Mono-N-methylation of functionalized anilines with alkyl methyl carbonates over NaY faujasites. 4. Kinetics and selectivity

[reaction: see text] In the presence of NaY faujasite as the catalyst, the reaction of bifunctional anilines (1-4: XC6H4NH2; X = OH, CO2H, CH2OH, and CONH2) with methyl alkyl carbonates [MeOCO2R': R' = Me or MeO(CH2)2O(CH2)2] proceeds with a very high mono-N-methyl selectivity (XC6H4NHMe up to 99%), and chemoselectivity as well, with other nucleophilic functions (OH, CO2H, CH2OH, CONH2) fully preserved from alkylation and/or transesterification reactions. Aromatic substituents, however, modify the relative reactivity of amines 1-4: good evidence suggests that, not only steric and electronic effects, but, importantly, direct acid-base interactions between substituents and the catalyst are involved. Weakly acidic groups (OH, CH2OH, CONH2, pKa > or = 10) may help the reaction, while aminobenzoic acids (pKa of 4-5) are the least reactive substrates. The solvent polarity also affects the reaction, which is faster in xylene than in the more polar diglyme. The mono-N-methyl selectivity is explained by the adsorption pattern of reagents within the zeolite pores: a B(Al)2 displacement of the amine on methyl alkyl carbonate should occur aided by the geometric features of the NaY supercavities. Different factors account for the reaction chemoselectivity. Evidence proves that the polarizability of the two nucleophilic terms (NH2 and X groups) of anilines is relevant, although adsorption and confinement phenomena of reagents promoted by the zeolite should also be considered.     

On the complex formation equilibria between iron (III) and sulfate ions

The equilibria have been investigated at 25 degrees C in 3 M NaClO4 using potentiometry, glass and redox Fe3+/Fe2+ half-cells, and UV optical absorptiometry. The concentration of the reagents was chosen in the intervals: 10(-4) < or = [Fe(III)] < or = 5.10(-3) M, 0.01 < or = [SO4(2-)]tot < or = 0.65 M. The value of [H+] was kept at 0.1 M or more to reduce the hydrolysis of the Fe3+ ion to less than 1%. Auxiliary constants, corresponding to the formation of Fe(II)-sulfate complexes and to the association of H+ with SO4(2-) ions, were taken from previous determinations. The experimental data could be explained with the equilibria [formula: see text] Equilibrium constants at infinite dilution, log beta 101 degrees = 3.82 +/- 0.17, log beta 102 degrees = 5.75 +/- 0.17 and log beta 111 degrees = 3.68 +/- 0.35, have been evaluated by applying the specific interaction theory.     

On the hydrolysis of the dioxouranium(VI) ion in sulfate solutions

The formation of ternary UO2(2+)-(OH-)-SO4(2-) complexes has been studied at 25 degrees C in 3 M NaClO4 ionic medium by measurements with a glass electrode. The solutions had uranium concentrations between 0.3 and 30 mM, sulfate between 20 and 200 mM, and 1.66 < or = [SO4(2-)]/[U(VI)] < or = 300. The hydrogen ion concentration ranged from 10(-3) M to incipient precipitation of basic sulfates. This occurred, depending on the metal concentration, at [H+] between 10(-4) and 10(-5.3) M. In the interpretation of the data the stabilities of binary complexes were assumed from independent sources. The data could be explained with the mixed complexes and equilibria (beta(pqr)(3sigma) refers to pUO2(2+) + qH2O + rSO4(2-) <==> (UO2)p(OH)q(SO4)r(2p-q-2r) + qH+): logbeta222 = -2.94 +/- 0.03, logbeta341 = -9.82 +/- 0.06, logbeta211 = -0.30 +/- 0.09, logbeta212 = 1.09 +/- 0.09, logbeta351 = -15.04 +/- 0.09 and logbeta462 = -14.40 +/- 0.06. The fit could be improved by including UO2OH+ with logbeta110 = -5.1 +/- 0.1. The identity of the minor species remains, however, an open question.     

On the genus of 4-dimensional products of manifolds

Summary We determine bounds for the regular genus of any 4-manifold, which is a product of by a closed 3-manifold, or a product of two closed surfaces. This is done by an explicit construction of a graph representing the manifold, and by finding a minimal regular imbedding of it.

