An Efficient Method for the Conjugation of Hydrophilic and Hydrophobic Components by Solid‐Phase‐Assisted Disulfide Ligation

Chemical conjugation between hydrophilic and hydrophobic components is difficult because of their extremely different solubility. Herein, we report a new versatile method with a solid‐phase‐assisted disulfide ligation to overcome the difficulty of conjugation attributed to solubility. The method involves two steps in a one‐pot process: 1) loading of a hydrophobic molecule onto a resin in an organic solvent, and 2) release of the solid‐supported hydrophobic molecule as a conjugate with a hydrophilic molecule into an aqueous solvent. This strategy allows the use of a suitable solvent system for the substrates in each step. Conjugates of a water‐insoluble drug, plinabulin, with hydrophilic carriers that could not be prepared by solution‐phase reactions were obtained in moderate yields (29–45 %). This strategy is widely applicable to the conjugation of compounds with solubility problems.     

Cationic ring‐opening polymerization of monothiocarbonate with a norbornene group

This work deals with the cationic ring‐opening polymerization of cyclic thiocarbonates with a norbornene or norbornane moiety, that is, 5,5‐(bicyclo[2.2.1]hept‐2‐ene‐5,5‐ylidene)‐1,3‐dioxane‐2‐thione ( TC1 ) or 5,5‐(bicyclo[2.2.1]heptane‐5,5‐ylidene)‐1,3‐dioxane‐2‐thione ( TC2 ), respectively. The reaction of TC1 initiated by trifluoromethanesulfonic acid (TfOH), methyl trifluoromethanesulfonate (TfOMe), boron trifluoride etherate (BF₃OEt₂), or triethyloxonium tetrafluoroborate (Et₃OBF₄) afforded unidentified products; however, TC1 underwent cationic ring‐opening polymerization with methyl iodide as an initiator to afford polythiocarbonate because the propagating end was stabilized by the covalent‐bonding property. The polymerization of TC2 initiated by TfOH, TfOMe, BF₃OEt₂, or Et₃OBF₄ afforded polythiocarbonate with good solubility in common organic solvents and a narrow molecular weight distribution because of the absence of a double‐bond moiety. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1698–1705, 2002     

Building a Simple Model of a Pulse-Frequency-Modulation Photosensor and Demonstration of a 128 x 128-pixel Pulse-Frequency-Modulation Image Sensor Fabricated in a Standard 0.35-$mUm Complementary Metal-Oxide Semiconductor Technology

We present a simple model of the pulse-frequency-modulation (PFM) photosensor that provides explicit relationships between circuit parameters and output characteristics. The model treats the PFM photosensor with a feedback loop as an open loop circuit. Several characteristics such as output pulse frequency for light intensity and photosensitivity are expressed by device parameters of a photodiode, reset transistor, and chain of inverters. The relationships derived from the proposed model help us to comprehend the results by simulation program with integrated circuit emphasis (SPICE) or experiments. We design and fabricate a 128 x 128-pixel PFM image sensor with photosensitivity of 0.15 Hz/lux. As a demonstration, a figure of a dinosaur is captured using the fabricated image sensor to discuss its operation. Characteristics of a normal pixel and white and black defect pixels are measured and discussed based on the results of formulations.     

Synthesis of Disaccharide Nucleosides by the O‐Glycosylation of Natural Nucleosides with Thioglycoside Donors

Disaccharide nucleosides constitute an important group of naturally‐occurring sugar derivatives. In this study, we report on the synthesis of disaccharide nucleosides by the direct O‐glycosylation of nucleoside acceptors, such as adenosine, guanosine, thymidine, and cytidine, with glycosyl donors. Among the glycosyl donors tested, thioglycosides were found to give the corresponding disaccharide nucleosides in moderate to high chemical yields with the above nucleoside acceptors using p‐toluenesulfenyl chloride (TolSCl) and silver triflate (AgOTf) as promoters. The interaction of these promoters with nucleoside acceptors was examined by ¹H NMR spectroscopic experiments.     

Quantitative Detection for Porphyromonas gingivalis in Tooth Pocket and Saliva by Portable Electrochemical DNA Sensor Linked with PCR

Here, a quantitative electrochemical analysis of periodontal bacteria in gingival crevicular fluid (GCF) and saliva by direct polymerase chain reaction (PCR) is presented. The electrochemical measurement was performed by mixing with PCR products and electrochemical indicator (bisbenzimidazole trihydrochloride). The peak current of indicator is reduced due to slower diffusion when the dye intercalates into the amplified DNA, and the degree of reduction in the peak current is correlates with the quantity of amplified DNA. Therefore, a quantitative analysis is possible by using our electrochemical method at the end point of PCR. In the GCF testing, The number of Porphyromonas gingivalis (Pg) detected by our electrochemical method at the end point of PCR were almost same compared with that were calculated by the conventional method of quantitative real? time PCR. In the saliva testing, the relationship between number of Pg in saliva and average pocket depth, and age‐dependence were also clearly observed. Since the saliva sample is obtained in a non‐invasive manner, this method is useful for the primary screening of periodontal disease. Moreover, our detection method is simple and uses a hand‐held potentiostat making it suitable for development of an on‐site periodontal diagnosis system.     

Highly sensitive determination of a polymeric hindered amine light stabilizer in polypropylene by reactive thermal desorption-gas chromatography using nitrogen-specific detection

Highly sensitive and specific determination of trace amounts of a polymeric hindered amine light stabilizer (HALS) in polypropylene (PP) materials could be established by improving reactive thermal desorption-gas chromatography (RTD-GC) in the presence of an organic alkali, tetramethylammonium hydroxide. By using nitrogen-phosphorus detection, highly selective detection of the HALS-related components was attained. In addition, the use of a polar poly(ethylene glycol) separation column alleviated the adsorption of minor specific pyrolysis products. This modified RTD-GC method allowed the determination of the polymeric HALS (Mr 1900) in PP even for trace concentrations between 100 and 500 ppm, through observing selectively the characteristic products containing a tetramethylpiperidine moiety, which had been impossible to detect under the previous RTD-GC conditions using a non-polar separation column and conventional flame ionization detection.     

Effect of the degree of polynomials in the Savitzky—Golay method for calculation of second-derivative spectra

The second-derivative spectra of absorption curves simulated by a Gaussian function were obtained by using Savitzky—Golay cubic (CPC) and quintic polynomial convolutions (QPC), based on 17 points assumed to be at 0.25-nm intervals. For data obtained directly from the simulated curves (real-type data), the second derivatives agreed with the true values if the widths at half height of the peaks were > 15 nm for CPC and 5 nm for QPC. But when integer values obtained from the real-type data were used to simulate a 12-bit A/D conversion, considerable noise appeared on the second-derivative spectra of peaks wider than the above values, obtained by both CPC and QPC. This occurred because the rounding errors introduced by the A/D conversion formed small shoulders on the digitally reproduced absorption curves, which were enhanced by the differentiation to generate noise. The noise was more intense in QPC than in CPC, thus CPC is preferable for peaks that are not very narrow.