Novel titanium complexes of a multidentate dicarbollide ligand. Synthesis and structural characterization of a constrained geometry complex

The multidentate dicarbollide ligand nido-7,8-(NMe2CH2)2-7,8-C2B9H11 has been prepared, structurally characterized, and employed in the preparation of the novel mono- and trimetallic titanium complexes [eta5:eta1-(NMe2CH2)C2B9H9CH2NMe2]Ti(NMe2)2 and [eta5:eta1-[(NMe2CH2)C2B9H9CH2NMe2]Ti(NMe2)]2-mu3-O-Ti(NMe2)2.     

Preparation of water‐soluble,syndiotacticity‐rich,low molecular weight poly(vinyl alcohol) microfibrils in high yields with the low‐temperature polymerization of vinyl pivalate in tetrahydrofuran and saponification

To prepare water‐soluble, syndiotacticity‐rich poly(vinyl alcohol) (PVA) microfibrils for various industrial applications, we synthesized syndiotacticity‐rich, low molecular weight PVA by the solution polymerization of vinyl pivalate (VPi) in tetrahydrofuran (THF) at low temperatures with 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN) as an initiator and successive saponification of poly(vinyl pivalate) (PVPi). Effects of the initiator and monomer concentrations and the polymerization temperature were investigated in terms of the polymerization behaviors and molecular structures of PVPi and the corresponding syndiotacticity‐rich PVA. The polymerization rate of VPi in THF was proportional to the 0.91 power of the ADMVN concentration, indicating the heterogeneous nature of THF polymerization. The low‐temperature solution polymerization of VPi in THF with ADMVN proved to be successful in obtaining water‐soluble PVA with a number‐average degree of polymerization (P_n) of 300–900, a syndiotactic dyad content of 60–63%, and an ultimate conversion of VPi into PVPi of over 75%. Despite the low molecular weight of PVA with P_n = 800, water‐soluble PVA microfibrillar fibers were prepared because of the high level of syndiotacticity. In contrast, for PVA with P_n = 330, shapeless and globular morphologies were observed, indicating that molecular weight has an important role in the in situ fibrillation of syndiotacticity‐rich PVA. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1103–1111, 2002     

Seed‐Mediated Synthesis of Gold Tetrahedra in High Purity and with Tunable,Well‐Controlled Sizes

We report a facile synthesis of Au tetrahedra in high purity and with tunable, well‐controlled sizes via seed‐mediated growth. The success of this synthesis relies on the use of single‐crystal, spherical Au nanocrystals as the seeds and manipulation of the reaction kinetics to induce an unsymmetrical growth pattern for the seeds. In particular, the dropwise addition of a precursor solution with a syringe pump, assisted by cetyltrimethylammonium chloride and bromide at appropriate concentrations, was found to be critical to the formation of Au tetrahedra in high purity. Their sizes could be readily tuned in the range of 30–60 nm by simply varying the amount of precursor added to the reaction solution. The current strategy not only enables the synthesis of Au tetrahedra with tunable and controlled sizes but also provides a facile and versatile approach to reducing the symmetry of nanocrystals made of a face‐centered cubic lattice.     

Significant change in water contact angle of electrospray‐synthesized SiO2 films depending on their surface morphology

Amorphous SiO₂ films were deposited by means of an electrospray technique. The relation between the water contact angle (WCA) of the deposited SiO₂ films and the surface morphology is investigated. The feeding rate of the electrospray process greatly affects the morphology of the synthesized SiO₂ films. There is also a significant change in the WCA on the surface of the films: the rougher the surface, the greater the WCA. A model based on the Cassie–Baxter formulation is used to explain the change observed in the WCA on the SiO₂ films. Copyright © 2012 John Wiley & Sons, Ltd.     

Site-selective C–H nitration of N-aryl-7-azaindoles under palladium(II) catalysis

The site-selective C–H nitration reaction of 7-azaindoles with t-butyl nitrite under palladium catalysis is described. This protocol provides an efficient method for the construction of ortho-nitrated N-aryl-7-azaindoles with excellent site-selectivity and functional group compatibility. The formed 7-azaindole derivatives can be readily transformed into 7-azaindoles containing an aniline functional group under palladium-catalyzed hydrogenation conditions.     

Sparse non-negative matrix factorizations for ultrasound factor analysis

Factor analysis is a powerful tool used for the analysis of dynamic studies. One of the major drawbacks of Factor Analysis of Dynamic Structures (FADS) is that the solution is not mathematically unique when only non-negativity constraints are used to determine factors and factor coefficients. In this paper, we introduce a novel method to correct FADS solutions by constructing and minimizing a new objective function. The method is improved from non-negative matrix factorizations (NMFs) algorithm by adding a sparse constraint that penalizes multiple components in the images of the factor coefficients. The technique is tested on computer simulations, and a patient ultrasound liver study. The results show that the method works well in comparison to the truth in computer simulations and to region of interest (ROI) measurements in the experimental studies.     

Investigation on the stress behavior of cellulose acetate and the development of highly moisture‐resistant optical films for display devices

An optical film with high optical anisotropy was prepared by the stretching of a cellulose acetate film and the consequential orienting of a retardation‐enhancing additive. The change in retardation in response to moisture absorption was explored and it was found that the degree of the retardation variation is strongly related to the stretching temperature. Stress generated by the stretching and its relaxation was systematically investigated to elucidate the effect of stretching temperature on the irreversible change in retardation upon moisture absorption. The results show that the magnitude of releasable stress plays an important role in controlling changes in optical properties. In addition, the difference in the deformation behavior between glassy and rubbery states should be taken into account in the development of a moisture‐resistant optical film. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1470–1478     

Quantitative determination of duloxetine and its metabolite in rat plasma by HPLC‐MS/MS

The major metabolite of duloxetine is a glucuronide conjugate of 4‐hydroxy duloxetine (4‐HD). However, interestingly, there have been no reports determining concentrations of 4‐HD and no fully validated method has been established for measuring duloxetine and 4‐HD in rat plasma. We developed a method for the simultaneous quantification of duloxetine and its metabolite in rat plasma using high‐performance liquid chromatography tandem mass spectrometry. Duloxetine and 4‐HD were analyzed on a reverse‐phase C₁₈ analytical column after protein precipitation of the plasma sample with methanol, using carbamazepine as an internal standard. The isocratic mobile phase of 5 mm ammonium acetate–methanol (4:6, v/v) was eluted at 0.4 mL/min. Quantification was performed on a triple‐quadrupole mass spectrometer using electrospray ionization, and the ion transition monitored in selective reaction monitoring mode. The coefficient of variation for assay precision was <18.0%, and the accuracy was 84.0–118.0%. This method was successfully used to measure the concentrations of duloxetine and its metabolite in plasma following the oral administration of a single 40 mg/kg dose in rats. Copyright © 2013 John Wiley & Sons, Ltd.