A convenient synthesis of pyrrolopyridines and 2-substituted indoles by gold-catalyzed cycloisomerization

We have developed a gold-catalyzed intramolecular cyclization of variously substituted acetylenic amines under mild conditions, which yields pyrrolopyridines and 2-substituted indoles, quantitatively. The cycloisomerization of acetylenic amines was achieved with AuCl₃ as catalyst without the use of base, acid or N-protecting group.     

Metal-free direct oxidative intermolecular diarylation of anilides at ambient temperature assisted by cascade selective formation of C-C and C-N bonds

A new atom-economical process of direct oxidative intermolecular functionalization of aniline derivatives by simple arenes was developed. The products were formed in a highly regioselective manner under metal-free conditions at ambient temperature.     

Velocity and conformation statistics based on reduced Karhunen–Loeve projection data from DNS of viscoelastic turbulent channel flow

To investigate the effectiveness of the Karhunen–Loeve (K–L) method as a data reduction approach, we study here its effect on the velocity and conformation statistics in a drag reducing turbulent polymer flow. The K–L method has been used to construct a set of basis velocity eigenfunctions from a large number of independent realizations of the velocity. Those were obtained from direct numerical simulation (DNS) of a viscoelastic turbulent channel flow using the Giesekus model. A subset of the K–L eigenfunctions, large enough to contain more than 90% of the fluctuating kinetic energy of the flow on the average, has then been subsequently used to obtain time series of projection coefficients of the velocity fields generated further from DNS. In a post-processing step, velocity fields were reconstructed using selected subsets of the projection coefficients. Those reconstructed velocity fields were then used to evaluate turbulent statistics as well as to integrate the constitutive equation. The turbulent statistics (r.m.s. velocities, Reynolds stress etc.) thus constructed showed good agreement with the full results from DNS. The Reynolds stress anisotropy was also calculated in this work for the first time. It was found to increase with viscoelasticity that was well reproduced in the reduced K–L data except near the channel centerline where the K–L data showed some loss of anisotropy. The biggest differences however between the K–L reduced data and the full DNS results were seen in the conformation statistics. The average polymer conformation extracted from the K–L reduced data was significantly less than that corresponding to the full DNS results anywhere except in the shear-dominated wall region. A further comparison of the energy and dissipation spectra between the full DNS and the K–L reconstructed data illustrated the impact of the K–L process in resulting to a significant damping of small turbulent scales even those contributing to the maximum in turbulent dissipation. This may also be the principal reason behind the poor quality of the K–L reconstructed conformation data.     

Coordination-driven self-assembly of 2D-metallamacrocycles using a shape-selective Pt(II)2-organometallic 90° acceptor: design, synthesis and sensing study

Synthesis of a series of two-dimensional metallamacrocycles via coordination-driven self-assembly of a shape-selective Pt(II)(2)-molecular building unit incorporating carbazole-ethynyl functionality is described. An equimolar (1?:?1) combination of a Pt(II)(2)-organometallic 90° acceptor, 1, with rigid linear ditopic donors (L(a) and L(b)) afforded [4 + 4] self-assembled octanuclear molecular squares, 2 and 3, in quantitative yields, respectively [L(a) = 4,4'-bipyridine; L(b) = trans-1,2-bis(4-pyridyl)ethylene]. Conversely, a similar treatment of 1 with an amide-based unsymmetrical flexible ditopic donor, L(c), resulted in the formation of a [2 + 2] self-sorted molecular rhomboid (4a) as a single product [L(c) = N-(4-pyridyl)isonicotinamide]. Despite the possibility of several linkage isomeric macrocycles (rhomboid, triangle and square) due to the different connectivity of L(c), the formation of a single and symmetrical molecular rhomboid (4a) as the only product is an interesting observation. All the self-assembled macrocycles (2, 3 and 4a) were fully characterized by multinuclear NMR ((1)H and (31)P) and ESI-MS analysis. Further structural insights about the size and shape of the macrocycles were obtained through energy minimization using density functional theory (DFT) calculations. Decoration of the starting carbazole building unit with Pt-ethynyl functionality enriches the assemblies to be more π-electron rich and luminescent in nature. Macrocycles 2 and 3 could sense the presence of electron deficient nitroaromatics in solution by quenching of the initial intensity upon gradual addition of picric acid (PA). They exhibited the largest quenching response with high selectivity for nitroaromatics compared to several other electron deficient aromatics tested.     

