Determining molecular structures and conformations directly from electron diffraction using a genetic algorithm.

A global optimization strategy, based upon application of a genetic algorithm (GA), is demonstrated as an approach for determining the structures of molecules possessing significant conformational flexibility directly from gas-phase electron diffraction data. In contrast to the common approach to molecular structure determination, based on trial-and-error assessment of structures available from quantum chemical calculations, the GA approach described here does not require expensive quantum mechanical calculations or manual searching of the potential energy surface of the sample molecule, relying instead upon simple comparison between the experimental and calculated diffraction pattern derived from a proposed trial molecular structure. Structures as complex as all-trans retinal and p-coumaric acid, both important chromophores in photosensing processes, may be determined by this approach. In the examples presented here, we find that the GA approach can determine the correct conformation of a flexible molecule described by 11 independent torsion angles. We also demonstrate applications to samples comprising a mixture of two distinct molecular conformations. With these results we conclude that applications of this approach are very promising in elucidating the structures of large molecules directly from electron diffraction data.     

Synthesis of (−)-mellein, (+)-ramulosin, and related natural products

(−)-Mellein, (+)-ramulosin, (−)-O-methylmellein, (−)-6-hydroxymellein, (−)-6-methoxymellein, and (+)-6-hydroxyramulosin were synthesized as optically active forms using one-pot esterification-Michael addition-aldol reaction of δ-hydroxy-α,β-unsaturated aldehyde and diketene as a key step.     

Tetrastrontium dimanganese copper nonaoxide,Sr4Mn2CuO9

Single crystals of Sr₄Mn_2.09Cu_0.91O₉ have been grown by flux synthesis and the structure, closely related to the hexagonal perovskite 2H, was solved from single‐crystal X‐ray data in space group P321. The structure of Sr₄Mn₂CuO₉ is composed of chains of face‐sharing polyhedra with a sequence of two octahedra and one trigonal prism. The octahedra are filled by Mn atoms and the Cu atoms are randomly distributed at the centres of the square faces of the trigonal prism. A stacking fault is observed within one of the two chains, which can be attributed to a shifting of the chain along the c axis.     

Reversible colorimetric probes for mercury sensing

The selectivity and sensitivity of two colorimetric sensors based on the ruthenium complexes N719 [bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) bis(tetrabutylammonium) bis(thiocyanate)] and N749 [(2,2':6',2' '-terpyridine-4,4',4' '-tricarboxylate)ruthenium(II) tris(tetrabutylammonium) tris(isothiocyanate)] are described. It was found that mercury ions coordinate reversibly to the sulfur atom of the dyes' NCS groups. This interaction induces a color change in the dyes at submicromolar concentrations of mercury. Furthermore, the color change of these dyes is selective for mercury(II) when compared with other ions such as lead(II), cadmium(II), zinc(II), or iron(II). The detection limit for mercury(II) ions--using UV-vis spectroscopy--in homogeneous aqueous solutions is estimated to be approximately 20 ppb for N719 and approximately 150 ppb for N749. Moreover, the sensor molecules can be adsorbed onto high-surface-area mesoporous metal oxide films, allowing reversible heterogeneous sensing of mercury ions in aqueous solution. The results shown herein have important implications in the development of new reversible colorimetric sensors for the fast, easy, and selective detection and monitoring of mercuric ions in aqueous solutions.     

Synthesis of imidazoles as novel emivirine and S‐DABO analogues

5‐Alkyl‐4‐benzyl‐1,3‐dihydroimidazol‐2‐ones ( 3a‐d ) and 5‐alkyl‐4‐benzyl‐1,3‐dihydroimidazole‐2‐thiones (7a‐d) were prepared via Dakin West reaction on DL‐phenylalanine with the appropriate aliphatic acid anhydrides followed by hydrolysis and reaction with potassium cyanate or potassium thiocyanate. Compounds 3a‐d were alkylated with ethoxymethyl chloride to give the alkylated imidazoles 5a‐d which were considered analogues of Emivirine with deletion of carbonyl group at the 4‐position. Alkylation of 7a‐d afforded the corresponding S‐alkylated derivatives 8a‐p which in a similar way were considered analogues of S‐DABO. However all the imidazole derivatives were devoid of activity against HIV.     

