Turning off phototriggered linkage isomerizations in ruthenium dimethyl sulfoxide complexes

We report on the spectroscopy, electrochemistry, and linkage isomerization in a family of [Ru(tpy)(L2)(dmso)](z)()(+) complexes (tpy is 2,2':6',2' '-terpyridine, dmso is dimethyl sulfoxide, and L2 is a variable ligand: 2,2'-bipyridine (bpy), 2-picolinate (pic), N,N,N',N'-tetramethylethylenediamine (tmen), acetylacetonate (acac), or malonate (mal)). The identity of this bidentate ligand serves to tune the absorption maxima (lambda(max) = 419-502 nm) and the reduction potential (E(1/2) = 1.67 to 0.82 V) of these complexes. Photochemical and electrochemical studies show that S-->O and O-->S linkage isomerization may be triggered through an electron transfer mechanism, resulting in dramatic shifts in both the absorption maxima and the reduction potential (for [Ru(tpy)(pic)(dmso)](+) S-bonded, 421 nm, 1.38 V vs Ag/AgCl; O-bonded, 527 nm, 1.38 V vs Ag/AgCl). Certain of these complexes [Ru(tpy)(acac)(dmso)](+) and [Ru(tpy)(mal)(dmso)] do not undergo isomerization. These results are discussed in the context of electron transfer triggered isomerization.     

Trace aluminum determination and sampling problems of archeological bone employing destructive neutron activation analysis

A destructive neutron activation analysis procedure was developed for determining trace aluminum content in bone. It was found that soil contamination can influence the aluninum bone levels in prehistoric bone specimens. These maximum aluninum content values for prehistoric bone are larger than those of modern bone and comparable to aluminum levels present in bone from renal patients.     

Room-temperature photochromism in cis- and trans-[Ru(bpy)2(dmso)2]2+

We report on phototriggered Ru-S --> Ru-O and thermal Ru-O --> Ru-S intramolecular linkage isomerizations in cis- and trans-[Ru(bpy)2(dmso)2]2+. The cis complex features only S-bonded sulfoxides (cis-[S,S]), whereas the trans isomer is characterized by S- and O-bonded dmso ligands. Both cis-[S,S] and trans-[S,O] exhibit photochromism at room temperature in dmso solution and ionic liquid (IL). Rates of reaction in IL were monitored by UV-visible spectroscopy and are similar to those reported in dmso solution (k(O-->S) ranges from approximately 10(-3) to 10(-4) s(-1)). Cyclic voltammetric measurements of cis-[S,S] and trans-[S,O] are consistent with an electrochemically triggered linkage isomerism mechanism. While both cis-[S,S] and trans-[S,O] are photochromic at room temperature, neither complex is emissive. However, upon cooling to 77 K, cis-[S,S] exhibits LMCT (ligand-to-metal charge transfer) emission typical of many ruthenium polypyridine complexes. In contrast to cis-[S,S], trans-[S,O] does not show any detectable emission even at 77 K.     

Automated synthesis of 3'-metalated oligonucleotides

We report the first synthesis of a metallonucleoside bound to a solid support and subsequent oligonucleotide synthesis with this precursor. Large-scale syntheses of metal-containing oligonucleotides are achieved using a solid support modified with [Ru(bpy)(2)(impy')](2+) (bpy is 2,2'-bipyridine; impy' is 2'-iminomethylpyridyl-2'-deoxyuridine). A duplex formed with the metal-containing oligonucleotide exhibits superior thermal stability when compared to the corresponding unmetalated duplex (T(m) = 50 degrees C vs T(m) = 48 degrees C). Electrochemical (E(1/2) = 1.3 V vs NHE), absorption (lambda(max) = 480 nm), and emission (lambda(max) = 720 nm, tau = 44 ns, Phi = 0.11 x 10(-)(3)) data for the ruthenium-modified oligonucleotides indicate that the presence of the oligonucleotide does not perturb the electronic properties of the ruthenium complex. The absence of any change in the emission properties upon duplex formation suggests that the [Ru(bpy)(2)(impy)](2+) chromophore will be a valuable probe for DNA-mediated electron-transfer studies. Despite the relatively high Ru(III/II) reduction potential, oxidative quenching of photoexcited [Ru(bpy)(2)(impy)](2+) does not lead to oxidative damage of guanine or other DNA bases.     

