Synthesis, characterization, and testing of supported Au catalysts prepared from atomically-tailored Au38(SC12H25)24 clusters

Nearly monodispersed Au(38)(SC(12)H(25))(24) clusters (1.7 ± 0.2 nm) were synthesized using a modified Brust process while utilizing a "thiol etching" approach for the ligand exchange. HRTEM, MALDI, FTIR, and XAS analysis confirmed the formation of the 38-atom clusters in solution. This solution was used to impregnate a microporous TiO(2) support to give 0.7% Au(38)/TiO(2) catalyst. Subsequent drying in air and treatment with H(2)/He at 400 °C removed most of the sulfur ligands, and also increased the Au cluster size to 3.9 ± 0.96 nm. XPS and EXAFS analysis of this supported catalyst showed trace levels of residual sulfides, apparently located at the Au-TiO(2) interface. CO oxidation tests on these supported clusters show an activation energy and range of TOFs comparable to those reported by others. These results suggest that supported Au clusters of controllable size can be prepared with this thiol-ligated solution-based method, providing a new approach to the synthesis of these catalysts.     

A Modular Approach for Interlocking Enzymes in Whatman Paper

A potentially universal approach is presented for enzyme attachment to cellulose that significantly enhances enzyme stability while retaining high activity, and involves no chemical functionalization of cellulose. Bovine serum albumin (BSA) was interlocked in cellulose to form a protein‐friendly surface (named BSA‐Paper), while also providing COOH and NH₂ groups for subsequent attachment of enzymes. The desired enzyme is then mixed with additional BSA and interlocked on BSA‐Paper. The second BSA layer dilutes and crosslinks the enzyme for improved stability. Laccase was tested as a model enzyme for interlocking on BSA‐Paper, and was found to retain over 100 % activity and was 240 times more stable at 25 °C (half life=180 d) than laccase. This new approach was also tested with a few other enzymes with encouraging results, thus providing a potentially universal method for stabilization of enzymes on cellulose with retention of high activities.     

Polymer- bound flavins. III. Effects of coil dimension and substrate structure on reaction kinetics in water/2-propanol mixtures

The strong influence of medium composition (water/2-propanol mixtures) on the rate of oxidation of 1-substituted dihydronicotinamides by a flavin-containing polyelectrolyte was studied. We found that the coil dimensions of the corresponding copolymer of styrene and vinylbenzyltriethylammoniumchloride without flavin groups dramatically depend on the solvent. Viscometric measurements revealed compact coil conformations in solvents of both high water and high 2-propanol content, but pronounced coil expansion in intermediate mixtures. These changes of polyelectrolyte coil dimensions are related to changes in electrostatic potential of the microreactors. Addition of 2-propanol also results in decrease of substrate enrichments, caused by weakening of nonpolar polymer–substrate interactions, as was demonstrated for 1-carbamoylmethyl-, 1-benzyl-, and 1 decyl-substituted 1,4-dihydronicotinamide substrates. The enormous decrease in rate constant for oxidation of DNAH by 2 upon increasing the 2-propanol content from 10 to 40% (v/v), from k = 3120 to 21 M^?1 s^?1, can thus be explained as a cooperation of both effects. Evidence for the formation of a charge transfer complex between the polyelectrolyte-bound flavin and the dihydronicotinamide having a long-wavelength absorption is also presented.     

A cluster of many small holes with negative imaginary surface impedances may generate a negative refraction index

We deal with the scattering of an acoustic medium modeled by an index of refraction n varying in a bounded region Ω of and equal to unity outside Ω. This region is perforated with an extremely large number of small holes D_m's of maximum radius a, a << 1, modeled by surface impedance functions. Precisely, we are in the regime described by the number of holes of the order M:=O(a^{β ? 2}), the minimum distance between the holes is d ～ a^t, and the surface impedance functions of the form λ_m～λ_m,0a^?β with β > 0 and λ_m,0 being constants and eventually complex numbers. Under some natural conditions on the parameters β,t, and λ_m,0, we characterize the equivalent medium generating approximately the same scattered waves as the original perforated acoustic medium. We give an explicit error estimate between the scattered waves generated by the perforated medium and the equivalent one, respectively, as a→0. As applications of these results, we discuss the following findings:

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An expeditious one-step entry to the tetracyclic core of integrastatins

Herein we describe a one-step assembly of structurally complex small molecules representing the central skeleton of integrastatins by employing a simple pinacol transform.     

