Discussion of “Second order topological sensitivity analysis” by J. Rocha de Faria et al.

The aim of this discussion is to expose incorrect results in a previous IJSS article.     

Photochemical expulsion of the neutral monodentate ligand L in Ru(terpy*)(diimine)(L)2+: a dramatic effect of the steric properties of the spectator diimine ligand

A series of photoreactive complexes of the type Ru(terpy*)(N-N)(L)(2+), where terpy* is 4'-(3,5-ditertiobutylphenyl)-2,2':6',2' '-terpyridine, N-N is the bidentate chelate phen or dmp (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline), and L is the monodentate ligand dms, MeBN, or MeOBN (dms = dimethyl sulfide, MeBN = 2,6-dimethyl benzonitrile, MeOBN = 2,6-dimethoxybenzonitrile), has been synthesized and fully characterized by proton NMR spectroscopy, electrospray mass spectrometry, and UV-vis spectroscopy. The X-ray structures of four complexes were also obtained. In neat pyridine, the quantum yields for the photosubsitution of L by pyridine were measured and showed dramatic variations depending on the steric interactions between the spectator bidentate ligand and the leaving monodentate ligand L. The use of dmp instead of phen multiplied the photosubstitution efficiency by a factor of 20-50, depending on L. This effect could be qualitatively correlated to the distortions observed in the X-ray structures of the corresponding complexes. The highly distorted structure of Ru(terpy)(dmp)(dms)(PF(6))(2) showed a very high photosubsitution quantum yield phi = 0.36 in neat pyridine. The high photoreactivity of some of the compounds makes them particularly promising as components of future light-driven molecular machines.     

Inclusion complexes of trivalent lutetium cations with an acidic derivative of per(3,6-anhydro)-alpha-cyclodextrin

The cyclodextrin derivative (hexakis (2-O-carboxymethyl-3,6-anhydro)-alpha-cyclodextrin) forms mono- and bimetallic complexes with lutetium(III) in aqueous solution; the X-ray structure of the binuclear complex [Lu2(ACX)(H2O)2] is the first example of a lanthanide-cyclodextrin inclusion complex.     

On HCO spaces. An uncountable compactT 2 space,different from ℵ1+1, which is homeomorphic to each of its uncountable closed subspaces,which is homeomorphic to each of its uncountable closed subspaces

LetX be an Hausdorff space. We say thatX is a CO space, ifX is compact and every closed subspace ofX is homeomorphic to a clopen subspace ofX, andX is a hereditarily CO space (HCO space), if every closed subspace is a CO space. It is well-known that every well-ordered chain with a last element, endowed with the interval topology, is an HCO space, and every HCO space is scattered. In this paper, we show the following theorems: Theorem (R. Bonnet):

1. Every HCO space which is a continuous image of a compact totally disconnected interval space is homeomorphic to β+1 for some ordinal β.
2. Every HCO space of countable Cantor-Bendixson rank is homeomorphic to α+1 for some countable ordinal α.

Theorem (S. Shelah):Assume \(\diamondsuit _{\aleph _1 } \) . Then there is a HCO compact space X of Cantor-Bendixson rankω ₁} and of cardinality ?₁ such that:

1. X has only countably many isolated points,
2. Every closed subset of X is countable or co-countable,
3. Every countable closed subspace of X is homeomorphic to a clopen subspace, and every uncountable closed subspace of X is homeomorphic to X, and
4. X is retractive.

In particularX is a thin-tall compact space of countable spread, and is not a continuous image of a compact totally disconnected interval space. The question whether it is consistent with ZFC, that every HCO space is homeomorphic to an ordinal, is open.     

Simultaneous microbatch screening of enantiorecognition on solid chiral selectors using selected mixtures of test-racemates: a case study on cellulose tris(alpha-phenylpropionate) with configurational diversity

An improved methodology for microbatch screening in the liquid-solid enantioselective adsorption of racemates by solid chiral selector is presented and illustrated by the evaluation of a series of six cellulose tris(alpha-phenylpropionate) presenting a configurational diversity and cellulose tris (4-methylbenzoate). Analyses were performed on 5 mg scale of chiral selector and 150 microL of supernatant containing a mixture of three test-racemates. Fifteen test-racemates were chosen according to their molecular diversity using a hierarchical clustering approach for seven selected three-dimensional molecular properties. The 15 racemates were sorted in five test mixtures composed of three racemates each according to the following constraints: each triplet of test-racemates can be analyzed without peak overlap on a commercially available chiral stationary phase (CSP). The designed five groups of three racemates may be used for the evaluation of other chiral selectors in view of the preparation of CSPs. This methodology improves the throughput of the evaluation and could be automated.     

Recherches sur la structure électronique de composés soufrés (méthode L.C.A.O. améliorée)

Improved L.C.A.O. method primitively built for conjugated molecules holding only atoms of second row in the periodic classification is extended to molecules holding atoms of the third row. The application is done for thiophen, thioketones, SO₂ and SO₃. d orbitals are not introduced in this study. Discussion about results shows that d orbitals must be introduced when the sulphur atom is strongly positively charged like in sulphur oxides.