The tidal prism as a dynamic response of a nonlinear harmonic system

As known, the empirical relationship between the equilibrium cross-sectional area of a lagoon inlet and the tidal prism was intuited for the first time by LeConte ["Discussion on the paper, "Notes on the improvement of river and harbor outlets in the United States"by D. A. Watt,"Trans. ASCE 55, 306-308 (1905).] and then formalized by O'Brien ["Estuary tidal prism related to entrance areas,"Civ. Eng. 1(8), 738-739 (1931)]. This relationship requires knowledge of the tidal prism, which can be estimated either using the cubature method or the current data method [Jarrett, Tidal Prism-Inlet Area Relationships (Coastal Engineering Research Center, US Army Corps of Engineers, Fort Belvoir, VA, 1976)], both of which involve the execution of a number of experimental measurements. However, these methods, besides being very expensive, can only provide the prism value in the present condition and do not allow for predictions in the case of significant morphological changes, of both natural and anthropic origin, to the tidal inlet. On the other hand, the hydrodynamic relationship, which links the tidal prism to the product of the tidal range and the basin extension, can only give a coarse estimate of the prism, especially when the value of the tide outside the lagoon is considered. In this work, we propose a simple hydrodynamic relationship based on the dynamic response of a nonlinear harmonic system. This is a relationship that requires the calibration of a single physically based parameter. Through this relationship, knowing the geometric characteristics, the bottom friction of the inlet channel, the surface of the basin, and the tide amplitude in the open sea, it is possible to estimate the tidal prism. The application of this relationship to real cases shows a good agreement with the experimental data

Kalai and Muller's Possibility Theorem: A Simplified Integer Programming Version

We provide a respecification of an integer programming characterization of Arrovian social welfare functions introduced by Sethuraman et al. (Math Oper Res 28:309–326, 2003). By exploiting this respecification, we give a new and simpler proof of Theorem 2 in Kalai and Muller (J Econ Theory 16:457–469, 1977)

Reactions of diiron MU-aminocarbyne complexes containing nitrile ligands

The acetonitrile ligand in the mu-aminocarbyne complexes [Fe-2{mu-CN(Me) R}(mu-CO)( CO)(NCMe)(Cp)(2)][SO3CF3] (R = Me, 2a, CH2Ph, 2b, Xyl, 2c) (Xyl = 2,6-Me2C6H3) is readily displaced by halides and cyanide anions affording the corresponding neutral species [Fe-2{mu-CN( Me) R}(mu-CO)(CO)(X)(Cp)(2)] (X = Br, I, CN). Complexes 2 undergo deprotonation and rearrangement of the coordinated MeCN upon treatment with organolithium reagents. Trimethylacetonitrile, that does not contain acidic a hydrogens has been used in place of MeCN to form the complexes [Fe-2{mu-CN(Me)R}(mu-CO)(CO)(NCCMe3)(Cp)(2)][SO3CF3] (7a-c). Attempts to replace the nitrile ligand in 3 with carbon nucleophiles ( by reaction with RLi) failed, resulting in decomposition products. However the reaction of 7c with LiC= CTol (Tol = C6H4Me), followed by treatment with HSO3CF3, yielded the imino complex [Fe-2{mu-CN(Me) Xyl}(mu-CO)(CO) {N(H) C(C= CC6H4Me-4) CMe3}(Cp)(2)][SO3CF3] (8), obtained via acetilyde addition at the coordinated NCCMe3

Addition of alkynes at bridging vinyliminium ligands in diiron complexes: Unprecedented diene formation by enyne-like metathesis

The zwitterionic bridging vinyliminium complex [Fe(2){mu-eta 1: eta 3-C(Tol)]=C(CS2)C] = N(Me)2}(mu-CO)(CO)( Cp)(2)] (5a) undergoes the addition of two equivalents of MeO(2)C-C C-CO(2)Me affording the bridging bis-alkylidene complex [Fe(2){mu-eta 1: eta 3-C(Me)C{C(CO(2)Me)C(CO(2)Me)CSC(CO(2)Me)C(CO(2)Me)S}CNMe(2)}(mu-CO)( CO)(Cp)(2)] (6). One alkyne unit inserts into a C-CS(2) bond of the bridging ligand, with consequent rearrangement that leads to the formation of a diene. The reaction shows analogies with the enyne metathesis. The second alkyne is incorporated into the bridging frame via cycloaddition at the thiocarboxylate function, affording a 1,3-dithiolene. The complexes [Fe(2){mu-eta(1): eta(3)-C(R')]=C(CS(2))C=N(Me)(R)}(mu-CO)(CO)(Cp)(2)] (R = Xyl, R' = Tol, 5b; R = p-C(6)H(4)OMe, R' = Me, 5c; Xyl = 2,6-Me(2)C(6)H(3)), treated with MeO(2)C-C C-CO(2)Me and then with HBF(4), undergo the cycloaddition of the alkyne with the dithiocarboxylate group and protonation of the dithiocarboxylate carbon, affording the complexes [Fe(2){mu-eta 1: eta 3-C(R')]=C{C(H)SC(CO(2)Me)C(CO(2)Me)S}C]=N(Me)(R)}(mu-CO)(CO)(Cp)(2)][BF(4)] (R = Xyl, R' = Tol, 7a; R= p-C(6)H(4)OMe, R' = Me, 7b), respectively. The X-ray molecular structure of 6 has been determined

