Functional Fluorescence Labeling of Carbohydrates and Its Use for Preparation of Neoglycoconjugates

Abstract

New bifunctional reagents, 2-amino-6-carboxyethylpyridine and 2-amino-6-cyanoethylpyridine, were designed and synthesized in order to provide a novel procedure for preparation of neoglycoconjugates from fluorescence-labeled and purified sugar chains. Labeling of model sugar chains with these reagents was effected by reductive amination using BH₃.Me₂NH to give corresponding 6-carboxyethylpyridylaminated (CEPA-) and 6-cyanoethylpyridylaminated (CNEPA-) derivatives, which were readily purified by reversed phase HPLC. The reagent parts of the labeled products possess the functional groups which then serve as linkers for coupling with matrices such as proteins and polymers. A CEPA-derivative of glucose was directly coupled with the ε-amino group of a Lys derivative to give a neoglycoprotein model. CNEPA-sugars were hydrogenated to give 6-aminopropylpyridylaminated (APPA-) derivatives, which can then be readily used for the preparation of various types of neoglycoconjugates by use of appropriate spacers as exemplified by the coupling of APPA-maltotriose with bovine serum albumin (BSA), biotin, and acrylic acid. The reaction of APPA-maltotriose with succinimidyl 3-(3-nitro-2-pyridyldithio)propionate gave the corresponding amide to be used for a disulfide formation with BSA. Condensation with biotin was effected by use of N-hydroxysuccinimidobiotin. The conjugation of APPA-maltotriose with acrylic acid was carried out by use of 4-acryloyloxyphenyldimethylsulfonium methylsulfate to give the corresponding acrylamide, which can be used for the preparation of sugar-acrylamide copolymers.     

The influence of magnetic field swept rate on the ultrasonic propagation velocity of magnetorheological fluids

Structure of magnetorheological (MR) fluids depends on the strength of the magnetic field applied and on the mode of its application. The ultrasonic wave propagation velocity changes under the effect of an external magnetic field as a result of formation of clusters arranged along the direction of the field in the MR fluids. Therefore, we propose a qualitative analysis of these clustering structures by measuring properties of ultrasonic propagation. Since the MR fluids are opaque, the non-contact inspection using this ultrasonic technique can be very useful. In this study, we measured ultrasonic propagation velocity in MR fluid influenced by an external magnetic field for different swept rate precisely. With increasing magnetic field intensity, the changes of the ultrasonic wave velocity are more pronounced. Sedimentation effect takes place in certain time for different swept rate due to magnetic particle size and it follows linear relationship in log scale. Significant differences of the ultrasonic wave velocity are established between the case when the field is swept at a constant rate and the case when it is stepped up.     

Dynamic nuclear polarization studies of nitroxyl spin probes in agarose gel using Overhauser‐enhanced magnetic resonance imaging

Agarose is a tissue‐equivalent material and its imaging characteristics similar to those of real tissues. Hence, the dynamic nuclear polarization studies of 3‐carboxy‐2,2,5,5‐tetramethyl‐pyrrolidine‐1‐oxyl (carboxy‐PROXYL) in agarose gel were carried out. The dynamic nuclear polarization parameters such as spin lattice relaxation time, longitudinal relaxivity, leakage factor, saturation parameter and coupling parameter were estimated for 2 mM carboxy‐PROXYL in phosphate‐buffered saline solution and water/agarose mixture (99 : 1). From these results, the spin probe concentration was optimized as 2 mM, and the reduction in enhancement was observed for carboxy‐PROXYL in water/agarose mixture (99 : 1) compared with phosphate‐buffered saline solution. Phantom imaging was also performed with 2 mM concentration of carboxy‐PROXYL in various concentrations of agarose gel at various radio frequency power levels. The results from the dynamic nuclear polarization measurements agree well with the phantom imaging results. These results pave the way for designing model system for human tissues suited to the biological applications of electron spin resonance/Overhauser‐enhanced magnetic resonance imaging.     

Continuous flame oxidation in supercritical water

Abstract

Continuous flames have been observed in Supercritical water oxidation (scWO) of isopropyl alcohol (IPA), using a vertical continuous reactor with sapphire windows and a mixing nozzle. Two types of continuous flame were confirmed: the one was long pale blue colored and the other was red short cone shaped, changing blue to red at around air ratio 2.0. The flame was strongly influenced by IPA concentration, air ratio and design of the mixing nozzle. Results for decomposition of PA are presented for IPA concentrations ranging from 600 up to 28260 ppm as TOC and initial reactor temperatures, were mostly around 490°C, at 25 MPa. Decomposition rate at steady state was over 99.9%. Experimentally measured CO₂ and O₂ concentrations at the flue gas were in good agreement with theoretically calculated values. Even for low air ratio as 1.1, high decomposition rate without CO, NO, NO₂ was achieved.     

Optimal threshold analysis of segmentation methods for identifying target customers

In CRM (Customer Relationship Management), the importance of a segmentation method for identifying good customers has been increasing. For evaluation of different segmentation methods, Accuracy often plays a key role. This indicator, however, cannot distinguish two types of errors. The purpose of this paper is to overcome this pitfall by introducing two different indicators: Recall and Precision. Assuming that a promotion is addressed exclusively to the selected target customers, the financial effectiveness of the underlying segmentation method is expressed as a function of Recall and Precision. An optimization problem is then formulated so as to maximize the financial measure by finding the optimal threshold level in terms of the severeness for estimating the target set. By introducing a functional form which represents correctness and mistakes about the target set, the unique optimal solution is derived explicitly. The proposed approach is validated by using real customer purchase data.     

Rapid time-decay and net force to the obstacles by the Stokes flow in exterior domains

Consider the nonstationary Stokes equations in exterior domains with the compact boundary . We show first that the solution decays like for all as . This decay rate is optimal in the sense that for some as occurs if and only if the net force exerted by the fluid on is zero. Received: 15 June 2000 / Published online: 18 June 2001