Synthesis and structural characterisation of a novel tris-methylene bridged compound (NO) 4Fe2 Se(μ-CH2)3

The tris-methylene bridged compound (NO)₄Fe₂Se(μ-CH₂)₃ has been isolated. It has been characterised by IR and ¹H, ¹³C, and ⁷⁷Se NMR spectroscopy. Its structure has been determined by single-crystal X-ray diffraction methods. The structure consists of a heavy atom triangle consisting of one Se and two Fe atoms. The Fe-Fe and the two Fe-Se edges are bridged by methylene groups.     

Sinulochmodins A-C, three novel terpenoids from the soft coral Sinularia lochmodes

An unprecedented C,C-linked dimeric norcembranoid (sinulochmodin A, 1), a novel isocembranoid (sinulochmodin B, 2), and a novel yonarane norditerpenoid (sinulochmodin C, 3) were isolated from the soft coral Sinularia lochmodes. The structures of these metabolites were elucidated by extensive spectroscopic analysis and on the basis of the absolute structures of two related norditerpenoids (4 and 5), which were determined for the first time by a modified Mosher method. A plausible pathway for the biosynthesis of 1 and 3-5 from 2 was postulated. [structure: see text]     

Dithiolate complexes of manganese and rhenium: X-ray structure and properties of an unusual mixed valence cluster Mn3(CO)6(mu-eta2-SCH2CH2CH2S)3

Treatment of Mn(2)(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO.2H(2)O in CH(2)Cl(2) at room temperature afforded the dinuclear complexes Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (1), and Mn(2)(CO)(6)(mu-eta(4)-SCH(2)CH(2)S-SCH(2)CH(2)S) (2), respectively. Similar reactions of Re(2)(CO)(10) with 3,4-toluenedithiol, 1,2-benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (3), Re(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S) (4), and Re(2)(CO)(6)(SCH(2)CH(2)S-SCH(2)CH(2)S) (5), respectively. In contrast, treatment of Mn(2)(CO)(10) with 1,3-propanedithiol afforded the trimanganese compound Mn(3)(CO)(6)(mu-eta(2)-SCH(2)CH(2)CH(2)S)(3) (6), whereas Re(2)(CO)(10) gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques.     

Facile reduction of aromatic nitro/azido functionality on solid support employing Al/NiCl2·6H2O and Al/NH4Cl: synthesis of pyrrolo[2,1-c][1,4]benzodiazepines

An efficient and mild method for the reduction of aromatic nitro and azido groups on solid support using Al/NiCl₂·6H₂O and Al/NH₄Cl is described. This solid phase reduction technique has been applied towards the synthesis of DNA binding pyrrolo[2,1-c][1,4]benzodiazepine antitumour antibiotics.     

Electronic phase separation in transition metal oxide systems

Electronic phase separation is increasingly getting recognized as a phenomenon of importance in understanding the magnetic and electron transport properties of transition metal oxides. The phenomenon dominates the rare-earth manganates of the formula Ln(1-x)A(x)MnO(3)(Ln = rare earth and A = alkaline earth) which exhibit ferromagnetism and metallicity as well as charge-ordering, depending on the composition, size of A-site cations and external factors such as magnetic and electric fields. We discuss typical phase separation scenarios in the manganates, with particular reference to Pr(1-x)Ca(x)MnO(3)(x= 0.3-0.4), (La(1-x)Ln(x))(0.7)Ca(0.3)MnO(3)(Ln = Pr, Nd, Gd and Y) and Nd(0.5)Sr(0.5)MnO(3). Besides discussing the magnetic and electron transport properties, we discuss electric field effects. Rare-earth cobaltates of the type Pr(0.7)Ca(0.3)CoO(3) and Gd(0.5)Ba(0.5)CoO(3) also exhibit interesting magnetic and electron transport properties which can be understood in terms of phase separation.