Size sorting of biological micro-particles by Newton-ring nano-gap device

The size determination and the size sorting of micrometer-sized particles were carried out by using a piezo-controlled nano-gap. The nano-gap was built by combining a plano-convex lens and a flat glass plate. The fabricated gap had a gradient, while the center of the lens was narrow and the outer side was wide. When the sample solution was injected into the gap, a meniscus force carried the sample particles toward the center of the lens with solvent evaporation; then the individual particle was trapped at the specific position where the particle diameter was equal to the gap distance. The size determination ability of this new method was certified by using the standard polystyrene particles and the size measurements of DNA molecules and yeast cells were demonstrated.     

Facile construction of sulfanyl-terminated poly(ethylene glycol)-brushed layer on a gold surface for protein immobilization by the combined use of sulfanyl-ended telechelic and semitelechelic poly(ethylene glycol)s

A sulfanyl-terminated poly(ethylene glycol) (PEG)-brushed layer was constructed on a gold sensor platform by consecutive treatment with a sulfanyl-ended semitelechelic PEG (2 kDa, hereafter "MeO-PEG-SH (2k)") and a sulfanyl-ended telechelic PEG (5 kDa, hereafter "SH-PEG-SH (5k)"). Our strategy of constructing the sulfanyl-terminated PEG-brushed gold surface is based on mixed-PEG-brush formation from the longer SH-PEG-SH (5k) and the shorter MeO-PEG-SH (2k), where the preimmobilized shorter MeO-PEG-SH (2k) prevents loop formation in the longer SH-PEG-SH (5k) on the surface and the free sulfanyl group at one end of the longer SH-PEG-SH is exposed to the mixed-PEG tethered-chain surface. From the experimental results obtained from surface plasmon resonance analysis, it became apparent that the immobilization density and the orientation of the longer SH-PEG-SH (5k) on the gold surface could be controlled by the amount of preimmobilized shorter MeO-PEG-SH (2k). Under the optimized conditions of MeO-PEG-SH (2k) premodification, the constructed MeO-PEG-SH (2k)/SH-PEG-SH (5k) mixed layer conjugated efficiently with the maleimide-installed proteins and the antibody Fab' fragments, accompanied by an appreciable nonfouling characteristic against bovine serum albumin as strong as that of the MeO-PEG-SH (5k)/MeO-PEG-SH (2k) mixed surface, which was reported in our previous work; it also showed a superior nonfouling characteristic compared to the commercially available carboxymethylated dextran surface (Uchida, K.; et al. Biointerphase 2007, 2 (4), 126-130). Furthermore, from the experimental results of the X-ray photoelectron spectrometry analysis, the presence of both Au-bound and Au-unbound sulfur species was confirmed on the SH-PEG-SH (5k)/MeO-PEG-SH (2k)-modified gold surface. These results clearly indicate that the preimmobilized shorter MeO-PEG-SH (2k) not only increased the nonfouling characteristic of the PEG tethered-chain surface but also prevented loop formation in the longer SH-PEG-SH (5k) on the gold surface. Since the protein-installed SH-PEG-SH (5k)/MeO-PEG-SH (2k)-modified surface showed a strongly nonfouling characteristic and recognized the target molecules selectively, this new mixed-brush-formation technique using longer sulfanyl-ended telechelic PEGs and shorter semitelechelic PEGs is a simple yet effective method of constructing a strongly nonfouling terminal-functionalized gold surface for protein immobilization.     

Some remarks on heat capacity measurements by temperature-modulated calorimetry

In temperature-modulated calorimetry, the condition in sample amount, especially thickness, required for high-accuracy heat capacity measurement should be made clear. We propose the condition of maximum thickness of a sample for measuring heat capacity within an accuracy of 1%. The other important factor for high-accuracy heat capacity measurement is thermal contact conductance between a sample and a sample pan and also that between a pan and a base plate of an apparatus. The conditions in these thermal contact conductances required for high-accuracy heat capacity measurement are discussed. Among them, if only thermal contact conductance between a pan and a base plate is significant, there is an ingenious method to measure heat capacity with high accuracy. Furthermore, if the thermal contact conductance between a pan and a base plate is infinite, we offer a simple method to obtain complex heat capacity.     

N(1)-C(5')-linked dimer hydrates of 5-substituted uracils produced by anodic oxidation in aqueous solution