On the foundation of monopoly in bilateral exchange

We address the problem of monopoly in general equilibrium in a mixed version of a monopolistic two-commodity exchange economy where the monopolist, represented as an atom, is endowed with one commodity and “small traders,” represented by an atomless part, are endowed only with the other. First we provide an economic theoretical foundation of the monopoly solution in this bilateral framework through a formalization of an explicit trading process inspired by Pareto (Cours d’économie politique. F. Rouge Editeur, Lausanne, 1896) for an exchange economy with a finite number of commodities, and we give the conditions under which our monopoly solution has the geometric characterization proposed by Schydlowsky and Siamwalla (Q J Econ 80:147–153, 1966). Then, we provide a game theoretical foundation of our monopoly solution through a two-stage reformulation of our model. This allows us to prove that the set of the allocations corresponding to a monopoly equilibrium and the set of the allocations corresponding to a subgame perfect equilibrium of the two-stage game coincide. Finally, we compare our model of monopoly with a bilateral exchange version of a pioneering model proposed by Forchheimer (Jahrbuch für Gesetzgebung, Verwaltung und Volkswirschafts im Deutschen Reich 32:1–12, 1908), known as a model of “partial monopoly” since there a monopolist shares a market with a“competitive fringe.” Journal of Economic Literature Classification Numbers: D42, D51

Addition of protic nucleophiles to alkynyl methoxy carbene ligands in diiron complexes

Different protic nucleophiles (i.e. Ph2C=NH, PhSH, MeCO2H, PhOH) can be added to the C equivalent to C bond of [Fe-2{mu-CN(Me)(Xyl)}-(mu-CO)(CO){C(OMe)C equivalent to CTol}(CP)(2)][SO3CF3] (1), affording new diiron alkenyl methoxy carbene complexes. The additions of Ph2C=NH and MeCO2H are regio and stereoselective, resulting in the formation of the 5-aza-1-metalla-1,3,5-hexatriene [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(OMe)C beta H=C-gamma(Tol)(N=CPh2)}(CP)(2)][SO3CF3](2), and the 2-(acyloxy)alkenyl methoxy carbene complex [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(OMe)C beta H=C-gamma(Tol)OC(O)Me)}(CP)(2)][CF3SO3] (5); the E isomer of the former and the Z of the latter are formed exclusively. Conversely, the addition of PhSH is regio but not stereoselective; thus, both the E and Z isomers of [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(OMe)C beta H=C-gamma(Tol)(SPh)}(CP)(2)][SO3CF3](3) are formed in comparable amounts. Compounds 3 and 5 are demethylated upon chromatography through Al2O3, resulting in the formation of the acyl complexes [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(O)C beta H=C-gamma(Tol)(SPh)}(Cp)(2)](4) and [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(O)C beta H=C-gamma(Tol)OC(O)Me}(CP)(2)](6), respectively, both with a Z configured C-beta=C-gamma bond. Finally, the reaction of 1 with PhOH proceeds only in the presence of an excess of Et3N affording the 2-(alkoxy)alkenyl acyl complex [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(O)C beta H=C-gamma(Tol)(OPh)}(CP)(2)](7). The crystal structures of 4 center dot CH2Cl2 and 7 center dot 0.5CH(2)Cl(2) have been determined by X-ray diffraction experiments

Effect of metabolic and antioxidant supplementation on sperm parameters in oligo-astheno-teratozoospermia, with and without varicocele: a double-blind placebo-controlled study

