Diferratricarbaboranes of the subcloso-[(eta5-C5H5)2Fe2C3B8H11] type, the first representatives of the 13-vertex dimetallatricarbaborane series

Treatment of the [2-Cp-9-tBuNH-closo-2,1,7,9-FeC(3)B(8)H(10)] (1) ferratricarbollide (Cp = eta(5)-C(5)H(5) (-)) with Na(+) C(10)H(8) (-) in 1,2-dimethoxyethane (DME) at room temperature produced an air-sensitive transient anion with a tentatively identified nido-[tBuNH-CpFeC(3)B(8)H(10)](2-) constitution. In-situ reaction of this low-stability ion with [CpFe(CO)(2)I] or [CpFe(CO)(2)](2) generated three violet diferratricarbaboranes identified as paramagnetic subcloso complexes [4,5-Cp(2-)-4,5,1,6,7-Fe(2)C(3)B(8)H(11)] (2; yield 2 %), [4,5-Cp(2-)-4,5,1,7,12-Fe(2)C(3)B(8)H(11)] (3; yield 2 %), and [7-tBuNH-4,5-Cp(2-)-4,5,1,7,12-Fe(2)C(3)B(8)H(10)] (4; yield 14 %). These first representatives of the 13-vertex dimetallatricarbaborane family were characterized by EPR and IR spectroscopy, and mass spectrometry, and their structures were determined by X-ray diffraction analysis.     

Characterization of embeddings of Sobolev-type spaces into generalized Hölder spaces defined by Lp-modulus of smoothness

We prove a sharp estimate for the k-modulus of smoothness, modelled upon a $L^p$-Lebesgue space, of a function f in $W^k{L}^{\frac{pn}{n+kp},p}(\mathrm{\Omega })$, where Ω is a domain with minimally smooth boundary and finite Lebesgue measure, $k,n\in \mathbb{N}$, $k<n$ and $\frac{n}{n?k}<p<+\infty$. This sharp estimate is used to establish necessary and sufficient conditions for continuous embeddings of Sobolev-type spaces into generalized Hölder spaces defined by means of the k-modulus of smoothness. General results are illustrated with examples. In particular, we obtain a generalization of the classical Jawerth embeddings.     

Alkynyltrifluoroborates as versatile tools in organic synthesis: a new route to spiroketals

[reaction: see text] A simple and efficient two-step approach to spiroketals is described. Key steps include the preparation of functionalized hydroxyl alpha-alkynones by ring-opening reactions of lactones with lithium alkynyltrifluoroborates followed by a palladium-catalyzed hydrogenation/spirocyclization of the prespiroketal intermediate.     

On the Parameterization of Rational Ringed Surfaces and Rational Canal Surfaces

Ringed surfaces and canal surfaces are surfaces that contain a one-parameter family of circles. Ringed surfaces can be described by a radius function, a directrix curve and vector field along the directrix curve, which specifies the normals of the planes that contain the circles. In particular, the class of ringed surfaces includes canal surfaces, which can be obtained as the envelopes of a one-parameter family of spheres. Consequently, canal surfaces can be described by a spine curve and a radius function. We present parameterization algorithms for rational ringed surfaces and rational canal surfaces. It is shown that these algorithms may generate any rational parameterization of a ringed (or canal) surface with the property that one family of parameter lines consists of circles. These algorithms are used to obtain rational parameterizations for Darboux cyclides and to construct blends between pairs of canal surfaces and pairs of ringed surfaces.     

Optimal Embeddings of Bessel-Potential-Type Spaces into Generalized Hölder Spaces Involving <Emphasis Type="Italic">k</Emphasis>-Modulus of Smoothness

We establish necessary and sufficient conditions for embeddings of Bessel potential spaces H ^σ X(IR ⁿ ) with order of smoothness σ?∈?(0, n), modelled upon rearrangement invariant Banach function spaces X(IR ⁿ ), into generalized Hölder spaces (involving k-modulus of smoothness). We apply our results to the case when X(IR ⁿ ) is the Lorentz-Karamata space \(L_{p,q;b}({{\rm I\kern-.17em R}}^n)\). In particular, we are able to characterize optimal embeddings of Bessel potential spaces \(H^{\sigma}L_{p,q;b}({{\rm I\kern-.17em R}}^n)\) into generalized Hölder spaces. Applications cover both superlimiting and limiting cases. We also show that our results yield new and sharp embeddings of Sobolev-Orlicz spaces W ^k?+?1 L ^n/k(logL) ^α (IR ⁿ ) and W ^k L ^n/k(logL) ^α (IR ⁿ ) into generalized Hölder spaces.     

