A photoactive isoprenoid diphosphate analogue containing a stable phosphonate linkage: synthesis and biochemical studies with prenyltransferases

A number of biochemical processes rely on isoprenoids, including the post-translational modification of signaling proteins and the biosynthesis of a wide array of compounds. Photoactivatable analogues have been developed to study isoprenoid utilizing enzymes such as the isoprenoid synthases and prenyltransferases. While these initial analogues proved to be excellent structural analogues with good cross-linking capability, they lack the stability needed when the goals include isolation of cross-linked species, tryptic digestion, and subsequent peptide sequencing. Here, the synthesis of a benzophenone-based farnesyl diphosphate analogue containing a stable phosphonophosphate group is described. Inhibition kinetics, photolabeling experiments, as well as X-ray crystallographic analysis with a protein prenyltransferase are described, verifying this compound as a good isoprenoid mimetic. In addition, the utility of this new analogue was explored by using it to photoaffinity label crude protein extracts obtained from Hevea brasiliensis latex. Those experiments suggest that a small protein, rubber elongation factor, interacts directly with farnesyl diphosphate during rubber biosynthesis. These results indicate that this benzophenone-based isoprenoid analogue will be useful for identifying enzymes that utilize farnesyl diphosphate as a substrate.     

The kinetics of a negative‐tone acrylic photoresist for 193‐nm lithography

Polymethacrylates with tert‐alcohol ester were synthesized as negative‐tone chemical amplification photoresists (CAMPs) for 193‐nm microlithography. The acid‐catalyzed dehydration reaction of the CAMPs was analyzed via Fourier transform infrared. The crosslinking behavior following the dehydration reaction of the exposed CAMPs made it possible for them to be used as negative‐tone photoresists. During the postexposure‐baking process of the resists, the decay of the active proton concentration due to the evaporation and trapping of the active acid was lumped to a time constant (τ). Kinetic studies revealed this dehydration reaction was the first order to the hydroxy group and proton concentration. The introduction of the isobornyl methacrylate monomer into the resists produced a higher glass‐transition temperature as well as a higher reactive ion etching resistance. The lithographic performance was investigated by use of isopropyl alcohol as a developer under various processing conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 954–961, 2000     

Thermosensitive lactitol-based polyether polyol (LPEP) hydrogels

A series of new thermosensitive polymer hydrogels were prepared by reacting acylated poly(ethylene glycol) bis(carboxymethyl) ether (PEGBCOCl) with lactitol-based polyether polyols (LPEP). The polyether polyols were generated from propoxylation of lactitol and have molecular weights ranging from 1337 to 4055 g/mol. The hydrogels absorb water up to 1000% of their dry weight and expel free water at temperatures at and above 30°C. The wide ranging swelling behavior and excellent thermosensitivity depend closely on the degree of crosslinking and the propylene oxide lengths in the polyols. Differential scanning calorimetry of the hydrogels showed two endotherms associated with the phase transitions of PO and EO segments in the hydrogel structures. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 979–984, 1998     

Phenylated poly(P-phenylene vinylenes) prepared via the chlorine precursor route (CPR)

The synthesis of several highly phenylated PPV derivatives by a chlorine precursor route (CPR) was investigated in order to understand its scope. Three 1,4-bis(chloromethyl)benzene monomers were prepared via a robust and versatile synthetic procedure involving the Diels-Alder reaction. The monomers were then polymerized to the corresponding precursor polymers with about 1.0 equivalent of potassium t-butoxide in THF. Only one monomer gave a soluble precursor polymer while the other two gave insoluble precursor polymers. The soluble precursor polymer was deposited as thin films and then converted to the corresponding PPV derivative, which showed green photoluminesence and electroluminesence.     

