STUDIES ON THE STRUCTURE OF PORPHYRINS CONTAINED IN PHOTOFRIN® II

Abstract Using three methods to attempt to identify the presence of ester-linked porphyrins in Photofrin® II, lithium aluminum hydride reduction, basic hydrolysis and proton NMR. it can be concluded that 40-50% of such linkages are present. The majority of the remaining material is cleaved by acid hydrolysis, which is consistent with the ether structure proposed earlier. earlier.     

SYNTHESIS AND PHOTOSENSITIZING ACTIVITY OF A DI-PORPHYRIN ETHER

Abstract A simple, well characterized porphyrin dimer with ether linkage was synthesized from 2- (1-hydroxyethyl)deuteroporphyrin dimethyl ester and found to be an effective in vivo photosensitizer in the murine SMT-F tumor system. The structure of the pure dimer was confirmed by NMR and mass spectroscopy.     

Caged phosphoproteins

We present the chemical and biological synthesis of caged phosphoproteins using the in vitro nonsense codon suppression methodology. Specifically, phosphoamino acid analogues of serine, threonine, and tyrosine with a single photocleavable o-nitrophenylethyl caging group were synthesized as the amino acyl tRNA adducts for insertion into full-length proteins. For this purpose, a novel phosphitylating agent was developed. The successful incorporation of these bulky and charged amino acids into the alpha-subunit of the nicotinic acetyl choline receptor (nAChR) and the vasodilator-stimulated phosphoprotein (VASP) using an in vitro translation system is reported.     

Cyclic Codes Over\mathbb{Z}_{4} of Even Length

We determine the structure of cyclic codes over for arbitrary even length giving the generator polynomial for these codes. We determine the number of cyclic codes for a given length. We describe the duals of the cyclic codes, describe the form of cyclic codes that are self-dual and give the number of these codes. We end by examining specific cases of cyclic codes, giving all cyclic self-dual codes of length less than or equal to 14. San Ling - The research of the second named author is partially supported by research Grants MOE-ARF R-146-000-029-112 and DSTA R-394-000-011-422.     

Local spectroscopy of image-potential-derived states: from single molecules to monolayers of benzene on Cu(111)

Stark-shifted image-potential states were measured with an STM tip for benzene adsorbed on a Cu(111) surface. A single benzene molecule locally shifts the position of the first image state toward the Fermi level by 0.2 eV relative to its position on the clean surface. The energetic position of this molecule-modified state shifts to lower energy with increasing coverage of benzene on the surface. This is attributed to local surface potential changes that are correlated with the lowering of the crystal work function due to adsorption of benzene.     

Phenyl species formation and preferential hydrogen abstraction in the decomposition of chemisorbed benzoate on Cu(110)

The adsorption and decomposition of benzoic acid on the Cu(110) surface has been investigated using temperature-programmed reaction (TPR) spectroscopy and scanning tunneling microscopy (STM). The benzoate species is found to exist in two conformations--a phase containing upright species at monolayer saturation and a phase containing many lying-down species at lower coverages. Thermal decomposition begins to occur near 500 K, yielding benzene and CO(2). It is found that phenyl species, generated preferentially from the lying-down benzoate species, efficiently abstract H atoms from undecomposed benzoate species to produce benzene in a rate-controlling process with an activation energy of about 29 kcal/mol. Using deuterium-atom substitution at the 4-C position on the benzoate ring it is found that the hydrogen-abstraction reaction is selective for 2,3 and 5,6 C-H bonds. This observation indicates that the mobile phenyl species is surface bound and preferentially attacks C-H bonds which are nearest the Cu surface and bind the benzoate species as either an upright species or a tilted species.     

Automatic correction of in-plane bulk motion artifacts in self-navigated radial MRI

Radial MRI is typically used for scans that are sensitive to unavoidable motion. While the translational motion artifact can be easily removed from the radial trajectory data by phase correction, correction of rotational motion still remains a challenge in radial MRI. We present a novel method to refocus the image corrupted by view-to-view motion in the view-interleaved radial MRI data. In this method, the error in rotational view angles was modeled as a polynomial function of the view order and the model parameters were estimated by minimizing the self-navigator image metrics such as image entropy, gradient entropy, normalized gradient squared and mean square difference. Translational motion correction was conducted by aligning the projection profiles. Simulation studies were conducted to demonstrate the robustness of both translational and rotational motion correction methods in different noise levels. The proposed method was successfully applied to correct for motion of healthy subjects. Substantial motion correction with relative error of less than 5% was achieved by using either first- or second-order model with the image metrics. This study demonstrates the potential of the method for motion-sensitive applications.     

The transient growth of ammonium chloride dendrites

We report measurements of the initial growth and subsequent transient response of dendritic crystals of ammonium chloride grown from supersaturated aqueous solution. Starting from a small, nearly spherical seed held in unstable equilibrium, we lower the temperature to initiate growth. The growth speed and tip radius approach the same steady state values independent of initial seed size. We then explore the response of the growing dendrite to changes in temperature. The crystal adjusts quickly and smoothly to the new growth conditions, maintaining an approximately constant value of vρ² throughout. Dissolving dendrites, on the other hand, are not characterized by the same value of vρ².     

Stability of self-assembled monolayers on titanium and gold

Methyl- and hydroxyl-terminated phosphonic acid self-assembled monolayers (SAMs) were coated on Ti from aqueous solution. Dodecyl phosphate and dodecyltrichlorosilane SAMs were also coated on Ti using solution-phase deposition. The stability of SAMs on Ti was investigated in Tris-buffered saline (TBS) at 37 degrees C using X-ray photoelectron spectroscopy, contact angle goniometry, and atomic force microscopy. For comparison purposes, a hydroxyl-terminated thiol SAM was coated on Au, and its stability was also investigated under similar conditions. In TBS, a significant proportion of phosphonic acid or phosphate molecules were desorbed from the Ti surface within 1 day, while the trichlorosilane SAM on Ti or thiol SAM on Au was stable for up to 7 days under similar conditions. The stability of hydroxyl-terminated phosphonic acid SAM coated Ti and thiol SAM coated Au was investigated in ambient air and ultraviolet (UV) light. In ambient air, the phosphonic acid SAM on Ti was stable for up to 14 days, while the thiol SAM on Au was not stable for 1 day. Under UV-radiation exposure, the alkyl chains of the phosphonic acid SAM were decomposed, leaving only the phosphonate groups on the Ti surface after 12 h. Under similar conditions, decomposition of alkyl chains of the thiol SAM was observed on the Au surface accompanied by oxidation of thiolates.     

A stereochemical test of a proposed structural feature of the nicotinic acetylcholine receptor

Understanding the gating mechanism of the nicotinic acetylcholine receptor (nAChR) and similar channels constitutes a significant challenge in chemical neurobiology. In the present work, we use a stereochemical probe to evaluate a proposed pin-into-hydrophobic socket mechanism for the alphaVal46 side chain of the nAChR. Utilizing nonsense suppression methodology we incorporated isoleucine (Ile), O-methyl threonine (Omt) and threonine (Thr) as well as their side chain epimers (the allo counterparts). Surprisingly, our results indicate that only the pro-S methyl group of the alphaVal46 side chain is sensitive to changes in hydrophobicity, consistent with the precise geometrical requirements of the pin-into-socket mechanism.