Building addressable libraries: the use of electrochemistry for spatially isolating a heck reaction on a chip

Pd(0) was generated at preselected sites on an electrochemically addressable chip and then utilized to effect a Heck reaction. The Pd(0) was confined to the preselected electrodes with the use of allylmethyl carbonate. Unlike most mediated electrochemical reactions, the electrolysis in this case was not used to convert a stoichiometric process into a catalytic one by recycling the metal. Instead, the unique environment of the chip was used to interfere with a catalytic process to make it stoichiometric. This was done to gain spatial control over the reaction. The development of a strategy for conducting Pd(0)-catalyzed reactions on the chips should greatly expand the synthetic chemistry available for building chip-based libraries.     

Toward artificial developmental regulators

A polyamide-peptide conjugate is designed which recruits sequence specifically the developmental regulator Exd to a cognate DNA site. In particular, an eight-ring hairpin polyamide (Im-Im-Py(C3H6NHR)-Py-gamma-Im-Py-Py-Py-beta-Dp) with a heptapeptide (R = Ac-Phe-Tyr-Pro-Trp-Met-Lys-Gly-) attached on a central ring was shown to induce cooperative binding of the Drosophila Hox protein cofactor Exd with a Kd of 4.4 nM in vitro, an order of magnitude more efficient than the natural Hox protein partner Ubx. The conjugate joins two sequence specific domains, one for DNA and one for the protein. This small molecule thus serves as a cooperative protein-DNA dimerizer, which mimics the natural Hox family of developmental regulators.     

A recycling technique for the chromatographic separation of enantiomers and diastereomers on triacetylcellulose

A simple and inexpensive equipment for the optical resolution of enantiomers (and separation of diastereomers) on triacetylcellulose in ethanol at elevated pressure is described. It involves a closed circuit of solvent (pump—column—detector—pump) allowing a continuous chromatography up to 16 cycles without stopping the flow or handling fractions.This useful and versatile method permitting also the determination of enantiomeric purities is illustrated by several examples of centro-, axial- and planarchiral arenes and metallocenes.Herrn Prof. Dr.U. Schmidt, Stuttgart, zum 60. Geburtstag gewidmet.     

Dimerer Zimtalkohol

Zusammenfassung Die Stammsubstanzen des Lignins gehören der Gruppe der p-Hydroxyzimtalkohole an. Sie werden durch wäßrige Mineralsäure polymerisiert. Um das Wesen dieser Reaktion kennenzulernen, wurde der Zimtalkohol selbst in verdünnter wäßriger Lösung der Wirkung von Säure ausgesetzt. Er bildet ein Dimeres der Konstitution VIII, die durch Abbau und Synthese bewiesen wurde. Es ist anzynehmen, daß die Polymerisation der p-Hydroxyzimtalkohole nacl, einem Schema verläuft, von dem die Dimerisation des Zimtalkohols die erste Stufe ist.Institut für die Chemie dei Holzes und der PolysaccharideKollegenA. Wacek in alter Freundschaft zum 60. Geburtstag gewidmet.K. Freudenberg.     

The Henicosaphosphide Iodides of Potassium and Rubidium,K4P21I and Rb4P21I

The novel ternary polyphosphides M₄P₂₁I (M = K, Rb) have been synthesized from the elements in single crystalline form, representing further examples for the formation of mixed crystals between simple salts and binary phosphides. They form as ruby‐red platelets and dark‐red prisms, respectively, and are only slightly sensitive to moisture and oxygen. The compounds are isotypic (Ccmm (no 63); Z = 4; oP104; K₄P₂₁I: a = 12.853Å; b = 21.795Å; c = 9.748Å; 1168 hkl, R = 0.033; Rb₄P₂₁I: a = 13.281Å; b = 21.868Å; c = 9.771Å; 777 hkl, R = 0.053) and feature corrugated 2D networks formed from two different types of polymerized P₇ units. The networks form large cavities filled by M⁺ and I^‐ ions. Zigzag chains of condensed trigonal M₆ prisms, centered by the I^‐ anions, separate the polyphosphide nets. The mean homoatomic P‐P bond length (d = 2.216Å) corresponds to a P‐P single bond. However, the individual P‐P distances vary with position and function (2.126 ‐ 2.247Å) and these are compared with those of the isolated P₂₁^‐3 anion.     

Effect of surfactants on the stability of thin liquid film flow on a rotating disk

The effect of surfactants on surface instabilities of thin liquid film flow on a rotating disk was studied at different flow rates Q (0.5相似文献   

Open-shell generalized perturbation theory

Open shell generalized perturbation theory (GPT) is a systematic scheme for the improvement of a multi-configurational zeroth order wavefunction that can be chosen so the lowest order corresponds to a sum-of-the-pairs- type theory of electron correlation (with or without pair-pair couplings) in the spirit of the theories of Kelly, Sinano?lu, and Nesbet for the single configurational case. Applications axe presented to the generalized perturbative solution for individual states and for the simultaneous solution for many nondegenerate states. The (2n+ 1)-rule of GPT and the interchange theorems of double Girl' are illustrated. A brief discussion is included concerning the use of GPT in ab initio evaluations of the true parameters that are customarily, only modeled and then fit to experiment in semi-empirical theories of molecular electronic structure. The conceptual value of expressing the results of ab initio calculations in terms of effective hamiltonians is stressed and the relationship between open shell GPT and other theories of electron correlation is also considered.     

Reference-free NOE NMR analysis

Nuclear Overhauser Effect (NOE) methods in NMR are an important tool for 3D structural analysis of small molecules. Quantitative NOE methods conventionally rely on reference distances, known distances that have to be spectrally separated and are not always available. Here we present a new method for evaluation and 3D structure selection that does not require a reference distance, instead utilizing structures optimized by molecular mechanics, enabling NOE evaluation even on molecules without suitable reference groups.