Ionic absorption of polypropylene functionalized by surface grafting and reactions

Plasma-induced surface graft copolymerization of acrylic acid on polypropylene fibers and the subsequent reactions of the grafted carboxylic groups are reported. The extents of grafting was controlled by the plasma conditions. Reactions of the carboxylic acid with selected amines resulted in ion-exchanging and chelating functionalities. In general, ion adsorption is enhanced by higher levels of grafting and by raising temperature during adsorption. The adsorption level and preferences among ions of these functionalized fibers depend on the structure of the functional groups, i.e., the structure of the spacer and terminal groups. The carboxylic acid groups of the PP-g-AA fibers which behave like weakly acidic ion-exchangers are attributed to the low metal ion adsorption and the lack of ion preference. The F1 fibers with flexible  CH₂CH₂ spacer and small terminal  OH in the functional group exhibits highest ion adsorption among all functionalized fibers studied here. With benzene spacers, metal adsorption can be enchanced by the electron-donating nature of the terminal group. With the same ester end group in the functional structure, F3 fibers which contain benzene ring spacers show higher ion adsorption than F4 and F5 which have CH₂ and NH spacers, respectively. The ion preference and adsorption ability of the functionalized fibers, i.e., equilibrium binding constants (K_b) and saturation constants (K_s) derived from adsorption isotherms, also depend on the functional group structures. K_b increases with increasing grafting yield, increasing the electron donor atom in either terminal bonds or spacer, and reducing the steric hindrance of spacer. The K_s values are affected by the accessibility of functional groups, the size of spacer, and the terminal group structure. © 1997 John Wiley & Sons, Inc.     

Passive mode-locking in diode-pumped c-cut Nd:LuVO<Subscript>4</Subscript> laser with a semiconductor saturable-absorber mirror

We demonstrated a diode-pumped passively mode-locked c-cut Nd:LuVO₄ picosecond laser with a semiconductor saturable-absorber mirror (SESAM) at a wavelength of 1067.8 nm. Due to the wide bandwidth of 0.48 nm, stable mode-locking has been generated with a duration as short as 3.7 ps, which is shorter than for the a-cut Nd:LuVO₄ laser. A maximum output power of 1.67 W was achieved to give a highest peak power of 3.47 KW at 18 W absorbed pump power.     

A mechanism for the formation of annealed compact oxide layers at the interface between anodic titania nanotube arrays and Ti foil

We propose a mechanism for the growth of crystalline anodic titanium-oxide (ATO) nanochannel arrays based on thermodynamic considerations and structural imperfections. Both amorphous and crystalline ATO films were obtained from the anodization of a titanium foil. Amorphous ATO nanotubes have a single-layer form, which makes them inefficient for use in photo-catalytic and solar-cell applications. Annealed ATO nanotubes are considered non-stoichiometric if the effect of oxygen partial pressure on the composition is significant. The driving force behind growing crystalline ATO nanotubes is the drawing of oxygen from the atmosphere to the oxygen site, which consequently decreases the concentration of oxygen vacancies in the anatase phase. The small ionization energies of titanium ions produce the stoichiometric defects. A diagram showing Gibbs energy and Kroger–Vink notation to indicate the strong influence of the non-stoichiometric ATO structure is deduced.     

Advances in Biomimetic Nanoparticles for Targeted Cancer Therapy and Diagnosis

Biomimetic nanoparticles have recently emerged as a novel drug delivery platform to improve drug biocompatibility and specificity at the desired disease site, especially the tumour microenvironment. Conventional nanoparticles often encounter rapid clearance by the immune system and have poor drug-targeting effects. The rapid development of nanotechnology provides an opportunity to integrate different types of biomaterials onto the surface of nanoparticles, which enables them to mimic the natural biological features and functions of the cells. This mimicry strategy favours the escape of biomimetic nanoparticles from clearance by the immune system and reduces potential toxic side effects. Despite the rapid development in this field, not much has progressed to the clinical stage. Thus, there is an urgent need to develop biomimetic-based nanomedicine to produce a highly specific and effective drug delivery system, especially for malignant tumours, which can be used for clinical purposes. Here, the recent developments for various types of biomimetic nanoparticles are discussed, along with their applications for cancer imaging and treatments.     

Fabrication of ferromagnetic (Ga,Mn)As by ion irradiation

Using Mn⁺ implantation following ion beam-induced epitaxial crystallization (IBIEC) annealing, high Curie temperature ferromagnetic (Ga,Mn)As thin film was fabricated. The crystalline quality of the Mn⁺ implanted layer was identified by X-ray diffraction (XRD) and transmission electron microscopy (TEM). A clear ferromagnetic transition at T_c 253 K was observed by magnetization vs. temperature measurement. We infer that IBIEC treatment is a useful method not only for the low-temperature annealing of (Ga,Mn)As thin films but also for other dilute magnetic semiconductor (DMS) samples.