Precise control and consecutive modulation of spin transition temperature using chemical migration in porous coordination polymers

Precise control of spin transition temperature (T(c)) is one of the most important challenges in molecular magnetism. A Hofmann-type porous coordination polymer {Fe(pz)[Pt(II)(CN)(4)]} (1; pz = pyrazine) exhibited cooperative spin transition near room temperature (T(c)(up) = 304 K and T(c)(down) = 284 K) and its iodine adduct {Fe(pz)[Pt(II/IV)(CN)(4)(I)]} (1-I), prepared by oxidative addition of iodine to the open metal sites of Pt(II), raised the T(c) by 100 K. DSC and microscopic Raman spectra of a solid mixture of 1-I and 1 revealed that iodine migrated from 1-I to 1 through the grain boundary after heating above 398 K. We have succeeded in precisely controlling the iodine content of {Fe(pz)[Pt(CN)(4)(I)(n)]} (1-In; n = 0.0-1.0), which resulted in consecutive modulation of T(c) in the range 300-400 K while maintaining the hysteresis width. Furthermore, it was demonstrated that iodine migration in the solid mixture was triggered by the spin transition of 1-I. The magnetically bistable porous framework decorating guest interactive open-metal-site in the pore surface makes it possible to modulate T(c) ad arbitrium through unique postsynthetic method using iodine migration.     

Effect of the chemical species of arsenic on sensitivity in graphite furnace atomic absorption spectrometry.

The sensitivity of graphite furnace atomic absorption spectrometry (GFAAS) to arsenobetaine (AB) was 1.3-times higher than to inorganic As. In order to understand the mechanism underlying this observation, the atomization processes for both chemical species were investigated in terms of the enthalpy change (DeltaH) during the atomization process in GFAAS. The enthalpy change of AB was slightly lower than that of inorganic As, which suggested that AB was atomized more efficiently than was inorganic As. Moreover, it was observed that some co-existing organic materials enhanced the analytical sensitivity of inorganic As. The sensitivity difference between inorganic As and AB depended upon the mechanisms of their atomization processes.     

Lagrange-type duality in DC programming

We show a Lagrange-type duality theorem for a DC programming problem, which is a generalization of previous results by J.-E. Martínez-Legaz, M. Volle [5] and Y. Fujiwara, D. Kuroiwa [1] when all constraint functions are real-valued. To the purpose, we decompose the DC programming problem into certain infinite convex programming problems.     

Estimation of single-nucleotide polymorphism allele frequency by alternately binding probe competitive polymerase chain reaction

A modified solvent microextraction with back extraction method (SME/BE) combined with high performance liquid chromatography and fluorescence detection (HPLC-FD) was developed for the determination of citalopram in human plasma. Extraction process was performed in a home-made total glass vial without using a teflon ring, usually employed in SME/BE. Citalopram was first extracted from 0.5 mL of plasma, modified with sodium hydroxide, into hexane. Back extraction step was then performed into 5.2 μL of 45 mM ammonium formate solution (pH 4) using a GC microsyringe. The extract was subsequently transferred into a liner-like vial and then injected into the HPLC system. An enrichment factor of 150 along with a good sample clean-up was obtained. The calibration curve showed linearity in the range of 1.0–130.0 ng mL⁻¹ with regression coefficient corresponding to 0.992. This range covers therapeutic window and even lower amounts which is important in pharmacokinetic studies. Limits of detection and quantification, based on a signal to noise ratio (S/N) of 3 and 10, were 0.3 and 0.8 ng mL⁻¹, respectively. The method was also applied for the determination of citalopram in plasma samples after oral administration of 40 mg single dose of citalopram.     

Mechanoluminescent light source for a fluorescent probe molecule

We have demonstrated an innovative ability of mechanoluminescent (ML) material as a light source for the first time. By appropriate smart size control and nondestructive mechanical stimulation, the ML particle can be considered a promising candidate of in situ light source for bio-imaging and photo-therapy even in a human body.     

Duality Theorems for Separable Convex Programming Without Qualifications

In the research of mathematical programming, duality theorems are essential and important elements. Recently, Lagrange duality theorems for separable convex programming have been studied. Tseng proves that there is no duality gap in Lagrange duality for separable convex programming without any qualifications. In other words, although the infimum value of the primal problem equals to the supremum value of the Lagrange dual problem, Lagrange multiplier does not always exist. Jeyakumar and Li prove that Lagrange multiplier always exists without any qualifications for separable sublinear programming. Furthermore, Jeyakumar and Li introduce a necessary and sufficient constraint qualification for Lagrange duality theorem for separable convex programming. However, separable convex constraints do not always satisfy the constraint qualification, that is, Lagrange duality does not always hold for separable convex programming. In this paper, we study duality theorems for separable convex programming without any qualifications. We show that a separable convex inequality system always satisfies the closed cone constraint qualification for quasiconvex programming and investigate a Lagrange-type duality theorem for separable convex programming. In addition, we introduce a duality theorem and a necessary and sufficient optimality condition for a separable convex programming problem, whose constraints do not satisfy the Slater condition.     

Some constraint qualifications for quasiconvex vector-valued systems

In this paper, we consider minimization problems with a quasiconvex vector-valued inequality constraint. We propose two constraint qualifications, the closed cone constraint qualification for vector-valued quasiconvex programming (the VQ-CCCQ) and the basic constraint qualification for vector-valued quasiconvex programming (the VQ-BCQ). Based on previous results by Benoist et al. (Proc Am Math Soc 13:1109–1113, 2002), and Suzuki and Kuroiwa (J Optim Theory Appl 149:554–563, 2011), and (Nonlinear Anal 74:1279–1285, 2011), we show that the VQ-CCCQ (resp. the VQ-BCQ) is the weakest constraint qualification for Lagrangian-type strong (resp. min–max) duality. As consequences of the main results, we study semi-definite quasiconvex programming problems in our scheme, and we observe the weakest constraint qualifications for Lagrangian-type strong and min–max dualities. Finally, we summarize the characterizations of the weakest constraint qualifications for convex and quasiconvex programming.     

Rapid and highly sensitive method for determination of methamphetamine and amphetamine in urine by electron-capture gas chromatography

A rapid and sensitive method for determination of methamphetamine and amphetamine in urine was developed by using electron-capture gas chromatography. The extraction procedure, the experimental conditions for pentafluorobenzoyl derivative formation and the percentage recovery of the drugs from urine are described. The pentafluorobenzoyl derivative of methamphetamine showed a higher electron-capture sensitivity and was detected in at least 23-fold lower concentration than the heptafluorobutyryl derivative which is commonly used as a derivatizing agent for the amine. The detection limit of pentafluorobenzoyl derivatives of methamphetamine and amphetamine was ca. 10 pg. A concentration as low as 10 ng/ml of methamphetamine and amphetamine in urine was easily detected by this method.     

Probing the oxygen activation reaction in intact whole mitochondria through analysis of molecular vibrations

The process of dioxygen reduction catalyzed by cytochrome c oxidase was investigated by examining intact porcine mitochondrial preparations using a novel time-resolved resonance Raman measurement system at experimental accuracy levels equivalent to those of the reaction system of the solubilized and purified enzyme. The resonance Raman bands assignable to the initial three intermediates were detected at frequencies identical to those observed with purified enzyme preparations. However, the lifetime of the initial intermediate (the oxygenated species) in the mitochondrial preparation was found to be significantly longer than that observed in purified preparations, suggesting that control of the stability of the oxygenated species is imposed by the mitochondrial membrane system.