Impact of extended pi conjugation on methyl rotor-induced IVR in aromatic molecules

Laser-induced fluorescence excitation and resolved fluorescence spectra following excitations of the single vibronic levels (SVL) of p-vinyltoluene (p-VT) and p-vinylfluorobenzene (p-VFB) have been measured in a seeded supersonic free-jet expansion. A complete vibronic assignment of the fluorescence spectrum measured following excitation of the 0(0)0-band of p-VT has been presented. Normal vibrational modes in the S0 and S1 states of the molecule have been calculated by CASSCF method, and the correlation between the two set of modes is made by expressing the excited-state normal modes in terms of those of the ground state. The calculations predict that in the excited state methyl and vinyl torsional motions of p-VT are extensively mixed with many of the out-of-plane modes of the aromatic ring. Our resolved fluorescence spectral data measured following SVL excitations essentially agree with such predictions. In the excited state, the molecule exhibits a dramatically low threshold for the rotor-induced IVR in a supersonic jet expansion. Several mechanisms have been discussed to explain the phenomenon.     

A sum-over-histories account of an EPR(B) experiment

We analyze a variant of the EPRB experiment within a framework for quantum mechanics that rests on a radical interpretation of the sum over histories. Within this framework, reality is (just as classically) a single history, e.g. a definite collection of particles undergoing definite motions; and quantum dynamics appears as a kind of stochastic law of motion for that history, a law formulated in terms of non-classical probability-amplitudes. No state vectors enter this framework, and their attendant nonlocality is therefore absent as well.1. That is, before pair creations and annihilations were discovered. (The electronic and nuclear spins might also be regarded as new aspects of their kinematics. But perhaps spin is better construed, within the sum-over-histories framework, as a quality of a more dynamical character, namely as a generalized sort of probability-amplitude.)2. A possible escape would be the so-called Everett interpretation, in which the collapse never occurs, but its effects are supposed to be recovered via a more careful analysis of closed systems in which measurement-like processes take place. Among other things, this approach tends to lead either to the view that nothing really happens [1] or to the view that everything really happens [2] (which perhaps is not that different from the former view).3. For example, the rule, collapse occurs along the past light cone (in the Heisenberg picture), appears to be consistent.4. And Bell's inequality shows thatany theory formulated in terms of an instantaneous state evolving in time would encounter the same trouble. Indeed, the trouble shows up even more glaringly if one adapts Bell's argument to spin-1 systems, using the results of Kochen and Specker[10]. In order to use the Kochen-Specker results in the EPR manner one needs a scheme for measuring the relevant observables, but this can be accomplished by means of suitably concatenated Stern-Gerlach analyzers with recombining beams [13]. Then, as Allen Stairs has pointed out [14], even the perfect correlations become impossible to reproduce, and no reference to probability theory is needed to establish a contradiction with locality. Recently, an analogous experiment using three spin 1/2 particles instead of two spin 1 particles has also been given [15].5. No technical problem obstructs an extension to fermionic fields (indeed the functional integral formalism for Quantum Field Theory is probably the most popular at present), but the realistic interpretation of the individual histories seems to get lost. One way out would be if all fermions were composites or collective excitations of fields quantized according to bosonic commutation relations. Another would be if the particle formulation were taken as basic, with the complementary field formulation being merely a mathematical artifice (at least for fermions).6. In the approach of Gell-Mann-Hartle and Griffiths for example, only a small subset of the possible partitions is granted meaning, in such a way that all interference terms are suppressed and quantum probabilities reduce to classical ones.7. In stating these rules we consider an idealized situation in which the spatio-temporal indeterminacy of particle-locationwithin a given one of our trajectories is ignored; or if you prefer, you can take the experiment as only a Gedanken one affording a simplified illustration of how EPR-like correlations are understood within the sum-over-histories framework. In this connection recall also that the semiclassical propagator is in fact exact for a free particle.8. This can be interpreted either as part of the specification of the initial conditions, or (as suggested by a referee) merely as an example of relativization of probabilities.9. Thus a state vector may be defined as an equivalence-class of sets of partial histories.10. One such generalization applies to open systems, for example to a particle in contact with a heat reservoir. For this example see [11], wherein the two-way path formalism of §5 above is used, and the influence of the reservoir results in an effective dynamics for the particle in which the forward and backward portions of its world-line are coupled to each other by a certain interaction term in the amplitude. In this type of situation a density-operator (though not a state vector ) can still be introduced, but it no longer summarizes all the relevant information about the past (and correspondingly its evolution lacks the Markov property that(t + dt) is determined by(t) alone). For quantum gravity, it may be that not even such a non-Markov will be exactly definable, and only the global probabilities themselves will make sense.11. Ironically it is just this property of the amplitudes which, as mentioned above, makes possible the introduction of the state vectors whose collapse then introduces such a strong appearance ofnonlocality into the theory.     

