain are presented in this study. The weather changes in the study area are grouped into three effective annual seasonal periods – winter fog, pre-monsoon and post-monsoon. The pronounced impact of seasonal variations is observed in LD characteristics, as ~46% of the winter fog period samples ranges in size between 2.5 and 20 µm with high magnetic susceptibility (up to 938.22 × 10^?8 m³ kg^?1). In comparison, 35% of the LD from pre-monsoon period occurs in the size range of 100–300 µm with low magnetic susceptibility (up to 43.29 × 10^?8 m³ kg^?1). The fractal analysis involving submicroscopic clast dimension of LD also reveals a seasonal influence. The toxic metals (Pb, Zn, Cd, Cr and Ni) in LD belonging to winter fog and post-monsoon periods increase in comparison to samples from pre-monsoon time. Multivariate statistical analysis of trace element data suggests that the LD collected from winter fog and post-monsoon periods originate predominantly from anthropogenic source, whereas those collected during pre-monsoon owe their origin to crustal and anthropogenic sources, mainly. The present study has demonstrated the role of seasonal variation in controlling the physical and chemical properties of particulate matter based on multiple parameter analyses, and the derivation of the dust load from a mixed source (upper continental crust, anthropogenic and vehicular) for the study area for the first time.     

Catalytic Asymmetric Epoxidation of Aldehydes with Two VANOL‐Derived Chiral Borate Catalysts

A highly diastereo‐ and enantioselective method for the epoxidation of aldehydes with α‐diazoacetamides has been developed with two different borate ester catalysts of VANOL. Both catalytic systems are general for aromatic, aliphatic, and acetylenic aldehydes, giving high yields and inductions for nearly all cases. One borate ester catalyst has two molecules of VANOL and the other only one VANOL. Catalysts generated from BINOL and VAPOL are ineffective catalysts. An application is shown for access to the side‐chain of taxol.     

Reactivity of amino acid nucleoside phosphoramidates: a mechanistic quantum chemical study

Recent experimental evidence (Maiti et al. Chem.-Eur. J., submitted) indicates that hydrolysis of nucleoside phosphoramidates is subjected to anchimeric influence by carboxyl moieties in the leaving group but also by the base in the nucleotide. A quantum chemical analysis of these findings is presented. First the intrinsic hydrolysis mechanism is investigated for simplified model compounds, and then both amino acid and nucleoside substituents are included. It is found that hydrolysis is assisted by the α-carboxyl group via formation of a five-membered intermediate and that the barrier for the reaction of this intermediate toward the product state can be influenced by the nucleobase. The adenine base protonated on N3 interacts with the transition state and considerably lowers the barrier for hydrolysis. The influence of several base modifications is explained by calculating the pK(a) for protonation on N3.     

Nonradiative inter- and intramolecular energy transfer from the aromatic donor anisole to a synthesized photoswitchable acceptor system

We report steady state and time resolved fluorescence measurements on acetonitrile (ACN) solutions of the model compounds, energy donor anisole (A) and a photoswitchable acceptor N,N′-1,2-phenylene di-p-tosylamide (B) and the multichromophore (M) where A and B are connected by a spacer containing both rigid triple (acetylenic) and flexible methylene bonds. Both steady state and time correlated single photon counting measurements demonstrate that though intermolecular energy transfer, of Forster type, between the donor and acceptor moieties occurs with rate 10⁸ s^?1 but when these two reacting components are linked by a spacer (multichromophore, M) the observed transfer rate (～10¹¹ s^?1) enhances. This seemingly indicates that the imposition of the spacer by inserting a triple bond may facilitate in the propagation of electronic excitation energy through bond. The time resolved fluorescence measurements along with the theoretical predictions using Configuration interaction singles (CIS) method by using 6-31G (d,p) basis set, implemented in the Gaussian package indicate the formations of the two excited conformers of B. The experimental findings made from the steady state and time resolved fluorescence measurements demonstrate that, though two different isomeric species of the acceptor B are formed in the excited singlet states, the prevailing singlet–singlet nonradiative energy transfer route was found from the donor A to the relatively longer-lived isomeric species of B.     

Investigations on the Photoreactions of Phenothiazine and Phenoxazine in Presence of 9-cyanoanthracene by Using Steady State and Time Resolved Spectroscopic Techniques

By using electrochemical, steady state and time resolved (fluorescence lifetime and transient absorption) spectroscopic techniques, detailed investigations were made to reveal the mechanisms of charge separation or forward electron transfer reactions within the electron donor phenothiazine (PTZH) or phenoxazine (PXZH) and well known electron acceptor 9-cyanoanthracene (CNA). The transient absorption spectra suggest that the charge separated species formed in the excited singlet state resulted from intermolecular photoinduced electron transfer reactions within the donor PTZH (or PXZH) and CNA acceptor relaxes to the corresponding triplet state. Though alternative mechanisms of via formations of contact neutral radical by H-transfer reaction have been proposed but the observed results obtained from the time resolved measurements indicate that the regeneration of ground state reactants is primarily responsible due to direct recombination of triplet contact ion-pair (CIP) or solvent-separated ion-pair (SSIP).     

Multicomponent catalytic asymmetric aziridination of aldehydes

The first multicomponent catalytic asymmetric aziridination reaction is developed to give aziridine-2-carboxylic esters with very high diastereo- and enantioselectivity from aromatic and aliphatic aldehydes. This new method pushes the boundary of the aziridination reaction to substrates that failed with preformed imines.     

A Design Criteria to Achieve Giant Ising-Type Anisotropy in CoII-Encapsulated Metallofullerenes

Discovery of permanent magnetisation in molecules just like in hard magnets decades ago led to the proposal of utilising these molecules for information storage devices and also as Q-bits in quantum computing. A significant breakthrough with a blocking temperature as high as 80 K has been recently reported for lanthanocene complexes. While enhancing the blocking temperature further remains one of the primary challenges, obtaining molecules that are suitable for the fabrication of the devices sets the bar very high in this area. Encouraged by the fact that our earlier predictions of potential single-molecule magnets (SMMs) in lanthanide-containing endohedral fullerenes have been verified, here we set out to undertake a comprehensive study on Co^II-ion-encapsulated fullerene as potential SMMs. To study this class of molecules, we have utilised an array of theoretical methods ranging from density functional to ab initio CASSCF/NEVPT2 methods for obtaining reliable estimate of zero-field splitting parameters D and E. Additionally, we have also employed, for the first time a combination of molecular dynamics based on DFT methods coupled with CASSCF/NEVPT2 methods to seek the role of conformational isomers in the relaxation of magnetisation. Particularly, we have studied, Co@C₂₈, Co@C₃₈ and Co@C₄₈ cages and their isomers as potential target molecules that could yield substantial magnetic anisotropy. Our calculations categorically reveal a very large Ising anisotropy in this class of molecules, with Co@C₄₈ cages predicted to yield D values as high as −127 cm⁻¹. Our calculations on the smaller cages reveal the free movement of Co^II ion inside the cage, leading to the likely scenario of faster relaxation of magnetisation. However, larger fullerene cages were found to solve this issue. Further models with incorporating units such as {CoOZn}, {CoScZnN} inside larger fullerenes yield axial zero-field splitting values as high as −200 cm⁻¹ with negligible E/D values. As these units represent a strong axiality coupled with a viable way to obtain air-stable low-coordinate Co^II complexes, this opens up a new paradigm in the search of SMMs in this class of molecules.