MRDCI study of the low-lying electronic states of PbSi

Electronic states of the PbSi molecule up to 4 eV have been studied by carrying out ab initio based MRDCI calculations which include relativistic effective core potentials (RECPs) of both the atoms. The use of semicore RECPs of Pb produces better dissociation limits than the full-core one. However, the (3)P(0)-(3)P(1) splitting due to Pb is underestimated by about 4000 cm(-1). At least 25 bound electronic states of the Λ-S symmetry are predicted for PbSi. The computed zero-field-splitting in the ground state is about 544 cm(-1). A strong spin-orbit mixing changes the nature of the potential energy curves of many Ω states. The overall splitting among the spin components of A(3)Π is computed to be 4067 cm(-1). However, the largest spin-orbit splitting is reported for the (3)Δ state. A number of spin-allowed and spin-forbidden transitions are predicted. The partial radiative lifetime for the A(3)Π-X(3)Σ(-) transition is of the order of milliseconds. The computed bond energy in the ground state is 1.68 eV, considering the spin-orbit coupling. The vertical ionization energy for the ionization to the X(4)Σ(-) ground state of PbSi(+) is about 6.93 eV computed at the same level of calculations.     

Ratiometric fluorescence signalling of fluoride ions by an amidophthalimide derivative

Fluorescence behaviour of 4-benzoylamido-N-methylphthalimide (1), designed and developed for selective detection of fluoride ions, is reported. 1 displays F⁻-induced colour change that allows its detection with the naked eye. The F⁻ specificity of the sensor system is evident from the fact that unlike F⁻, other halides do not affect the absorption characteristics of 1. Apart from the colorimetric response, the fluorescence output of 1 is also modulated by F⁻ in a manner that permits ratiometric fluorescence signalling of F⁻ as well. It is found that the system can detect F⁻ in the concentration range of 10–60 μM. The results of the experiments and theoretical calculations unambiguously suggest that the changes of the electronic absorption and fluorescence behaviour of 1, which have been exploited for signalling purpose, are due to F⁻-induced deprotonation of the 4-amido moiety of the sensor system.     

Post-scission dynamics in fission

A dynamical model for fission from the classical turning point to scission and beyond is presented. We consider the fissioning nucleus as well as the fission fragments as incompressible irrotational deformable charged liquid drops. We focus on the post-scission time evolution of the neck, stretching of the fragments, kinetic energy and excitation energy.     

Photoionization and photoelectron angular distribution for H2

Photoionization of H₂(¹Σ_g⁺) in a vibrational υ″ and rotational N″ state into H₂⁺(²Σ_g⁺) in a vibrational υ′ and rotational N′ state is studied theoretically. The differential cross section, after summing over the final states, is expressed in the well-known simple form of $\text{(}\text{σ}{}_{\mathrm{T}}\text{4π}\text{)[1 + βP}{}_2\text{(}\text{cos}\text{θ)]}$. Parallel expressions are obtained for H₂⁺ in a specific υ′ state (in terms of σ(υ′) and β(υ′)) and for H₂⁺ in a rotational fine level υ′N′ (in terms of σ(υ′N′) and β(υ′N′)). Asymmetry parameters β, β(υ′) and β υ′N′), which are expressed in terms of Racah and Clebsch-Gordan coefficients and electronic transition moments, can be reduced approximately to 2 lineary polarized light and to -1 for unpolarized light. Using single-center electronic wave functions and including partial eaves l = 1, 3, and 5, σ(υ′) and β(υ′) are computed as a function of υ′ at 584 Å. The computed σ(υ′) divided by the Frank-Condon overlap, in agreement with experimental results, increases monotonically with υ′; σ_T and β are computed in the incident photon energy range of 600–4000 Å and the results compare favorably with previous calculations.     

Dynamical model for neck formation in the entrance channel of a heavy ion collision

The formation of the neck in the entrance channel is studied using a classical dynamical model. The dependence of neck radius on bombarding energy, mass or charge and angular momentum is discussed.     

The distribution of 3p12 strength in 209Bi

An optimized Woods-Saxon potential, which gives excellent fits to the observed proton states in ²⁰⁹Bi and ²⁰⁷Tl, is used to calculate the excitation energy of the unbound $\text{3p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ proton state in ²⁰⁹Bi. Using the wave functions given by the above potential, the strength of the core-particle interaction is calculated. The effect of the vibration of the core on the fragmentation of the $\text{3p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state is estimated. It is found that the $\text{3p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state at 5.123 MeV loses more than 80% of its strength to five $\text{1}\text{2}{}^{\mathrm{?}}$ collective states in ²⁰⁹Bi and the observed $\text{3p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state at 3.64 MeV is actually an almost equal mixture of the $\text{3p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ single-proton state and the ($\text{4}{}^{\mathrm{+}}\text{, 1}\text{h}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$) collective state.