Determination of vanadium in serum by pre-irradiation and post-irradiation chemistry and neutron activation analysis

Vanadium in serum was investigated by pre-irradiation chemistry neutron activation analysis employing anion exchange chromatography and post-irradiation neutron activation employing solvent extraction techniques. From a comparison of these techniques it is concluded that vanadium is present in human serum in the sub-ppb range.     

Formation of ultrasharp vertically aligned Cu-Si nanocones by a DC plasma process

We report an effective method for the production of ultrasharp vertically oriented silicon nanocones with tip radii as small as 5 nm. These silicon nanostructures were shaped by a high-temperature acetylene and ammonia dc plasma reactive ion etch (RIE) process. Thin-film copper deposited onto Si substrates forms a copper silicide (Cu3Si) during plasma processing, which subsequently acts as a seed material masking the single-crystal cones while the exposed silicon areas are reactive ion etched. In this process, the cone angle is sharpened continually as the structure becomes taller. Furthermore, by lithographically defining the seed material as well as employing an etch barrier material such as titanium, the cone location and substrate topography can be controlled effectively.     

Hard X‐ray phase‐contrast tomography of non‐homogeneous specimens: grating interferometry versus propagation‐based imaging

X‐ray phase‐contrast imaging is an effective approach to drastically increase the contrast and sensitivity of microtomographic techniques. Numerous approaches to depict the real part of the complex‐valued refractive index of a specimen are nowadays available. A comparative study using experimental data from grating‐based interferometry and propagation‐based phase contrast combined with single‐distance phase retrieval applied to a non‐homogeneous sample is presented (acquired at beamline ID19‐ESRF). It is shown that grating‐based interferometry can handle density gradients in a superior manner. The study underlines the complementarity of the two techniques for practical applications.     

Phototriggered S --> O isomerization of a ruthenium-bound chelating sulfoxide

We have prepared and characterized [Ru(bpy)2(OS)]+ (bpy = 2,2'-bipyridine; OS = 2-methylthiobenzoate) and the chelating sulfoxide S-[Ru(bpy)2(OSO)]+ (OSO = methylsulfonylbenzoate) by 1H NMR (1-D and 2-D COSY), IR, UV-visible spectroscopy, electrochemistry, and X-ray crystallography. Many of the metrical and crystal parameters are nearly identical between the two structures. The sulfoxide is produced from m-cpba oxidation of the thioether. Photolysis of S-[Ru(bpy)2(OSO)]+ results in a dramatic shift in the metal-to-ligand charge-transfer (3MLCT) transition from 396 to 496 nm, with a new higher-energy 3MLCT transition appearing at 355 nm. Concomitant with this change, the Ru3+/2+ reduction potential shifts from 1.25 V vs Ag/AgCl to 0.9 V vs Ag/AgCl. These changes are ascribed to phototriggered excited-state isomerization of the sulfoxide from S- to O-bonded. Examination of the 1H NMR spectra in a CD3OD solvent before, during, and after irradiation shows the presence of two O-bonded complexes that revert to the structurally characterized S-bonded ground state. This represents the first report of isomerization of a chelating sulfoxide in a photochromic Ru complex.     

Reversible electrowetting of vertically aligned superhydrophobic carbon nanofibers

Reversible electrostatically induced wetting (electrowetting) of vertically aligned superhydrophobic carbon nanofibers has been investigated. Carbon nanofibers on a 5 x 5 microm pitch were grown on Si substrates, electrically insulated with a conformal dielectric, and hydrophobized with fluoropolymer. This nanostructured scaffold exhibited superhydrophobic behavior for saline (theta approximately 160 degrees). Electrowetting induced a contact angle reduction to theta approximately 100 degrees. Competitive two-liquid (dodecane/saline) electrowetting exhibited reversibility on the same nanostructured scaffold. Without applied bias, ultra-fine-point tip (approximately 25 nm radius) nanofibers result in effectively zero capacitance with the overlying saline layer. Complete electrowetting of the substrate is confirmed as capacitance values increase by several orders of magnitude with increased wetting. These results demonstrate the applicability of reversible electrowetting on nanostructured scaffolds and use of nanofabricated structures that can be integrated with various micro- and nanoelectronic technologies.