Metallacycles of porphyrins as building blocks in the construction of higher order assemblies through axial coordination of bridging ligands: solution- and solid-state characterization of molecular sandwiches and molecular wires

Treatment of the octahedral Ru(II)-dimethyl sulfoxide complexes trans-RuCl(2)(dmso-S)(4) (1), trans-RuCl(2)(dmso-O)(2)(CO)(2) (2), and trans-RuCl(2)(dmso)(3)(CO) (3) with a stoichiometric amount of 5,10-bis(4'-pyridyl)-15,20-diphenylporphyrin (4'-cis-DPyP) yields, after chromatographic purification, the novel 2+2 molecular squares of formula [trans,cis,cis-RuCl(2)(dmso-S)(2)(4'-cis-DPyP)](2) (4), [trans,cis,cis-RuCl(2)(CO)(2)(4'-cis-DPyP)](2) (5), and [trans,cis,cis-RuCl(2)(dmso-S)(CO)(4'-cis-DPyP)](2) (6), respectively. Compound 6 exists as an equimolar mixture of the isomeric metallacycles 6a and 6b, depending on whether the 4'-N(py) rings of 4'-cis-DPyP's are trans to CO or to dmso-S. Compounds 4-6 were fully characterized by NMR and IR spectroscopy and by FAB mass spectrometry. Treatment of 5 with excess zinc acetate in chloroform/methanol mixtures led to the isolation of the corresponding zinc adduct [trans,cis,cis-RuCl(2)(CO)(2)(Zn x 4'-cis-DPyP)](2) (5Zn). Treatment of 5Zn with 1 equiv of a trans ditopic N-donor ligand L (L = 4,4'-bipy, 5,15-bis(4'-pyridyl)-2,8,12,18-tetra-n-propyl-3,7,13,17-tetramethylporphyrin (4'-trans-DPyP-npm), or 5,15-bis(4'-pyridyl)-10,20-diphenylporphyrin (4'-trans-DPyP)) leads readily and selectively, according to (1)H NMR spectroscopy, to the quantitative assembling of 2:2 supramolecular adducts of stacked metallacycles of formula [(5Zn)(2)(mu-L)(2)] (7-9), which were thoroughly characterized in solution by NMR spectroscopy. NMR features indicate that, at ambient temperature, the equilibrium between 5Zn and L to yield [(5Zn)(2)(mu-L)(2)] has an intermediate to slow rate on the NMR time scale (relatively broad signals for L) and is totally shifted toward the 2:2 product (all or nothing process). Single-crystal X-ray investigations showed that, depending on the nature of the bridging ligand, in the solid state these sandwich structures can either be maintained or originate polymeric chains formulated as [(5Zn)(mu-L)](infinity). When L = 4'-trans-DPyP, both solution- and solid-state data indicate that [(5Zn)(2)(mu-4'-trans-DPyP)(2)] (9) is a discrete supramolecular assembly of two molecular squares of metalloporphyrins axially connected through other porphyrins. In this molecular box, the two bridging porphyrins are coplanar at a distance of about 11.4 A. When L = 4,4'-bipy, the corresponding adduct 7 has the anticipated sandwich-like discrete architecture [(5Zn)(2)(mu-4,4'-bipy)(2)] in solution, but it assumes a stair-like polymeric wire structure in the solid state. The polymer [(5Zn)(mu-4,4'-bipy)](infinity) is made by 5Zn squares bridged by 4,4'-bipy ligands which are axially coordinated alternatively on the two opposite sides of each square. Our work clearly established that relatively simple supramolecular adducts of porphyrins, such as molecular squares, are suitable building blocks for the construction of more elaborate assemblies of higher order by axial coordination of bridging ligands.     

