Scalable Total Syntheses and Structure–Activity Relationships of Haouamines A,B, and Their Derivatives as Stable Formate Salts

Haouamines A, B, and their derivatives were synthesized via Suzuki–Miyaura coupling and three key cyclization reactions as follows: the newly developed palladium(0)-catalyzed arylative cyclization of phenylalanine-derived alkyne–aldehydes with 2-bromoarylboronic acid (an “anti-Wacker”-type cyclization); BF₃ ⋅ OEt₂-promoted Friedel–Crafts-type cyclization of symmetrical electron-rich aromatic rings adjacent to a tertiary allylic alcohol leading to the indeno-tetrahydropyridine skeleton; and (cyanomethyl)trimethylphosphonium iodide-mediated macrocyclization of amino alcohols to afford aza-paracyclophane precursors. The palladium-catalyzed reduction of mono- and di-triflate intermediates in the later stages enabled the alteration of both the position and number of hydroxyl groups on the C-ring. The instability of haouamine B was dramatically improved by salt formation with formic acid. An unambiguous evaluation of the cytotoxicity of the prepared haouamine derivative formates with and without hydroxyl groups at different positions on the C-ring indicated that the catechol structure in haouamine B produced weak cytotoxicity.     

Positive Operator Majorization and <Emphasis Type="Italic">p</Emphasis>-hyponormality

In this note we examine the relationships between p-hyponormal operators and the operator inequality . This leads to a method for generating examples of p-hyponormal operators which are not q-hyponormal for any . Our methods are also shown to have implications for the class of Furuta type inequalities.     

Integer Decomposition Property of Free Sums of Convex Polytopes

Let \({\mathcal{P} \subset \mathbb{R}^{d}}\) and \({\mathcal{Q} \subset \mathbb{R}^{e}}\) be integral convex polytopes of dimension d and e which contain the origin of \({\mathbb{R}^{d}}\) and \({\mathbb{R}^{e}}\), respectively. We say that an integral convex polytope \({\mathcal{P}\subset \mathbb{R}^{d}}\) possesses the integer decomposition property if, for each \({n\geq1}\) and for each \({\gamma \in n\mathcal{P}\cap\mathbb{Z}^{d}}\), there exist \({\gamma^{(1)}, . . . , \gamma^{(n)}}\) belonging to \({\mathcal{P}\cap\mathbb{Z}^{d}}\) such that \({\gamma = \gamma^{(1)} +. . .+\gamma^{(n)}}\). In the present paper, under some assumptions, the necessary and sufficient condition for the free sum of \({\mathcal{P}}\) and \({\mathcal{Q}}\) to possess the integer decomposition property will be presented.     

Generalized Aluthge transformation on -hyponormal operators

We shall introduce a generalized Aluthge transformation on -
hyponormal operators and also, by using the Furuta inequality, we shall give several properties on this generalized Aluthge transformation as further extensions of some results of Aluthge.

     

Analysis of transient queues with semidefinite optimization

We derive upper bounds on the tail distribution of the transient waiting time in the GI/GI/1 queue, given a truncated sequence of the moments of the service time and that of the interarrival time. Our upper bound is given as the objective value of the optimal solution to a semidefinite program (SDP) and can be calculated numerically by solving the SDP. We also derive the upper bounds in closed form for the case when only the first two moments of the service time and those of the interarrival time are given. The upper bounds in closed form are constructed by formulating the dual problem associated with the SDP. Specifically, we obtain the objective value of a feasible solution of the dual problem in closed from, which turns out to be the upper bound that we derive. In addition, we study bounds on the maximum waiting time in the first busy period.     

A note on the reducibility of automorphisms of the Klein curve and the -invariant of mapping tori

We give a characterization for the reducibility of automorphisms of the genus 3 Klein curve in terms of the -invariant of finite order mapping tori.

     

Circular autocorrelation of stationary circular Markov processes

The stationary Markov process is considered and its circular autocorrelation function is investigated. More specifically, the transition density of the stationary Markov circular process is defined by two circular distributions, and we elucidate the structure of the circular autocorrelation when one of these distributions is uniform and the other is arbitrary. The asymptotic properties of the natural estimator of the circular autocorrelation function are derived. Furthermore, we consider the bivariate process of trigonometric functions and provide the explicit form of its spectral density matrix. The validity of the model was assessed by applying it to a series of wind direction data.     

Synthetic studies toward swinhoeisterol A,a novel steroid with an unusual carbon skeleton

Swinhoeisterol A is a novel steroid with unusual 6/6/5/7 tetracyclic skeleton. The model compound with BCD rings is constructed by Friedel–Crafts acylation and an oxidative dearomatization as key steps.     

Identification of conjugation positions of urinary glucuronidated vitamin D3 metabolites by LC/ESI–MS/MS after conversion to MS/MS‐fragmentable derivatives

A liquid chromatography/electrospray ionization–tandem mass spectrometry‐based method was developed for the identification of the conjugation positions of the monoglucuronides of 25‐hydroxyvitamin D₃ [25(OH)D₃] and 24,25‐dihydroxyvitamin D₃ [24,25(OH)₂D₃] in human urine. The method employed derivatization with 4‐(4‐dimethylaminophenyl)‐1,2,4‐triazoline‐3,5‐dione to convert the glucuronides into fragmentable derivatives, which provided useful product ions for identifying the conjugation positions during the MS/MS. The derivatization also enhanced the assay sensitivity and specificity for urine sample analysis. The positional isomeric monoglucuronides, 25(OH)D₃‐3‐ and ‐25‐glucuronides, or 24,25(OH)₂D₃‐3‐, ‐24‐ and ‐25‐glucuronides, were completely separated from each other under the optimized LC conditions. Using this method, the conjugation positions were successfully determined to be the C3 and C24 positions for the glucuronidated 25(OH)D₃ and 24,25(OH)₂D₃, respectively. The 3‐glucuronide was not present for 24,25(OH)₂D₃, unlike 25(OH)D₃, thus we found that selective glucuronidation occurs at the C24‐hydroxy group for 24,25(OH)₂D₃.     

SUPER TOUGH GELS WITH A DOUBLE NETWORK STRUCTURE

 Living tissues work with fantastic functions in soft and wet gel-like state. Thus, hydrogels have attracted much attention as excellent soft & wet materials, suitable for making artificial organs for medical treatments.However, conventional hydrogels are mechanically too weak for practical uses. We have created double network (DN) hydrogels with extremely high mechanical strength in order to overcome this problem. DN gels are interpenetrating network (IPN) hydrogels consisting of rigid polyelectrolyte and soft neutral polymer. Their excellent mechanical properties cannot be explained by the standard fracture theories. In this paper, we discuss about the toughening mechanism of DN gels in accordance with their characteristic behavior, such as large hysteresis and necking phenomenon. We also describe the results on tissue engineering application of DN gels.