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Sunto Determiniamo una limitazione del genere regolare di una 4-varieta prodotto di per una 3-varieta chiusa, o prodotto di due superficie chiuse, costruendo esplicitamente un grafo che la rappresenta, e trovandone un'immersione regolare minimale.

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This work was performed under the auspieces of the G.N.S.A.G.A. of the C.N.R. (National Research Council) of Italy.     

Conservative logic

Conservative logic is a comprehensive model of computation which explicitly reflects a number of fundamental principles of physics, such as the reversibility of the dynamical laws and the conservation of certainadditive quantities (among which energy plays a distinguished role). Because it more closely mirrors physics than traditional models of computation, conservative logic is in a better position to provide indications concerning the realization of high-performance computing systems, i.e., of systems that make very efficient use of the computing resources actually offered by nature. In particular, conservative logic shows that it is ideally possible to build sequential circuits with zero internal power dissipation. After establishing a general framework, we discuss two specific models of computation. The first uses binary variables and is the conservative-logic counterpart of switching theory; this model proves that universal computing capabilities are compatible with the reversibility and conservation constraints. The second model, which is a refinement of the first, constitutes a substantial breakthrough in establishing a correspondence between computation and physics. In fact, this model is based on elastic collisions of identical balls, and thus is formally identical with the atomic model that underlies the (classical) kinetic theory of perfect gases. Quite literally, the functional behavior of a general-purpose digital computer can be reproduced by a perfect gas placed in a suitably shaped container and given appropriate initial conditions.This research was supported by the Defense Advanced Research Projects Agency and was monitored by the Office of Naval Research under Contract No. N000 14-75-C-0661.     

Supramolecular microcontact printing and dip-pen nanolithography on molecular printboards

The transfer of functional molecules onto self-assembled monolayers (SAMs) by means of soft and scanning-probe lithographic techniques-microcontact printing (muCP) and dip-pen nanolithography (DPN), respectively-and the stability of the molecular patterns during competitive rinsing conditions were examined. A series of guests with different valencies were transferred onto beta-cyclodextrin- (beta-CD-) terminated SAMs and onto reference hydroxy-terminated SAMs. Although physical contact was sufficient to generate patterns on both types of SAMs, only molecular patterns of multivalent guests transferred onto the beta-CD SAMs were stable under the rinsing conditions that caused the removal of the same guests from the reference SAMs. The formation of kinetically stable molecular patterns by supramolecular DPN with a lateral resolution of 60 nm exemplifies the use of beta-CD-terminated SAMs as molecular printboards for the selective immobilization of printboard-compatible guests on the nanometer scale through the use of specific, multivalent supramolecular interactions. Electroless deposition of copper on the printboard was shown to occur selectively on the areas patterned with dendrimer-stabilized gold nanoparticles.     

Adsorption of d-alaninol on Cu(1 0 0)

Adsorption of d-alaninol on Cu(1 0 0) at room temperature has been investigated by photoelectron spectroscopy in the soft X-ray and VUV energy range and low energy electron diffraction (LEED). d-Alaninol was found by LEED to self-assemble at full coverage; core and valence photoemission spectra are presented at low and full coverage. Chemisorption occurs at room temperature. The bonding at low coverage takes place at the hydroxylic group; at full coverage there is evidence of bonding for both hydroxylic and amino groups.     

Stringy Chern classes of singular varieties

Motivic integration [M. Kontsevich, Motivic integration, Lecture at Orsay, 1995] and MacPherson's transformation [R. MacPherson, Chern classes for singular varieties, Ann. of Math. 100 (1974) 423-432] are combined in this paper to construct a theory of “stringy” Chern classes for singular varieties. These classes enjoy strong birational invariance properties, and their definition encodes data coming from resolution of singularities. The singularities allowed in the theory are those typical of the minimal model program; examples are given by quotients of manifolds by finite groups. For the latter an explicit formula is proven, assuming that the canonical line bundle of the manifold descends to the quotient. This gives an expression of the stringy Chern class of the quotient in terms of Chern-Schwartz-MacPherson classes of the fixed-point set data.