Magnetic circular dichroism studies XXXII

CNDO calculations of the MCD spectra of 7- and 9-methyladenine have been carried out in two approximations. A minor modification of the CNDO/S method of Jaffé and coworkers shows an improvement over Jaffé's parameterization with respect to band separations and the signs of the MCDB terms, but is not applicable ton→ π* transitions.     

Fibrous twists and turns: early ceramic technology revealed through computed tomography

While the emergence of pottery manufacturing is a wide-spread historical occurrence, and one that has garnered the attention of archaeologists for decades, we know very little about how these ancient vessels were created. Through the application of radiographic scanning and computed tomography this paper provides insights into the manufacturing techniques used by the earliest potters in North America. While x-rays have been used to investigate ceramic manufacturing techniques for decades, this paper provides a reassessment of radiography in light of advances in both computed tomography and reconstructive software.     

Synthesis and thermal properties of a new styryl-functionalized pentafulvene glassy carbon precursor

The first preparation of a styryl-functionalized aryl pentafulvene 4 was carried out. In the crystal structure of 4, the packing of fulvene molecules results in the shortest intermolecular contacts between aligned vinyl groups. Thermal reactivity studies of 4 (DSC and TGA, under N₂) revealed a small difference between the melting point (120 °C) and the T_onset for cross-linking (125 °C), and provided strong evidence for the production of a network material (net4) due to reactivity of the attached styryl group. Pyrolysis of net4 under N₂ gave a glassy carbon product in low yield as revealed by powder X-ray and TGA analyses (carbon yield (TGA) of 38% (900 °C)).     

Developments in microscale and nanoscale sensors for biomedical sensing

The widespread use of point of care testing in biomedical and clinical applications is a major aim of the electrochemical field. A large number of groups are working on lab-on-a-chip systems or sensor arrays which are underpinned by electrochemical detection methodologies. Miniaturized transducers have the potential to be adopted in such systems for diagnosis of a range of diseases in both clinical and nonclinical settings. In this review, we will present the current trends and state of the art for a selection of miniaturized sensing elements (microelectrodes, nanoelectrodes, and field-effect transistors) and provide an impression of current technologies, their associated performance characteristics, and also considering the major barriers to adoption and how they might be surmounted in future so these technologies can fulfil their early promise.     

Glycoconjugated Metallohelices have Improved Nuclear Delivery and Suppress Tumour Growth In Vivo

Monosaccharides are added to the hydrophilic face of a self‐assembled asymmetric Fe^II metallohelix, using CuAAC chemistry. The sixteen resulting architectures are water‐stable and optically pure, and exhibit improved antiproliferative selectivity against colon cancer cells (HCT116 p53^+/+) with respect to the non‐cancerous ARPE‐19 cell line. While the most selective compound is a glucose‐appended enantiomer, its cellular entry is not mainly glucose transporter‐mediated. Glucose conjugation nevertheless increases nuclear delivery ca 2.5‐fold, and a non‐destructive interaction with DNA is indicated. Addition of the glucose units affects the binding orientation of the metallohelix to naked DNA, but does not substantially alter the overall affinity. In a mouse model, the glucose conjugated compound was far better tolerated, and tumour growth delays for the parent compound (2.6 d) were improved to 4.3 d; performance as good as cisplatin but with the advantage of no weight loss in the subjects.     

A fluorogenic 1,3-dipolar cycloaddition reaction of 3-azidocoumarins and acetylenes

Copper(I)-catalyzed 1,3-dipolar cycloaddition reaction of nonfluorescent 3-azidocoumarins and terminal alkynes afforded intense fluorescent 1,2,3-triazole products. The mild condition of this reaction allowed us to construct a large library of pure fluorescent coumarin dyes. Since both azide and alkyne are quite inert to biological systems, this reaction has potential in bioconjugation and bioimaging applications. [reaction: see text]     

Optimization of Biocompatibility for a Hydrophilic Biological Molecule Encapsulation System

Despite considerable advances in recent years, challenges in delivery and storage of biological drugs persist and may delay or prohibit their clinical application. Though nanoparticle-based approaches for small molecule drug encapsulation are mature, encapsulation of proteins remains problematic due to destabilization of the protein. Reverse micelles composed of decylmonoacyl glycerol (10MAG) and lauryldimethylamino-N-oxide (LDAO) in low-viscosity alkanes have been shown to preserve the structure and stability of a wide range of biological macromolecules. Here, we present a first step on developing this system as a future platform for storage and delivery of biological drugs by replacing the non-biocompatible alkane solvent with solvents currently used in small molecule delivery systems. Using a novel screening approach, we performed a comprehensive evaluation of the 10MAG/LDAO system using two preparation methods across seven biocompatible solvents with analysis of toxicity and encapsulation efficiency for each solvent. By using an inexpensive hydrophilic small molecule to test a wide range of conditions, we identify optimal solvent properties for further development. We validate the predictions from this screen with preliminary protein encapsulation tests. The insight provided lays the foundation for further development of this system toward long-term room-temperature storage of biologics or toward water-in-oil-in-water biologic delivery systems.     

Fast,Facile and Solvent-Free Dry-Melt Synthesis of Oxovanadium(IV) Complexes: Simple Design with High Potency towards Cancerous Cells

A range of oxobis(phenyl-1,3-butanedione) vanadium(IV) complexes have been successfully synthesized from cheap starting materials and a simple and solvent-free one-pot dry-melt reaction. This direct, straightforward, fast and alternative approach to inorganic synthesis has the potential for a wide range of applications. Analytical studies confirm their successful synthesis, purity and solid-state coordination, and we report the use of such complexes as potential drug candidates for the treatment of cancer. After a 24 hour incubation of A549 lung carcinoma cells with the compounds, they reveal cytotoxicity values elevenfold greater than cisplatin and remain non-toxic towards normal cell types. Additionally, the complexes are stable over a range of physiological pH values and show the potential for interactions with bovine serum albumin.