Since sperm require high energy levels to perform their specialised function, it is vital that essential nutrients are available for spermatozoa when they develop, capacitate and acquire motility. However, they are vulnerable to a lack of energy and excess amounts of reactive oxygen species, which can impair sperm function, lead to immotility, acrosomal reaction impairment, DNA fragmentation and cell death. This monocentric, randomised, double-blind, placebo-controlled trial investigated the effect of 6 months of supplementation with l-carnitine, acetyl-l-carnitine and other micronutrients on sperm quality in 104 subjects with oligo- and/or astheno- and/or teratozoospermia with or without varicocele. In 94 patients who completed the study, sperm concentration was significantly increased in supplemented patients compared to the placebo (p =.0186). Total sperm count also increased significantly (p =.0117) in the supplemented group as compared to the placebo group. Both, progressive and total motility were higher in supplemented patients (p =.0088 and p =.0120, respectively). Although pregnancy rate was not an endpoint of the study, of the 12 pregnancies that occurred during the follow-up, 10 were reported in the supplementation group. In general, all these changes were more evident in varicocele patients. In conclusion, supplementation with metabolic and antioxidant compounds could be efficacious when included in strategies to improve fertility

Diiron-aminocarbyne complexes with amine or imine ligands: C-N coupling between imine and aminocarbyne ligands promoted by tolylacetilyde addition to [Fe2{m-CN(Me)R}(m-CO)(CO)(NH=CPh2)(Cp)2][SO3CF3]

A terminally coordinated CO ligand in the complexes [Fe2{m-CN(Me)R}(m-CO)(CO)2(Cp)2][SO3CF3] (R = Me, 1a; R = Xyl, 1b; Xyl = 2,6-Me2C6H3), is readily displaced by primary and secondary amines (L), in the presence of Me3NO, affording the complexes [Fe2{m-CN(Me)R}(m-CO)(CO)(L)(Cp)2][SO3CF3] (R = Me, L = NH2Et, 4a; R = Xyl, L = NH2Et, 4b; R = Me, L = NH2Pri, 5a; R = Xyl, L = NH2Pri, 5b; R = Xyl, L = NH2C6H11, 6; R = Xyl, L = NH2Ph, 7; R = Xyl, L = NH3, 8; R = Me, L = NHMe2, 9a; R = Xyl, L = NHMe2, 9b; R = Xyl, L= NH(CH2)5, 10). In the absence of Me3NO, NH2Et gives addition at the CO ligand of 1b, yielding [Fe2{CN(Me)(Xyl)}(m-CO)(CO)C(O)NHEt(Cp)2] (11). Carbonyl replacement is also observed in the reaction of 1a-b with pyridine and benzophenone imine, affording [Fe2{m-CN(Me)R}(m-CO)(CO)(L)(Cp)2][SO3CF3] (R= Me, L= Py, 12a; R = Xyl, L= Py, 12b; R= Me, L= HN=CPh2, 13a; R = Xyl, L= HN=CPh2, 13b). The imino complex 13b reacts with p-tolylacetylide leading to the formation of the m-vinylidene-diaminocarbene compound [Fe2-C=C(Tol)C(Ph)2N(H)CN(Me)(Xyl)(m-CO)(CO)(Cp2)] (15) which has been studied by X-ray diffraction

Nitrile ligands activation in dinuclear aminocarbyne complexes

The diiron complexes [Fe(Cp)(CO){μ-η2:η2-C[N(Me)(R)]NC(C6H3R′)CCH(Tol)}Fe(Cp)(CO)] (R = Xyl, R′ = H, 3a; R = Xyl, R′ = Br, 3b; R = Xyl, R′ = OMe, 3c; R = Xyl, R′ = CO2Me, 3d; R = Xyl, R′ = CF3, 3e; R = Me, R′ = H, 3f; R = Me, R′ = CF3, 3g) are obtained in good yields from the reaction of [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(p-NCC6H4R′)(Cp)2]+ (R = Xyl, R′ = H, 2a; R = Xyl, R′ = Br, 2b; R = Xyl, R′ = OMe, 2c; R = Xyl, R′ = CO2Me, 2d; R = Xyl, R′ = CF3, 2e; R = Me, R′ = H, 2f; R = Me, R′ = CF3, 2g) with TolCCLi. The formation of 3 involves addition of the acetylide at the coordinated nitrile and C–N coupling with the bridging aminocarbyne together with orthometallation of the p-substituted aromatic ring and breaking of the Fe–Fe bond. Complexes3a–e which contain the N(Me)(Xyl) group exist in solution as mixtures of the E-trans and Z-trans isomers, whereas the compounds 3f,g, which posses an exocyclic NMe2 group, exist only in the Z-cis form. The crystal structures of Z-trans-3b, E-trans-3c, Z-trans-3e and Z-cis-3g have been determined by X-ray diffraction experiments