Synthetic Studies on Selectin Ligands/Inhibitors: One-Pot Synthesis of the Mono- and Oligo-Sulfated 2-(Tetradecyl)Hexadecyl β-D-Galacto- and Lactopyranosides as the Sulfatide Mimetics 1

Abstract

The ¹³C NMR spectra of inulin oligomers in D₂O with degree of polymerization (DP) of 3 through 9, along with two other inulin oligomer mixtures of average DP = 17 and DP = 31 were recorded. Significant variations in the chemical shift of some fructofuranose carbon signals indicates that unlike glucans, simple helical structures are not the predominant conformation for inulin oligomers—at least up to DP = 9. Models of the DP = 5 oligomer show that it should prefer a single helical conformation which however, would not be accessible to longer DP oligomers due to severe steric interactions.     

Enantioselective synthesis of the carbacephem antibiotic loracarbef via Mitsunobu and Dieckmann cyclization from an unnatural amino acid

The nucleus of the carbacephem antibiotic loracarbef was synthesized in a highly efficient and enantioselective fashion from 2S,3S-2-amino-3-hydroxy-6-heptenoic acid (AHHA), which was derived from enzyme-catalyzed condensation of glycine and 4-pentenaldehyde. The bicyclic framework of this compound was established through sequential Mitsunobu reaction and aldol condensations.     

New methods for determining the thermal activation energies of light sensitive traps

Two methods have been developed for determining the thermal activation energies of light sensitive traps in systems with either one or two trap types and a single type of recombination centre. No assumptions about the kinetic order are needed for the methods to be successful, although the two- trap case requires sufficient difference in trap activation energies. There is potential to apply the methods to more complex systems, and the theory is readily transferred to the traps used in ESR.     

Absorbing Interface Conditions for the Simulation of Wave Propagation on Non-Uniform Meshes

We proposed absorbing interface conditions for the simulation of linear wave propagation on non-uniform meshes. Based on the superposition principle of second-order linear wave equations, we decompose the interface condition problem into two subproblems around the interface: for the first one the conventional artificial absorbing boundary conditions is applied, while for the second one, the local analytic solutions can be derived. The proposed interface conditions permit a two-way transmission of low-frequency waves across mesh interfaces which can be supported by both coarse and fine meshes, and perform a one-way absorption of high-frequency waves which can only be supported by fine meshes when they travel from fine mesh regions to coarse ones. Numerical examples are presented to illustrate the efficiency of the proposed absorbing interface conditions.     

Spontaneous Reconstitution of Functional Transmembrane Proteins During Bioorthogonal Phospholipid Membrane Synthesis

Transmembrane proteins are critical for signaling, transport, and metabolism, yet their reconstitution in synthetic membranes is often challenging. Non‐enzymatic and chemoselective methods to generate phospholipid membranes in situ would be powerful tools for the incorporation of membrane proteins. Herein, the spontaneous reconstitution of functional integral membrane proteins during the de novo synthesis of biomimetic phospholipid bilayers is described. The approach takes advantage of bioorthogonal coupling reactions to generate proteoliposomes from micelle‐solubilized proteins. This method was successfully used to reconstitute three different transmembrane proteins into synthetic membranes. This is the first example of the use of non‐enzymatic chemical synthesis of phospholipids to prepare proteoliposomes.     

Profiling monoterpenol glycoconjugation in Vitis vinifera L. cv. Muscat of Alexandria using a novel putative compound database approach,high resolution mass spectrometry and collision induced dissociation fragmentation analysis

In this work we present a novel approach for the identification of plant metabolites using ultrahigh performance liquid chromatography coupled to accurate mass time-of-flight mass spectrometry. The workflow involves developing an in-house compound database consisting of exact masses of previously identified as well as putative compounds. The database is used to screen accurate mass spectrometry (MS) data to identify possible compound matches. Subsequent tandem MS data is acquired for possible matches and used for structural elucidation. The methodology is applied to profile monoterpene glycosides in Vitis vinifera cv. Muscat of Alexandria grape berries over three developmental stages. Monoterpenes are a subclass of terpenes, the largest class of plant secondary metabolites, and are found in two major forms in the plant, “bound” to one or more sugar moieties or “free” of said sugar moieties. In the free form, monoterpenes are noted for their fragrance and play important roles in plant defense and as attractants for pollinators. However, glycoconjugation renders these compounds odorless, and it is this form that the plant uses for monoterpene storage. In order to gain insight into monoterpene biochemistry and their fate in the plant an analysis of intact glycosides is essential. Eighteen monoterpene glycosides were identified including a monoterpene trisaccharide glycoside, which is tentatively identified here for this first time in any plant. Additionally, while previous studies have identified monoterpene malonylated glucosides in other grapevine tissue, we tentatively identify them for the first time in grape berries. This analytical approach can be readily applied to other plants and the workflow approach can also be used for other classes of compounds. This approach, in general, provides researchers with data to support the identification of putative compounds, which is especially useful when no standard is available.     

In search of physical parameters influenced by flow patterns in a heterogeneous two-phase mixture in microchannels using concomitant measurements

Space transportation systems require high-performance thermal protection and fluid management for systems ranging from cryogenic fluid devices to primary structures, and for propulsion systems exposed to extremely high temperatures, and other space systems, e.g., integrated circuits and cooling/environment control devices for advanced space suits. Although considerable developmental effort is underway to bring promising technologies to a readiness level for practical use, new and innovative methods are still needed. One such method is the Advanced Micro Cooling Module (AMCM), essentially a compact two-phase heat exchanger constructed of microchannels and designed to rapidly remove large quantities of heat from critical systems by incorporating phase transition. This paper describes the results of experimental research in two-phase flow phenomena, encompassing both an experimental and an analytical approach to the incorporation of flow patterns for air–water mixtures flowing in microchannels. Specifically addressed are: (1) design and construction of a sensitive two-phase experimental system which measures both ac and dc components of in situ physical mixture parameters including spatial concentration, using concomitant methods; (2) data acquisition and analysis in the amplitude, time, and frequency domains; and (3) analysis of results including evaluation of in situ physical parameters, and assessment of their validity for application in flow pattern determination.