Molecular assembly of metallacarboranes in water: light scattering and microscopy study

Polyhedral metallacarboranes are used mainly as ion-pairing agents and recently have been recognized as potent inhibitors of HIV protease. They are characterized by exceptional hydrophobicity, rigid geometry, delocalized negative charge, ion-pairing behavior, and strong acidity of their conjugated acids. The completely novel phenomenon, association of these promising pharmaceutical tectons in aqueous solutions, is described here. The behavior of two structural types of metallacarboranes, [bis(1,2-dicarbollide)cobaltate(1-)] and bis[(3)-1,2-dicarbollylcobalt]-(3,6)-1,2-dicarbacanastide(2-)], in aqueous solution was studied by a combination of static and dynamic light scattering and microscopy methods. Spherical aggregates with radii of ca. 100 nm and fairly monodisperse nanostructures were found in aqueous solutions. The behavior of nanoaggregates is fairly complex and depends on the concentration and aging of the solutions. The particles are stabilized in the solution by counterions. The formation of larger clusters upon dilution of bis(1,2-dicarbollide)cobaltate(1-) solutions was observed. The secondary aggregation can be suppressed by addition of NaCl. Gel permeation chromatography measurements of sodium bis(1,2-dicarbollide)cobaltate(1-) show that the majority of matallacarborane molecules form nanoaggregates and only a small amount of the metallacarborane remains molecularly soluble or forms small oligomers.     

Assessment of enveloping distribution sampling to calculate relative free enthalpies of binding for eight netropsin-DNA duplex complexes in aqueous solution

The performance of enveloping distribution sampling (EDS) simulations to estimate free enthalpy differences associated with seven alchemical transformations of A-T into G-C base pairs at the netropsin binding site in the minor groove of a 13-base pair DNA duplex in aqueous solution is evaluated. It is demonstrated that sufficient sampling can be achieved with a two-state EDS Hamiltonian even for large perturbations such as the simultaneous transformation of up to three A-T into three G-C base pairs. The two parameters required to define the EDS reference state Hamiltonian are obtained automatically using a modified version of a scheme presented in earlier work. The sensitivity of the configurational sampling to a variation of these parameters is investigated in detail. Although for relatively small perturbations, that is, one base pair, the free enthalpy estimate depends only weakly on the EDS parameters, the sensitivity is stronger for the largest perturbation. Yet, EDS offers various convenient measures to evaluate the degree of sampling and thus the reliability of the free enthalpy estimate and appears to be an efficient alternative to the conventional thermodynamic integration methodology to obtain free energy differences for molecular systems.     

Path and path deviation equations for <Emphasis Type="Italic">p</Emphasis>-branes

Path and path deviation equations for neutral, charged, spinning and spinning charged test particles, using a modified Bazanski Lagrangian, are derived. We extend this approach to strings and branes. We show how the Bazanski Lagrangian for charged point particles and charged branes arises à la Kaluza-Klein from the Bazanski Lagrangian in 5-dimensions.     

Derivations of noncommutative Banach algebras II

Supported in part by a grant from the Ministry of Science of Slovenia.     

Influence of the side chain protecting group on the stereoselectivity of the 1,3-dipolar cycloaddition of d-talo-configured nitrones

Two new five-membered cyclic d-talo-configured nitrones were synthesized from d-mannose, and examined in 1,3-dipolar cycloadditions with vinyl acetate and vinylene carbonate. The stereoselectivity of the cycloadditions depends greatly on the protecting group of the vicinal diol attached to the nitrone C-5 carbon atom. Methyl protection resulted in limited syn/anti-selectivity, giving mixtures of the two isomeric exo-syn and exo-anti isoxazolidines in comparable amounts. On the other hand, the cyclohexylidene-substituted nitrone reacted more selectively in favour of the syn isomer. The difference in the diastereoselectivity was attributed to the specific spatial orientation of the nitrone C-5 substituent.     

Synthese von Tetracyanoniccolat-clathraten mit Benzol Kurze Mitteilung

Zusammenfassung Durch Ersetzung des Cadmiums im Clathrat Cden[Ni(CN)₄]·2C₆H₆ wurden drei Verbindungen des TypsM(en) _m[Ni(CN)₄]·nC₆H₆ (M ²⁺=Ni, Cu, Zn;m=2–3;n=0.14–0.28) hergestellt und charakterisiert.