Mono- and dinuclear bioxazoline-palladium complexes for the stereocontrolled synthesis of CO/styrene polyketones

The coordination chemistry of the chiral bioxazoline ligand (4S,4'S)-2,2'-bis(4-isopropyl-4,5-dihydrooxazole) to Pd(II) provides evidence that the ligand bonding can occur either through chelation of one Pd(II) ion leading to a mononuclear species with the expected cis geometry, or by double bridging of two Pd(II) ions giving a dinuclear complex with trans geometry. The species in solution are identified by 1H NMR spectroscopy. Both the mononuclear and the dinuclear complexes promote the CO/styrene copolymerization, yielding the corresponding polyketone with a fully or a predominantly isotactic microstructure, depending on the reaction medium. The nature of the anion present in the palladium precatalysts affects the polyketone stereochemistry. MALDI-TOF analysis of the copolymers synthesized reveals the presence of p-hydroxyphenolic end-groups, thus confirming and explaining the role of 1,4-hydroquinone as a molecular weight regulator.     

A proteomic approach to study protein variation in GM durum wheat in relation to technological properties of semolina

Genetic manipulation of durum wheats by tobacco rab-1 genes influence the trafficking of gluten proteins through the secretory system by up- or down-regulating the transport step from the ER to the Golgi apparatus which may in turn modify functional performance of the grain. Gluten proteins were extracted from two genetically manipulated lines - Svevo B730 1-1 and Ofanto B688 1-2 - and their control lines and were analyzed by two dimensional gel electrophoresis. When the two-dimensional maps were compared by image analysis no significant differences between the GM line with an up-regulated trafficking containing the wild type tobacco rab1 (Svevo B730 1-1) and its control (Svevo control). By contrast, significant differences were found between the GM line with a down-regulated trafficking due to the tobacco rab1 mutant form (Ofanto B688 1-2) and its control (Ofanto control). Of the new protein spots detected in the down-regulated Ofanto B688 1-2 map, only a beta-amylase was identified. The remaining spots were susceptible to chymotripsin action but not to trypsin one, as in the case of the gluten protein. Rheological measurements showed that gluten quality was enhanced in the down-regulated Ofanto B688 1-2 without an increase in the amount of gluten. Proteomics is a useful and powerful tool for investigating protein changes in GMOs and in understanding events in food science and technology.     

Synthesis of Polysubstituted Pyrrolizidines from Proline Derivatives and Conjugated Nitroolefins

The stereochemistry of 1,3-dipolar cycloaddition of azomethine ylides derived from aromatic aldehydes and i-proline alkyl esters with several nitroolefins was investigated. Cyclic and acyclic nitroolefins add to the anti form of the ylide in a highly diastereoselective but poorly regioselective manner to give pyrrolizidine derivatives. In a few cases, the stereochemical results strongly support a stepwise mechanism.     

Design,synthesis and X‐ray structural studies of novel [acetonitrile‐benzyl‐3‐N‐(2, 4 dihydroxyphenylmethylene) hydrazinecarbodithioato‐κ3‐N′, S,O] nickel(ll) complex that potently inhibit cell proliferation through regulation of apoptosis related genes

Nickel is a fundamental element for healthy life for human and higher animals. For biological importance, its complexation with bioactive ligand is worth to be studied with the aim to understand its function. Using mouse peritoneal cancer model, MTT colorimetric assay and anticancer activity analysis, we examined the role of nickel(ll) complex in growth inhibition of cancer cells. A novel nickel(ll) complex was synthesized and characterized using physico‐chemical and spectroscopic techniques. The study indicated that both the ligand and complex were capable of inhibiting Ehrlich Ascites Carcinoma (EAC) cells growth by 28.21% and 44.52%, respectively, when administered 0.3 mg/kg/day body weight intraperitoneally for five consecutive days in Swiss Webstar mice. Determination the LD₅₀ of the complex (55 mg/kg) allowed adjusting the dose as 2.75 mg/kg and upon administration, inhibition increased to 69.36%. The ligand and complex have shown an inhibitory effect in the range of 4.86%–67.3% and 6.1%‐ 89.37%, respectively, against EAC cells (concentration range of 31.25–500 μg/ml) in RPMI‐1640 medium as determined by MTT colorimetric assay. Apoptotic cell morphological alteration was determined through optical and fluorescence microscopy. Up regulation of P⁵³, Bax, Cas‐8, Cas‐3 and Fas and down regulation of NF‐kB and Bcl‐2 gene expression were observed in the cells treated with the nickel(ll) complex for five consecutive days. In conclusion, the newly synthesized nickel(ll) complex has shown anti‐proliferative activity and can further be optimized to be used as a lead molecule for anticancer drug.     

