Adsorption of Carboxylic Acids by Diethylenetriamine Intercalation Compound of α-Zr(HPO4)2 · H2O

Abstract

Two kinds of diethylenetriamine (2E3A) intercalation compounds of α-zirconium phosphate with different interlayer distances could be obtained by regulating the reaction time and temperature. Phase I (d = 10.2 Å) slowly transforms to Phase II(d = 15. 8 Å) with transformation enthalpy of 30 kJ-mol^?1 in 2E3A aqueous solution. The conformation of 2E3A in Phase I and Phase II were confirmed to be bent and all trans (straight) forms by³¹P MAS NMR and XRD measurements. Two phases have different adsorption behavior for gaseous carboxylic acids. Phase II can adsorb considerable amount of carboxylic acids whereas Phase I adsorb a little.     

Synthesis of photocatalytic active fibrous titania by the solvothermal reactions

Abstract

Fibrous titania was synthesized by the solvothermal reactions of H₁Ti₄O₉ nH₂in different media. H₂Ti₄O₉·nH₂O transformed in steps to H₂Ti₈O₁₇, monoclinic TiO_z, anatase and rutile. The phase transformation temperature and microstructure of the products changed significantly depending on the heating environment. The critical temperature at which anatase appeared in liquid media was much lower than that in air. The titania fibers consisted of nanocrystals of TiO₂. The crystallite size and crystallinity of titania decreased with decreasing the dielectric constant of the reaction medium. Consequently, the photocatalytic activity of titania changed with heat treatment media in the following sequence: ethanol, methanol > water > air, i.e., fibrous titania possessing excellent photocatalytic activity could be obtained by the solvothermal reactions using alcohol such as methanol and ethanol. Titania powders crystallized by the solvothermal reaction in methanol also possessed excellent thermal stability.     

Coupon collector’s problems with statistical applications to rankings

Some new exact distributions on coupon collector’s waiting time problems are given based on a generalized Pólya urn sampling. In particular, usual Pólya urn sampling generates an exchangeable random sequence. In this case, an alternative derivation of the distribution is also obtained from de Finetti’s theorem. In coupon collector’s waiting time problems with $m$ kinds of coupons, the observed order of $m$ kinds of coupons corresponds to a permutation of $m$ letters uniquely. Using the property of coupon collector’s problems, a statistical model on the permutation group of $m$ letters is proposed for analyzing ranked data. In the model, as the parameters mean the proportion of the $m$ kinds of coupons, the observed ranking can be intuitively understood. Some examples of statistical inference are also given.     

Whole-body distribution of <Superscript>14</Superscript>C-labeled silica nanoparticles and submicron particles after intravenous injection into Mice

We analyzed the whole-body distribution of ¹⁴C–ADP-labeled silica nanoparticles (¹⁴C–ADP–SiO₂ nanoparticles) and submicron particles (¹⁴C–ADP–SiO₂ submicron particles) after intravenous injection into ICR mice. The ¹⁴C–ADP–SiO₂ nanoparticles and submicron particles were synthesized before the injection and the particle size was 19.6 and 130 nm, respectively. Similarly, the shape was spherical and the crystallinity was amorphous. After the synthesis, we injected mice with the ¹⁴C–ADP–SiO₂ nanoparticles or the ¹⁴C–ADP–SiO₂ submicron particles and dissected tissues after 1, 2, 4, 8 and 24 h. The radioactivity in the tissues was measured with a liquid scintillation counter. As a result, the retention percentage in bone, skin, lymph nodes, and the digestive mixture was at least twofold higher in the ¹⁴C–ADP–SiO₂ nanoparticles-exposed mice, whereas the retention percentage in the kidney was statistically higher in the ¹⁴C–ADP–SiO₂ submicron particles-exposed mice. Both types of ¹⁴C–ADP–SiO₂ particles mainly translocated to the muscle, bone, skin, and liver, but hardly translocated to the brain and olfactory bulb. Furthermore, the ¹⁴C–ADP–SiO₂ nanoparticles had a higher retention percentage (62.4 %) in the entire body at 24-h post-injection than did the ¹⁴C–ADP–SiO₂ submicron particles (50.7 %). Therefore, we suggested that the ¹⁴C–ADP–SiO₂ nanoparticles might be more likely than the ¹⁴C–ADP–SiO₂ submicron particles to be retained in the body, and consequently they might be gradually accumulated by chronic exposure.     

Synthesis of functionalized hydroxy-thiophene motifs as amido- and sulfonamido-phenol bioisosteres

Novel highly substituted hydroxy thiophene motifs were designed and synthesized as viable amido phenol and sulfonamido phenol bioisosteres. Hydroxy group-directed regioselective bromination and palladium-catalyzed amination of thienyl bromide via Buckwald protocol are the key elements of the synthetic approach. The hydroxy thiophene-containing compounds displayed good binding inhibitions.     