Polymer-bound bulky-phosphite modified rhodium hydroformylation catalysts

Attachment of phosphites to styrene copolymers is described which are used as rhodium hydroformylation catalysts. The influence of the chain loading on the activity and complex formation of three types of copolymer-bound rhodium hydroformylation catalysts in comparison with their low molecular weight analogues has been studied. The catalytic activity of the polystyrene-bound system with the most bulky phosphite, the first system studied, is identical to that of the low molecular weight analogue. The catalysts show a high activity towards the hydroformylation of the otherwise unreactive cyclooctene. It was found that only one phosphite is coordinated to the rhodium complex in its active form. An equilibrium between this complex and an inactive complex without phosphite ligands prohibits its use in continuous flow reactors. Secondly, as polymer support a perfectly random copolymer of styrene and less bulky 3,3′,5,5′-tetra-tert-butylbiphenyl-2,2′-diyl p-vinylphenylphosphite was used. The chain loading α of this copolymer with phosphite ligands has a large influence on the complex formation of the catalyst. With high chain loadings moderately active bis-phosphite catalysts are formed. Low chain loadings give active, easily accessible, monophosphite complexes. The active species in the hydroformylation of sterically hindered alkenes is a mono-phosphite rhodium complex. The activity of the copolymer-bound catalyst towards the hydroformylation of cyclooctene is found to be as high as the activity of its low molecular weight analogue. For styrene, this polymer catalyst yields a slower catalyst than the low-molecular weight analogue. The third part demonstrates that silica-grafted polymer-bound phosphite modified rhodium complexes can be used in continuous flow reactors. The hydroformylation of styrene was carried out at moderate pressure (pCO/H₂ = 3 MPa) and temperature (T = 100°C), yielding constant conversions over a period of at least ten days. These positive results were obtained in benzene as a solvent and for a ligand to rhodium ratio of only four.     

Radical polymerization of methyl methacrylate in the presence of stereoregular poly(methyl methacrylate). IV. Influence of solvent type

Methyl methacrylate (MMA) was polymerized by radical initiation at 25°C or 35°C in various solvents in the presence of stereoregular poly(methyl methacrylate) (PMMA). The occurrence of stereospecific replica polymerization appeared to be related to the capability of stereoassociation of isotactic and syndiotactic PMMA. The solvents can be roughly divided into three types. Type A solvents are polar solvents, which promote stereoassociation resulting in gelation and precipitation. Examples are dimethylformamide, dimethyl sulfoxide, and acetone. Type B solvents are nonpolar aromatic solvents like benzene and toluene, wherein stereoassociation is weaker but still leads to gelation. Type C solvents are very good solvents, in which stereoassociation does not occur. Chloroform and dichloromethane belong to this class. In solvents of type A as well as type B, polymerization in the presence of i-PMMA as a polymer matrix was syndiospecific. However, in the presence of s-PMMA as a polymer matrix the polymerization was isospecific only in type A solvents. The syndiotactic or isotactic triad contents of the polymer formed could be as high as ca. 90% at low conversions. In solvents of type C, polymerization in the presence of stereoregular PMMA proceeds according to a normal radical mechanism. Syndiotacticity was always less than 70%. Stereocomplexes formed in situ during replica polymerization were partly crystalline as detected by x-ray diffraction. The highest crystallinity was detected in those formed in type A solvents.     

Contributions of hydroxyethyl groups to the DNA binding affinities of anthracene probes

Contributions of hydroxyethyl functions to the DNA binding affinities of substituted anthracenes are evaluated by calorimetry and spectroscopy. Isothermal titration calorimetry indicated that binding of the ligands to calf thymus DNA (5 mM Tris buffer, 50 mM NaCl, pH 7.2, 25 degrees C) is exothermic. The binding constants increased from 1.5 x 10(4) to 1.7 x 10(6) M(-1) as a function of increase in the number of hydroxyethyl functions (0-4). DNA binding was accompanied by red-shifted absorption (approximately 630 cm(-1)), strong hypochromism (>65%), positive induced-circular dichroism bands, and negative linear dichroism signals. DNA binding, in general, increased the helix stabilities to a significant extent (DeltaT(m) approximately 7 degrees C, DeltaDeltaH approximately 3 kcal/mol, DeltaDeltaS approximately 6-20 cal/K.mol). The binding constants showed a strong correlation with the number of hydroxyethyl groups present on the anthracene ring system. Analysis of the binding data using the hydrophobicity parameter (Log P) showed a poor correlation between the binding affinity and hydrophobicity. This observation was also supported by a comparison of the affinities of probes carrying N-ethyl (Kb = 0.8 x 10(5) M(-1)) versus N-hydroxyethyl side chains (Kb = 5.5 x 10(5) M(-1)). These are the very first examples of a strong quantitative correlation between the DNA binding affinity of a probe and the number of hydroxyethyl groups present on the probe. These quantitative findings are useful in the rational design of new ligands for high-affinity binding to DNA.