Linking numbers in local quantum field theory

Linking numbers appear in local quantum field theory in the presence of tensor fields, which are closed two-forms on Minkowski space. Given any pair of such fields, it is shown that the commutator of the corresponding intrinsic (gauge-invariant) vector potentials, integrated about spacelike separated, spatial loops, are elements of the center of the algebra of all local fields. Moreover, these commutators are proportional to the linking numbers of the underlying loops. If the commutators are different from zero, the underlying two-forms are not exact (i.e. there do not exist local vector potentials for them). The theory then necessarily contains massless particles. A prominent example of this kind, due to J.E. Roberts, is given by the free electromagnetic field and its Hodge dual. Further examples with more complex mass spectrum are presented in this article.

     

Magnesium perchlorate as efficient Lewis acid for the Knoevenagel condensation between β-diketones and aldehydes

A new protocol for the Knoevenagel condensation between β-diketones and aliphatic and aromatic aldehydes promoted by Mg(ClO₄)₂ under mild conditions is reported.     

Polyfunctionalized pyrrolidines by Ugi multicomponent reaction followed by palladium-mediated SN2' cyclizations

A 4-component Ugi reaction with a suitable isocyanide, followed by a novel secondary transformation involving a Pd(II)-mediated (R5 = H) or a Pd(0)-mediated (R5 = CO2Me) SN2' cyclization to give highly functionalized N-acyl-2-vinylpyrrolidines, is reported. The overall yields are usually good and in most cases the Pd(0)-catalyzed reaction gave the final product in almost quantitative yield.     

Conformational behavior of pyrazine-bridged and mixed-bridged cavitands: a general model for solvent effects on thermal "vase-kite" switching

The controllable switching of suitably bridged resorcin[4]arene cavitands between a "vase" conformation, with a cavity capable of guest inclusion, and a "kite" conformation, featuring an extended flattened surface, provides the basis for ongoing developments of dynamic molecular receptors, sensors, and molecular machines. This paper describes the synthesis, X-ray crystallographic characterization, and NMR analysis of the "vase-kite" switching behavior of a fully pyrazine-bridged cavitand and five other mixed-bridged quinoxaline-bridged cavitands with one methylene, phosphonate, or phosphate bridge. The pyrazine-bridged resorcin[4]arene cavitand displayed an unexpectedly high preference for the kite conformation in nonpolar solvents, relative to the quinoxaline-bridged analogue. This observation led to extensive solvent-dependent switching studies that provide a detailed picture of how solvent affects the thermal vase-kite equilibration. As for any thermodynamic process in the liquid phase, the conformational equilibrium is affected by how the solvent stabilizes the two individual states. Suitably sized solvents (benzene and derivatives) solvate the cavity of the vase form and reduce the propensity for the vase-to-kite transition. Correspondingly, the kite geometry becomes preferred in bulky solvents such as mesitylene, incapable of penetrating the vase cavity. As proposed earlier by Cram, the kite form is preferred at low temperatures due to the more favorable enthalpy of solvation of the enlarged surface. Furthermore, the kite conformation is more preferred in solvents with substantial hydrogen-bonding acidity: weak hydrogen-bonding interactions between the mildly basic quinoxaline and pyrazine nitrogen atoms and solvent molecules are more efficient in the open kite than in the closed vase form. Vase-to-kite conversion is entirely absent in dipolar aprotic solvents lacking any H-bonding acidity. Thermal vase-kite switching requires fully quinoxaline- or pyrazine-bridged cavitands, whereas pH-controlled switching is also applicable to systems incorporating only two or three such bridges.     

Functionalized gold nanoparticles for ultrasensitive DNA detection

A major challenge in the area of DNA detection is the development of rapid methods that do not require polymerase chain reaction (PCR) amplification of the genetic sample. The PCR amplification step increases the cost of the assay, the complexity of the detection, and the quantity of DNA required for the assay. In this context, methods that are able to perform DNA analyses with ultrasensitivity have recently been investigated with the aim of developing new PCR-free detection protocols. Functionalized gold nanoparticles have played a central role in the development of such methods. Here, possibilities offered by functionalized gold nanoparticle in the ultrasensitive detection of DNA are discussed. The different functionalization protocols available for gold nanoparticles and the principal DNA detection methods that are able to detect DNA at the femtomolar to attomolar level are presented.     

Template effects in the formation of [2]pseudo-rotaxanes containing diazapyrenium units

The template effects exerted by guests 14 and 15 in the ring closure reaction of 3 have been quantitatively evaluated. The rate largely increases in the presence of the two templates. The results are compared with those relative to the ring closure reaction of 1 yielding cyclobis(paraquat-p-phenylene), 2. The comparison indicates that the formation of tetracationic aromatic cycles templated by aromatic donors benefits from the use of extended pi surfaces both in the acceptor and in the donor components.     

Equilibrium dynamics of an associating polymer melt in narrow slits by computer simulation

Molecular dynamics simulations have been used to study the dynamics of a coarse-grained model of a melt of polymer chains with associating terminal groups, confined in a narrow slit by two layers of Lennard-Jones sites. Simulations were carried out as a function of wall separation and attracting strength. We found that confinement has an important effect on the overall dynamics of the system. Strongly attracting walls can significantly modify the dynamics of the melt, giving an aggregation structure with extremely long relaxation times. A noticeable degree of anisotropy was found for the dynamics of both the individual chains and the aggregates formed by the associating terminal groups.     

X-ray and mössbauer studies of tricyclohexyltin(IV) halides. The crystal structures of (cyclo-C6H11)3SnX (X = F,Br and I)

The structures of tricyclohexyltin fluoride (I), bromide (II) and iodide (III) have been determined by X-ray analysis. Compound I crystallizes in the space group P2₁/m with a = 10.422(6), b = 17.238(9), c = 5.769(3) Å, β = 104.6(1)° and Z = 2. Compounds II and III crystallize in the space group Pcmn with a = 10.427(6), b = 16.914(9), c = 11.366(6) Å, Z = 4; and a = 10.400(6), b = 16.900(10), c = 11.400(4) Å, Z = 4, respectively. All three structures consist of discrete tetrahedral (cyclo-C₆H₁₁)₃SnX units.The temperature dependence of the Mössbauer resonance areas has been examined in order to obtain information about the relationship between chemical structure and lattice dynamics.     

TiO2-based photocatalysts impregnated with metallo-porphyrins employed for degradation of 4-nitrophenol in aqueous solutions: role of metal and macrocycle

Photodegradation of organic compounds in water solutions by means of economically advantageous and environment-friendly processes is a topic of growing interest. In recent years a great attention has been devoted to TiO₂-based photocatalysts for the oxidative degradation of various organic pollutants. In this context, we have prepared new photo-catalytic polycrystalline TiO₂ systems impregnated with sensitizers, i.e., copper, iron or manganese porphyrins, and investigated their photoactivity for 4-nitrophenol oxidation compared with that of bare TiO₂. A significant improvement of the photoreactivity was observed in the case of TiO₂ impregnated with copper porphyrin, while only a slight beneficial effect was observed in the case of iron porphyrin. In contrast, the presence of manganese porphyrin appeared to be detrimental.