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Synthesis of ethylendiamine-(metal II)-tetracyanoniccolate dibenzene clathrate compounds

Replacing cadmium ion in Cden[Ni(CN)₄]·2C₆H₆ clathrate compound three compounds ofM(en) _m[Ni(CN)₄]·nC₆H₆ type (M ²⁺=Ni, Cu, Zn;m=2–3;n=0.14–0.28) were prepared and characterized.

     

Complexation of molybdenum(V) with glycolic acid: an unusual orientation of glycolato ligand in {Mo2O4}2+ complexes

(PyH)5[Mo(V)OCl4(H2O)]3Cl2 and (PyH)n[Mo(V)OBr4]n reacted with glycolic acid (H2glyc) or its half-neutralized ion (Hglyc(-)) to afford a series of novel glycolato complexes based on the {Mo(V)2O4}2+ structural core: (PyH)3[Mo2O4Cl4(Hglyc)]. (1)/ 2CH 3CN (1), (PyH) 3[Mo 2O 4Br 4(Hglyc)].Pr(i)OH(2), (PyH)2[Mo2O4(glyc) 2Py 2] (3), (PyH) 4[Mo 4O 8Cl 4(glyc) 2].2EtOH (4), and [Mo 4O 8(glyc) 2Py 4] (5) (Py = pyridine, C 5H 5N; PyH(+) = pyridinium cation, C 5H 5NH (+) and glyc (2-) = a doubly ionized glycolate, (-)OCH 2COO (-)). The compounds were fully characterized by X-ray crystallography and infrared spectroscopy. The Hglyc (-) ion binds to the {Mo 2O 4} (2+) core through a carboxylate end in a bidentate bridging manner, whereas the glyc (2-) ion adopts a chelating bidentate coordination through a deprotonated hydroxyl group and a monodentate carboxylate. The orientations of glyc (2-) ions in 3- 5 are such that the alkoxyl oxygen atoms occupy the sites opposite the multiply bonded oxides. {(C6H5) 4P}[Mo(VI)O 2(glyc)(Hglyc)] ( 6), an oxidized complex, features a reversed orientation of the glyc(2-) ion. The theoretical DFT calculations on the [Mo(V)2O4(glyc) 2Py 2](2-) and [Mo(VI)O2(glyc)2](2-) ions confirm that binding of glycolate with the alkoxyl oxygen to the site opposite the MoO bond is energetically more favorable in {Mo(V)2O4}(2+) species, whereas a reversed orientation of the ligand is preferred in Mo(VI) complexes. An explanation based on the orbital analysis is put forward.     

Synthesis of new functionalized imidazo[2,1‐b]thiazoles and thiazolo[3,2‐a]pyrimidines

5‐Oxo‐5H‐[1,3]thiazolo[3,2‐a]pyrimidine‐6‐carboxylic acid ( 4 ), and 6‐methylimidazo[2,1‐b]thiazole‐5‐carboxylic acid ( 17 ) were reacted with amines 6a‐i by the reaction with oxalyl chloride and N, N‐di methyl‐formamide as a catalyst into primary and secondary amide derivatives 7‐14 and 19‐22. From compound 24 N,N'‐disubstituted ureas 26, 27 and perhydroimidazo[1,5‐c]thiazole 29 derivatives of imidazo[2,1‐b]thiazole were prepared. By nmr analysis of compound 29 , the existence of two stereoisomers resulting from both optical, due to centre of chirality at C7′a, and conformational isomerism, due to restricted C5? N6′ bond rotation were proved.     

Photolysis of 10,10-difluorophenanthren-9(10H)-one. Evidence for solvent-assisted α-cleavage

The photolysis of 10,10-difluorophenanthren-9(10H)-one 1 in different solvents shows that the major competing reaction of the diradical formed by α-cleavage: recombination and hydrogen atom abstraction depends on the hydrogen atom donating ability of the solvent. Photolysis of 1 in cyclohexane in the presence of air or oxygen leads mainly to α-cleavage while photoreduction with the formation of 10-fluoro-9-phenanthrol occurs when the solution is deaerated prior to irradiation. In acetonitrile, a poor hydrogen donor, recombination of the diradical back to starting compound 1 is the sole process.