Hyperpolarization of Amino Acids in Water Utilizing Parahydrogen on a Rhodium Nanocatalyst

NMR offers many possibilities in chemical analysis, structural investigations, and medical diagnostics. Although it is broadly used, one of NMR spectroscopies main drawbacks is low sensitivity. Hyperpolarization techniques enhance NMR signals by more than four orders of magnitude allowing the design of new contrast agents. Parahydrogen induced polarization that utilizes the para-hydrogen's singlet state to create enhanced signals is of particular interest since it allows to produce molecular imaging agents within seconds. Herein, we present a strategy for signal enhancement of the carbonyl ¹³C in amino acids by using parahydrogen, as demonstrated for glycine and alanine. Importantly, the hyperpolarization step is carried out in water and chemically unmodified canonical amino acids are obtained. Our approach thus offers a high degree of biocompatibility, which is crucial for further application. The rapid sample hyperpolarization (within seconds) may enable the continuous production of biologically useful probes, such as metabolic contrast agents or probes for structural biology.     

Development of novel flexible black silicon

We report a new type of black silicon: flexible black silicon. A silicon-on-insulator (SOI) wafer is irradiated by automatically scanning a femtosecond laser and then split by etching out the SOI silica middle layer. Large-area, uniform micro spikes on the surface of a very thin flexible silicon layer are obtained. The black silicon shows good flexibility and optical properties. The absorption spectrum of the flexible black silicon is as high as 97% in the visible and insensitive to the change of the incident angle of the light, which makes it a potential good candidate as an absorber for the solar-thermo generator.     

Emergent rotational symmetries in disordered magnetic domain patterns

Uniaxial systems often form labyrinthine domains that exhibit short-range order but are macroscopically isotropic and would not be expected to exhibit precise symmetries. However, their underlying frustration results in a multitude of metastable configurations of comparable energy, and driving such a system externally might lead to pattern formation. We find that soft x-ray speckle diffraction patterns of the labyrinthine domains in CoPd/IrMn heterostructures reveal a diverse array of hidden rotational symmetries about the magnetization axis, thereby suggesting an unusual form of emergent order in an otherwise disordered system. These symmetries depend on applied magnetic field, magnetization history, and scattering wave vector. Maps of rotational symmetry exhibit intriguing structures that can be controlled by manipulating the applied magnetic field in concert with the exchange bias condition.     

Synthesis of diindolocarbazoles by Cadogan reaction: route to ladder oligo(p-aniline)s

Symmetric and nonsymmetric diindolocarbazoles were successfully synthesized for the first time by a Cadogan ring closure using N-alkyl-2,7-disubstituted carbazole precursors. Cyclization reaction on N-alkyl-2,7-di(2'-nitrophenyl) carbazole derivatives is not regioselective and produced a separable mixture of symmetric and nonsymmetric diindolocarbazoles. A carbazole derivative with methyl protective groups at the 1- and 8-positions was therefore used to obtain a symmetric ladder oligo(p-aniline) (compound 22). Optical and electrochemical properties of compound 22 indicate that its neutral semiconducting form is stable in air. This novel class of electroactive ladder oligomers should create new opportunities in micro- and nanoelectronics.     

Preparation and photocatalytic behavior of MoS2 and WS2 nanocluster sensitized TiO2

A new approach has been developed for the fabrication of visible light photocatalysts. Nanoclusters of MoS2 and WS2 are coupled to TiO2 by an in situ photoreduction deposition method taking advantage of the reducing power of the photogenerated electrons from TiO2 particles. The photocatalytic degradation of methylene blue and 4-chlorophenol in aqueous suspension has been employed to evaluate the visible light photocatalytic activity of the powders. The blue shift in the absorption onset confirms the size quantization of MS2 nanoclusters, which act as effective and stable sensitizers, making it possible to utilize visible light in photocatalysis. Quantum size effects alter the energy levels of the conduction and valence band edges in the coupled semiconductor systems, which favors the interparticle electron transfer. In addition, the coupled systems are believed to act in a cooperative manner by increasing the degree of charge carrier separation, which effectively reduces recombination.     

Facile fabrication and characterization of hierarchically porous calcium carbonate microspheres

Higher-order porous calcite microspheres exhibiting high specific surface areas, unusual morphologies and textures were fabricated by a simple precipitation reaction of CaCO3 in the presence of PSMA as a crystal modifier.     

Versatile and facile synthesis of diverse semisynthetic tetracycline derivatives via Pd-catalyzed reactions

A diverse collection of tetracycline derivatives has been synthesized utilizing Heck, Suzuki, and other palladium-coupling reactions via tetracycline arenediazonium and iodoarene salts. Large numbers of tetracyclines are now possible via these reactions, including numerous upper periphery derivatives of doxycycline, minocycline, sancycline, and methacycline modified at positions C7, C9, and C6-C13 on the tetracycline naphthacene ring. Application of palladium-coupling reactions to the tetracyclines has yielded new tetracycline classes with differing structural attributes, greatly increasing the structural diversity of this family of antibiotics, one of the last of the early antibiotic families to be expanded by organic and medicinal chemistry.     

Powder preparation and UV absorption properties of selected compositions in the CeO2-Y2O3 system

Several approaches have been investigated to prepare fluorite-type compositions within the (1−x) CeO₂-xYO_1.5 system. The optical properties of the resulting modified-ceria materials have been characterized in order to evaluate their potential abilities as inorganic UV absorbers. Diffuse reflectance analyses reveal a strong optical absorption between 390 and 400 nm for all substituted compositions and the spectral selectivities are estimated suitable for the targeted application. Additionally, time resolved microwave conductivity (TRMC) and phenol photodegradation analyses do not indicate any photocalatytic activity for these compositions. Aqueous colloidal suspensions of the Ce_0.7Y_0.3O_1.85 UV absorber have been carried out.