Intrauterine devices and uterine peristalsis: evaluation with MRI

Intrauterine devices (IUDs) have been viewed as an effective form of contraception. However, the mechanism by which IUDs disturb fertility remains controversial. This study aimed to evaluate the effects of IUDs on uterine contractility using cine MR. Eleven healthy female volunteers of reproductive age bearing IUDs and 12 women not bearing IUDs were evaluated during the periovulatory phase. MR images were obtained with a 1.5-T magnet, acquiring 60 serial images every 3 s via half-Fourier acquisition single-shot turbo spin echo to be displayed on cine mode. Assessments were based on (a) the presence of peristaltic waves, (b) the frequency and direction of peristaltic waves and (c) the extent of peristaltic waves. Static images were evaluated for thickness of the junctional zone (JZ) and myometrium. A fundo-cervical (FC)-directed peristaltic wave was identified in 4 of 11 IUD-bearing subjects and in only 1 of 12 subjects from the control group. FC waves extended through more than half of the thickness of the myometrium. Peristaltic frequency in IUD users (5.0/3 min) was less than that of the control group (6.5/3 min). The JZ and myometrium were significantly thicker in IUD users. FC-directed waves were more often observed in IUD-bearing subjects, which might explain the inhibition of active sperm transport.     

Tocopheryl Phosphate Inhibits Rheumatoid Arthritis-Related Gene Expression In Vitro and Ameliorates Arthritic Symptoms in Mice

Anti-rheumatoid arthritis (RA) effects of α-tocopherol (α-T) have been shown in human patients in a double-blind trial. However, the effects of α-T and its derivatives on fibroblast-like synoviocytes (FLS) during the pathogenesis of RA remain unclear. In the present study, we compared the expression levels of genes related to RA progression in FLS treated with α-T, succinic ester of α-T (TS), and phosphate ester of α-T (TP), as determined via RT-PCR. The mRNA levels of interleukin (IL)-6, tumor necrosis factor-α (TNF-α), matrix metalloproteinase (MMP)-3, and MMP-13 were reduced by treatment with TP without cytotoxicity, while α-T and TS did not show such effects. Furthermore, intraperitoneal injection of TP ameliorated the edema of the foot and joint and improved the arthritis score in laminarin-induced RA model mice. Therefore, TP exerted anti-RA effects through by inhibiting RA-related gene expression.     

Short-step synthesis and structure-activity relationship of cortistatin A analogs

An improved method for synthesizing structurally simplified analogs of cortistatin A (1), a novel anti-angiogenic steroidal alkaloid from a marine sponge, was developed. In contrast to previous methods, step- and redox-economical synthesis was achieved using a known α-bromoketone as the starting material. The structure-activity relationship study revealed that the isoquinoline portion was strictly recognized by the target molecule. Surprisingly, the introduction of the acetamide moiety on the A-ring structure dramatically enhanced the selective antiproliferative activity against endothelial cells. This new method can be easily applied to gram-scale synthesis and enabled us to prepare various analogs, which were focused on the participation of the side chain and A-ring structure.     

Sooner and later waiting time problems in a two-state Markov chain

LetX ₁,X ₂,... be a time-homogeneous {0, 1}-valued Markov chain. LetF ₀ be the event thatl runs of 0 of lengthr occur and letF ₁ be the event thatm runs of 1 of lengthk occur in the sequenceX ₁,X ₂, ... We obtained the recurrence relations of the probability generating functions of the distributions of the waiting time for the sooner and later occurring events betweenF ₀ andF ₁ by the non-overlapping way of counting and overlapping way of counting. We also obtained the recurrence relations of the probability generating functions of the distributions of the sooner and later waiting time by the non-overlapping way of counting of 0-runs of lengthr or more and 1-runs of lengthk or more.     

Electrochemical fluorination of acetamide and formamide in molten KH2F3

The electrofluorination of acetamide (CH₃CONH₂) and formamide (HCONH₂) on the anode was studied in molten KH₂F₃ at 120°C. Amorphous carbon was used as the anode and Pt-rod as the reference electrode. Anodic products were analyzed by both gas chromatography and infrared spectroscopy.In the cases of both CH₃CONH₂ and HCONH₂, the anode effect occurred often in electrolysis at the current density range of 3～20 mA·cm^?2 and the anode gas was then composed 5of N₂(+O₂), NF₃, CF₄, C₂F₆, N₂O, CO₂(+COF₂) and so on. The addition of 1.0 wt% LiF into the electrolyte decreased the yield of NF₃.From these results, it is suggested that CH₃CONH₂ and HCONH₂ would react chemically with atomic fluorine produced on the (C_xF)n [x > 2] film by the discharge of fluoride ion. The mechanism of electrofluorination of CH₃CONH₂ or HCONH₂ in this melt is as follows;