Electrochemical dimerization reactivity has been studied for 5-substituted uracils (5XU) including thymine (1a: X = Me) and 5-halouracil derivatives (1b: X = F; 1c: X = Cl; 1d: X = Br; 1e: X = I). Upon galvanostatic electrolysis of Ar-saturated aqueous solution 1a underwent anodic oxidation to produce N(1)-C(5')- and N(1)-C(6')-linked dimer hydrates, 1-(6'-hydroxy-5',6'-dihydrothymin-5'-yl)thymine (5a) and 1-(5'-hydroxy-5',6'-dihydrothymin-6'-yl)thymine (6a), as the major products. These N-C-linked dimerizations were accompanied by the formation of novel stereoisomeric C(5)-C(5')-linked dimers (meso isomer: 13a[meso]; racemic isomer: 13a[rac]) with a condensed tetrahydrofuran ring skeleton. Similar electrolyses of 5-fluorouracil (1b) and 5-chlorouracil (1c) also afforded the corresponding N(1)-C(5')-linked dimer hydrates, 1-(5'-fluoro-6'-hydroxy-5',6'-dihydrouracil-5'-yl)-5-fluorouracil (5b) and 1-(5'-chloro-6'-hydroxy-5',6'-dihydrouracil-5'-yl)-5-chlorouracil (5c), respectively, while resulting in neither N(1)-C(6')-linked dimer analogues nor C(5)-C(5')-linked dimers, unlike the reactivity of 1a. In contrast to 1a-c, no dimeric products were obtained from 5-bromouracil (1d) and 5-iodouracil (1e). The present electrochemical method was applicable to the cross-dimerization into N(1)-C(5')-linked heterodimer hydrates composed of binary 5-substituted uracils that occurred in competition with the formation of homodimer hydrates. A mechanism of the N(1)-C(5')-linked dimerization of 1a-c has been proposed, by which allyl-type radical intermediates with limiting mesomeric forms of N(1)-centered and C(5)-centered pyrimidine radicals (2a-c [N(1)]/2a-c [C(5)]) are generated via anodic one-electron oxidation and subsequent deprotonation at N(1) and undergo a head-to-tail coupling.     

Application of Infrared ATR Spectroscopy to Liquid Crystals. III

Infrared absorption measurements of nematic N-(p-ethoxybenzylidene)-p'-cyanoaniline (EBCA) under a DC electric field were performed by means of our previously reported ATR method. DC voltages up to 15V were applied to the nematic liquid crystal 15 μm thick between a silicon ATR prism (probing electrode) and an In₂O₃-coated glass electrode (opposite electrode). By using this method the orientational behavior of molecules in boundary layers about 1 μm thick at the Si electrode was investigated.

The threshold voltage for the dielectric orientation varied from 2 to 6 V depending upon the boundary conditions at the opposite electrode, and the maximum degree of order of homeotropic orientation was found to be 0.6–0.7. A storage effect, in which a homeotropic texture induced by the electric field remains unaltered even if the field is removed or reversed, was observed.     

Imaging sequential dehydrogenation of methanol on Cu(110) with a scanning tunneling microscope

Adsorption of methanol and its dehydrogenation on Cu(110) were studied by using a scanning tunneling microscope (STM). Upon adsorption at 12 K, methanol preferentially forms clusters on the surface. The STM could induce dehydrogenation of methanol sequentially to methoxy and formaldehyde. This enabled us to study the binding structures of these products in a single-molecule limit. Methoxy was imaged as a pair of protrusion and depression along the [001] direction. This feature is fully consistent with the previous result that it adsorbs on the short-bridge site with the C-O axis tilted along the [001] direction. The axis was induced to flip back and forth by vibrational excitations with the STM. Two configurations were observed for formaldehyde, whose structures were proposed based on their characteristic images and motions.     

Synthesis of dithia- and tetrathiacyclophanes incorporating isoxazole units

The reaction of 5-bromomethyl-3-(p-bromomethylphenyl)isoxazole with o-, m-, and p-bis(mercap-tomethyl)benzenes gave the corresponding dithia- and/or tetrathiaisoxazolophanes, whose relative yields strongly depended upon the nature of the mercaptomethyl compound. The above isoxazole dibromide reacted with the bis(mercaptomethyl)isoxazole to afford a mixture of two isomeric dithiaisoxazolophanes.     

Current molecular design of intelligent drugs and imaging probes targeting tumor-specific microenvironments

To address the specific challenges of cancer therapy and diagnosis, a number of approaches have been advocated for the development of tumor-targeting antitumor drugs/prodrugs and non-invasive tumor molecular imaging probes. These intelligent drugs and probes are constructed from multi-functional molecular systems. This review focuses on the molecular design of drugs and imaging probes that target tumor-specific microenvironments such as angiogenesis and hypoxia.     

Fracture prediction in stretch forming using finite element simulation combined with ductile fracture criterion

Summary  A criterion for ductile fracture is introduced in the finite element simulation of sheet metal forming. From the calculated histories of stress and strain in each element, the fracture initiation site and the critical stroke are predicted by means of the ductile fracture criterion. The calculations are carried out for axisymmetric stretch forming of various aluminium alloy sheets and their laminates clad by mild steel sheets. The predictions so obtained are compared with experimental observations. The results show that the combination of the finite element simulation and the ductile fracture criterion enables the prediction of forming limit in a wide range of sheet metals. Accepted for publication 11 August 1996     

The clinical usefulness of preoperative dynamic MRI to select decompression levels for cervical spondylotic myelopathy

The study subjects included 54 patients with cervical spondylotic myelopathy who underwent a selective laminoplasty. The patients were divided into three groups according to the number of decompressed levels: two levels, three levels and four or five levels. The number of cord compressions at every intervertebral level was determined in the flexion, neutral, and extension position using a dynamic magnetic resonance imaging (MRI) scan in consideration of both static and dynamic compressions. For each group, the clinical outcomes were evaluated. Moreover, the patients were divided into two groups according to their age. Then, the appearance ratios of cord compression between the neutral and extension position were compared at each intervertebral level. The clinical outcomes were satisfactory. There were no statistical differences among the three groups, except for the age and operation time. The position of the neck influenced the number of cord compressions. The appearance ratios of cord compression, which were especially prominent at C2/3, C3/4 and C4/5, showed high scores in the aged. The preoperative dynamic MRI scan was clinically useful. In the aged, attention should be given to C2/3, C3/4 and C4/5.