Direct Introduction of an Alkylsulfonamido Group on C-sites of Isomeric Dicarba-closo-dodecaboranes: The Influence of Stereochemistry on Inhibitory Activity against the Cancer-Associated Carbonic Anhydrase IX Isoenzyme

Carbonic anhydrase IX (CA IX), a tumor-associated metalloenzyme, represents a validated target for cancer therapy and diagnostics. Herein, we report the inhibition properties of isomeric families of sulfonamidopropyl-dicarba-closo-dodecaboranes group(s) prepared using a new direct five-step synthesis from the corresponding parent cages. The protocol offers a reliable solution for synthesis of singly and doubly substituted dicarba-closo-dodecaboranes with a different geometric position of carbon atoms. The closo-compounds from the ortho- and meta-series were then degraded to corresponding 11-vertex dicarba-nido-undecaborate(1−) anions. All compounds show in vitro enzymatic activity against CA IX in the low nanomolar or subnanomolar range. This is accompanied by clear isomer dependence of the inhibition constant (K_i) and selectivity towards CA IX. Decreasing trends in K_i and selectivity index (S_I) values are observed with increasing separation of the cage carbon atoms. Interactions of compounds with the active sites of CA IX were explored with X-ray crystallography, and eight high-resolution crystal structures uncovered the structural basis of inhibition potency and selectivity.     

"Chemical ligation": a versatile method for nucleoside modification with boron clusters

A general approach to the synthesis of nucleoside conjugates containing carborane and metallocarborane complexes, based on Huisgen 1,3-dipolar cycloaddition ("chemical ligation"), is described. Boron-cluster-donors bearing terminal azide or ethynyl groups were prepared in the ring-opening reaction of dioxane-boron-cluster adducts and an azide anion or suitable alkynol-derived alcoholate nucleophile. Analogous derivatives bearing terminal sulfhydryl groups were also prepared. Nucleosides with various spacers containing terminal azide or ethynyl groups, located within nucleobases or sugar residues, were used as boron-cluster acceptors. The proposed methodology provides a convenient way to synthesize libraries of boron-cluster-modified nucleosides for various applications.     

Determining the vapour pressures of plant volatiles from gas chromatographic retention data

The frequently used vapour pressure versus Kováts retention index relationship has been evaluated in terms of its universal applicability, highlighting the problems associated with predicting the vapour pressures of structurally divergent organic compounds from experimentally measured isothermal Kováts retention indices. Two models differing in approximations adopted to express the activity coefficient ratio have been evaluated using 32 plant volatiles of different structural types as a test set. The validity of these models was established by checking their ability to reproduce 22 vapour pressures known from independent measurements. Results of the comparison demonstrated that (i) the original model, based on the assumption of equal activity coefficients for the test and reference substances, led, as expected, to a poor correlation (r2 = 89.1% only), with significantly deviating polar compounds and (ii) the model showed significant improvement after incorporating a new empirical term related to vaporization entropy and boiling point. The addition of this term allowed more than 99% of the vapour pressure variance to be accounted for. The proposed model compares favourably with existing correlations, while having an added advantage of providing a convenient tool for vapour pressure determination of chemically divergent chemicals.     

Exploration of the electrophoretic behaviour of borane cluster anions and of the capability of capillary electrophoresis to separate them chirally

Mobilities of investigated boron cluster compounds in 3-(N-morpholino)propanesulfonic and phosphate buffers adjusted to pH 7 either with sodium hydroxide or with tris(hydroxymethyl)aminomethane depend on both buffer ions. The zone width and zone asymmetry, which are usually markedly higher than those of organic or common inorganic ions of comparable size, depend on the type of the borane cluster anion. Unusual shapes of zones of two investigated compounds have been found in tris phosphate buffer. Acetonitrile was superior to methanol as an organic additive to separation systems from the viewpoint of the zone symmetry and separation speed. Narrow trigonal zones, typical of organic ions non-interacting with the capillary wall, have been observed for some bridged sandwich cobalt complexes in run buffers with the addition of acetonitrile. The interaction of borane cluster anions with beta-cyclodextrin cavity is excessively strong in purely aqueous solutions. Methanol and acetonitrile, which generally weaken the interaction, sometimes affect the separation enantioselectivity of various compounds in different ways in addition to the weakening effect. Chiral discrimination was reached for all ten investigated anions, which belong to four different structural types of cluster boranes. Stability constants estimated for some analyte-beta-cyclodextrin complexes range between 100 and 1800 l/mol in acceptable separations. The relative difference of the constants was from 3 to 20%.     

Separation of enantiomers of butorphanol and cycloamine by capillary zone electrophoresis

Butorphanol tartrate is a synthetic opioid agonist-antagonist used as analgesic, possessing three chiral centres in the basic part of the molecule. Its chiral purity is routinely controlled only by optical rotation. A new capillary zone electrophoresis method, capable to separate the enantiomers of butorphanol and intermediate of its synthesis, cycloamine, was developed. Different electrolyte composition (type and concentration of carrier ion, pH, and organic solvent addition), and type and concentration of several chiral selectors (natural and modified cyclodextrins) were tested. Using the optimized conditions (acidic electrolyte with the addition of highly sulphated gamma-cyclodextrin) as low as 0.05% of undesirable enantiomers can be detected. Selected method characteristics, i.e., linearity (0-50 mg/l), precision (2.5% at 20 mg/l), and accuracy (101 +/- 2% at 20 mg/l) were evaluated. The optimized method was applied for the analysis of real batches of butorphanol and cycloamine. It was found that butorphanol tartrate manufactured by IVAX Pharmaceuticals contains less than 0.05% of undesirable enantiomer.