Condensed 2-pyrrolidinone-1,2-oxazines from lithium enolate of 1-benzyl-5-oxo-3-pyrrolidinecarboxylic acid and β-aryl, β-nitroenamines

The reaction of the lithium enolate of 1-benzyl-5-oxo-3-pyrrolidinecarboxylic acid 3 with a series of β-aryl, β-nitroenamines unexpectedly afforded 6-aryl-2-benzyl-4-oxa-1-oxo-3a-methoxycarbonyl-2,5-diazaindenes 9a-d, whose structure was determined by analytical and NMR spectroscopical analysis. The structure of 9b was further confirmed by X-ray analysis. A reasonable mechanism for their formation is given.     

Significance of Truckenbrodt's Energy and Momentum Coefficients for Loss Calculation in Ramified Pipe Systems

For one-dimensional simulation of flow in ramified pipe systems loss prediction in junctions is essential. In the standard literature (e.g. [1]) total pressure loss coefficients serve this purpose. Elementary formulas follow from the principle of momentum and some simple assumptions [2]. They yield rather crude estimates, often twice as large as experimental values. Modifications described by Idelchik [3] look nice, but after all turn out to be not more accurate. We explain deviations and propose improved loss formula based on Truckenbrodt's energy and momentum coefficients [4], thus paying regard to velocity distributions over pipe cross-sections. We further discuss extraction of the coefficient's values from experiments. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

fac-[Re(CO)3(dmso-O)3](CF3SO3): a new versatile and efficient Re(I) precursor for the preparation of mono and polynuclear compounds containing fac-[Re(CO)3]+ fragments

We show here that the new complex fac-[Re(CO)3(dmso-O)3](CF3SO3) (1), efficiently prepared in one step from [ReBr(CO)5] and featuring a broad range of solubility, is, in general, a better precursor for the one-step synthesis of mono- and polynuclear inorganic compounds containing fac-[Re(CO)3]+ fragments compared to the commonly used (NEt4)2fac-[ReBr3(CO)3] and fac-[Re(CO)3(CH3CN)3](Y) (Y = PF6, BF4, ClO4) species. Compound 1 is the first example of a Re(I)-dmso complex structurally characterized and confirms the rule that dmso is always O-bonded when trans to CO. The reactivity of 1 was tested in the one-step preparation of several new and known complexes. The O-bonded sulfoxides of 1 are replaced under mild conditions by tri- (L3) and bidentate ligands (L2) to produce fac-[Re(CO)3(L3)]+ and fac-[Re(CO)3(L2)(dmso-O)]+ compounds, respectively. An excess of monodentate ligands (L) and more forcing conditions are needed to prepare fac-[Re(CO)3(L)3]+ compounds. The new compounds include fac-[Re(CO)3(bipy)(dmso-O)](CF3SO3) (4), that turned out to be an excellent precursor for binding the luminescent fac-[Re(CO)3(bipy)]+ fragment to polytopic ligands for the construction of more elaborate assemblies. One example reported here is the two-step preparation of fac-[{Re(CO)3(bipy)}(mu-4,4'-bipy){Ru(TPP)(CO)}](CF3SO3) (8) (TPP = tetraphenylporphyrin). The X-ray structures of the new compounds 1, 4, of the bis-porphyrin complex fac-[Re(CO)3Cl(4'MPyP)2] (13) (4'MPyP = 5-(4'pyridyl)-10,15,20-triphenylporphyrin), and of the rhenium-cyclophane [{(CO)3Re(mu-OH)2Re(CO)3}2(micro-4,4'-bipy)2] (15), among others, are described. Compound 1 might find useful applications in supramolecular chemistry (metal-mediated assembly of large architectures), in the in situ preparation of stable Re compounds to be used in nuclear medicine, and for the labeling of biomolecules.