ipso-Nitrosation of arylboronic acids with chlorotrimethylsilane and sodium nitrite

Nitroso compounds are versatile reagents in synthetic organic chemistry. Herein, we disclose a feasible protocol for the ipso-nitrosation of aryl boronic acids using chlorotrimethylsilane–sodium nitrite unison as nitrosation reagent system.     

Highly chemoselective reduction of azides to amines by Fe(0) nanoparticles in water at room temperature

A highly chemoselective reduction of aryl, heteroaryl, acyl and sulfonyl azides to the corresponding amines has been achieved by Fe(0) nanoparticles in water at room temperature in the absence of external hydride source. Several readily reducible functionalities including alkene, alkyne, S-S linkage, OTBDMS remain unaffected during reduction.     

Selective fluorescence and naked eye detection of histidine in aqueous medium via hydrogen bonding assisted Schiff base condensation

Visible light excitable rhodamine B derivative (TARDHD) has been developed for fluorescence and naked eye detection of histidine in aqueous medium. TARDHD shows 45 fold fluorescence enhancement in the presence of histidine. It forms Schiff base with histidine and stabilizes via intra-molecular H-bonding. TARDHD can efficiently detect intracellular histidine.     

Dosimetric gelator probes and their application as sensors

Supramolecular gels formed by the self-assembly of organic molecules are useful in many areas from materials to medicine. Of the different applications, exploitation of gels for the visual detection of analytes is a fairly recent trend in gel chemistry. Most of the gel-based sensors rely on non-covalent interactions between the gelator molecules and the added chemical analytes and therefore, often suffer from less selectivity and long response time. In this context, dosimetric gelator probes are superior to other gel-based sensors with high selectivity and fast response time. Unlike non-covalent binding sites, dosimetric gelators typically contain a reaction centre and undergo a specific chemical reaction selective to an analyte resulting in either formation or rupturing of covalent bonds. In this review, we provide an up-to-date report of various reaction-based gel systems applied for the sensing of analytes. We elaborately discuss the concept, design principles, self-assembly properties, and reaction mechanisms of such gelators. We also highlight the limitations, challenges, and the necessity of further exploration of dosimetric gels in this domain.     

An overview of heterogeneous photocatalysis for the degradation of organic compounds: A special emphasis on photocorrosion and reusability

Heterogeneous photocatalysis has been extensively investigated for the degradation of organic pollutants from wastewater. The remarkable advantages of the heterogeneous photocatalysis process depend upon its ability to produce reactive oxygen species under visible/UV/solar light irradiation. However, the long-term stability and reuse potential of these catalysts are of great concern these days, yet understudied. This review aims to systematically present a state of the art understanding of such catalysts' reuse potential. Various important surface characteristics of the photocatalysts for improving the photostability and activity of the catalyst are discussed. Besides, the synergistic effect of different surface modified materials, composite materials and their surface characteristics for their enhanced activity are also covered. Finally, a discussion on various regeneration processes used for such catalysts is also presented, identifying some vital research needs in this field.