A quantitative Nuclear Overhauser Effect (NOE) analysis approach that avoids the use of and internal reference distance to perform molecular configuration selection.     

Octahedral (cis-cyclam)iron(III) complexes with O,N-coordinated o-iminosemiquinonate(1-) pi radicals and o-imidophenolate(2-) anions

Three octahedral complexes containing a (cis-cyclam)iron(III) moiety and an O,N-coordinated o-iminobenzosemiquinonate pi radical anion have been synthesized and characterized by X-ray crystallography at 100 K: [Fe(cis-cyclam)(L(1-3)(ISQ))](PF(6))(2) (1-3), where (L(1-3)(ISQ)) represents the monoanionic pi radicals derived from one-electron oxidations of the respective dianion of o-imidophenolate(2-), L(1), 2-imido-4,6-di-tert-butylphenolate(2-), L(2), and N-phenyl-2-imido-4,6-di-tert-butylphenolate(2-), L(3). Compounds 1-3 possess an S(t) = 0 ground state, which is attained via strong intramolecular antiferromagnetic exchange coupling between a low-spin central ferric ion (S(Fe) = 1/2) and an o-imino-benzosemiquinonate(1-) pi radical (S(rad) = 1/2). Zero-field M?ssbauer spectra of 1-3 at 80 K confirm the low-spin ferric electron configuration: isomer shift delta = 0.26 mm s(-1) and quadrupole splitting DeltaE(Q) = 1.96 mm s(-1) for 1, 0.28 and 1.93 for 2, and 0.33 and 1.88 for 3. All three complexes undergo a reversible, one-electron reduction of the coordinated o-imino-benzosemiquinonate ligand, yielding an [Fe(III)(cis-cyclam)(L(1-3)(IP))](+) monocation. The monocations of 1 and 2 display very similar rhombic signals in the X-band EPR spectra (g = 2.15, 2.12, and 1.97), indicative of low-spin ferric species. In contast, the monocation of 3 contains a high-spin ferric center (S(Fe) = 5/2) as is deduced from its M?ssbauer and EPR spectra.     

Ruthenium Complexes Containing "Noninnocent" o-Benzoquinone Diimine/o-Phenylenediamide(2-) Ligands. Synthesis and Crystal Structure of the Nitrido-Bridged Complex [{LRu(o-C(6)H(4)(NH)(2))}(2)(&mgr;-N)](PF(6))(2).3CH(3)CN.C(6)H(5)CH(3)

Reaction of LRu(III)Cl(3) (L = 1,4,7-trimethyl-1,4,7-triazacyclononane) with 1,2-phenylenediamine (opdaH(2)) in H(2)O in the presence of air affords [LRu(II)(bqdi)(OH(2))](PF(6)) (1), where (bqdi) represents the neutral ligand o-benzoquinone diimine. From an alkaline methanol/water mixture of 1 was obtained the dinuclear species [{LRu(II)(bqdi)}(2)(&mgr;-H(3)O(2))](PF(6))(3) (1a). The coordinated water molecule in 1 is labile and can be readily substituted under appropriate reaction conditions by acetonitrile, yielding [LRu(II)(bqdi)(CH(3)CN)](PF(6))(2) (2), and by iodide and azide anions, affording [LRu(II)(bqdi)I](PF(6)).0.5H(2)O (3) and [LRu(bqdi)(N(3))](PF(6)).H(2)O (4), respectively. Heating of solid 4 in vacuum at 160 degrees C generates N(2) and the dinuclear, nitrido-bridged complex [{LRu(o-C(6)H(4)(NH)(2))}(2)(&mgr;-N)](PF(6))(2) (5). Complex 5 is a mixed-valent, paramagnetic species containing one unpaired electron per dinuclear unit whereas complexes 1-4 are diamagnetic. The crystal structures of 1, 1a.3CH(3)CN, 3, 4.H(2)O, and 5.3CH(3)CN.0.5(toluene) have been determined by X-ray crystallography: 1 crystallizes in the monoclinic space group P2(1)/m, Z = 2, with a = 8.412(2) ?, b = 15.562(3) ?, c = 10.025 ?, and beta = 109.89(2) degrees; 1a.3CH(3)CN, in the monoclinic space group C2/c, Z = 4, with a = 19.858(3) ?, b = 15.483(2) ?, c = 18.192(3) ?, and beta = 95.95(2) degrees; 3, in the orthorhombic space group Pnma, Z = 4, with a = 18.399(4) ?, b = 9.287(2) ?, and c = 12.052(2) ?, 4.H(2)O, in the monoclinic space group P2(1)/c, Z = 4, with a = 8.586(1) ?, b = 15.617(3) ?, c = 16.388(5) ?, and beta = 90.84(2) degrees; and 5.3CH(3)CN.0.5(toluene), in the monoclinic space group P2(1)/c, Z = 4, with a = 15.003(3) ?, b = 16.253(3) ?, c = 21.196(4) ?, and beta = 96.78(3) degrees. The structural data indicate that in complexes 1-4 the neutral o-benzoquinone diimine ligand prevails. In contrast, in 5 this ligand has predominantly o-phenylenediamide character, which would render 5 formally a mixed-valent Ru(IV)Ru(V) species. On the other hand, the Ru-N bond lengths of the Ru-N-Ru moiety at 1.805(5) and 1.767(5) ? are significantly longer than those in other crystallographically characterized Ru(IV)=N=Ru(IV) units (1.72-1.74 ?). It appears that the C(6)H(4)(NH)(2) ligand in 5 is noninnocent and that formal oxidation state assignments to the ligands or metal centers are not possible.