Temperature‐modulated differential scanning calorimetry studies on the origin of double melting peaks in isothermally melt‐crystallized poly(L‐lactic acid)

In this work, the melting behaviors of nonisothermally and isothermally melt‐crystallized poly(L ‐lactic acid) (PLLA) from the melt were investigated with differential scanning calorimetry (DSC) and temperature‐modulated differential scanning calorimetry (TMDSC). The isothermal melt crystallizations of PLLA at a temperature in the range of 100–110 °C for 120 min or at 110 °C for a time in the range of 10–180 min appeared to exhibit double melting peaks in the DSC heating curves of 10 °C/min. TMDSC analysis revealed that the melting–recrystallization mechanism dominated the formation of the double melting peaks in PLLA samples following melt crystallizations at 110 °C for a shorter time (≤30 min) or at a lower temperature (100, 103, or 105 °C) for 120 min, whereas the double lamellar thickness model dominated the formation of the double melting peaks in those PLLA samples crystallized at a higher temperature (108 or 110 °C) for 120 min or at 110 °C for a longer time (≥45 min). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 466–474, 2007     

Nucleophilic catalysis with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) for the esterification of carboxylic acids with dimethyl carbonate

1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) is an effective nucleophilic catalyst for carboxylic acid esterification with dimethyl carbonate (DMC). The reaction pathway of this new class of nucleophilic catalysis has been studied. A plausible, multistep mechanism is proposed, which involves an initial N-acylation of DBU with DMC to form a carbamate intermediate. Subsequent O-alkylation of the carboxylate with this intermediate generates the corresponding methyl ester in excellent yield. In the absence of DBU or in the presence of other bases, such as ammonium hydroxide or N-methylmorpholine, the same reaction affords no desired product. This method is particularly valuable for the synthesis of methyl esters that contain acid-sensitive functionality.     

Prominin‐1‐Specific Binding Peptide‐Modified Apoferritin Nanoparticle Carrying Irinotecan as a Novel Radiosensitizer for Colorectal Cancer Stem‐Like Cells

Resistance of cancer stem cells to radiotherapy remains a major obstacle to successful cancer management. Prominin‐1 (PROM1) is a cancer stem cell marker. Nanoparticle (NP) chemotherapeutics preferentially accumulate in tumors and are able to target cancer and cancer stem‐like cells through cancer cell‐specific ligands, making them uniquely suited as radiosensitizers for chemoradiation therapy. Using a biocompatible apoferritin NP, a PROM1‐targeted NP carrying irinotecan (PROM1‐NP) is engineered. The synergistic effect of the NP and irradiation is evaluated in PROM1‐overexpressing HCT‐116 colorectal cancer cell lines in vitro and in vivo. PROM1‐NP has a size of 17.2 ± 0.2 nm and surface charge of ?13.5 ± 0.2 mV. It demonstrates higher intracellular uptake than nontargeted NP or irinotecan alone. Treatment with PROM1‐NPs decreases HCT‐116 cell proliferation in a dose‐ and time‐dependent manner. In vitro radiosensitization reveals that PROM1‐NP is significantly more effective as a radiosensitizer than nontargeted NP or irinotecan. HCT‐116 tumor xenograft growth is markedly slower following treatment with PROM1‐NP plus irradiation, suggesting that PROM1‐NP is more effective as a radiosensitizer than irinotecan and nontargeted NP in vivo. This study provides the first preclinical evidence of the effectiveness of PROM1‐targeted NP formulation of irinotecan as a radiosensitizer.     

Phase-transformation-induced microstructure in lead-free ferroelectric ceramics based on (Bi0.5Na0.5)TiO3–BaTiO3–(Bi0.5K0.5)TiO3

Lead-free ferroelectric ceramics with a morphotropic phase boundary (MPB) composition 85.4% (Bi_0.5Na_0.5)TiO₃–2.6%BaTiO₃–12.0% (Bi_0.5K_0.5)TiO₃ (BNT-BT-BKT at a molar ratio of 85.4: 2.6: 12.0) doped with 0.8?mol% Nb₂O₅ were studied for their crystalline phases and microstructure. The crystalline phases were identified using X-ray diffractometry (XRD) with the contents determined using the Rietveld refinement technique. The phase-transformation-induced microstructure was analyzed using transmission electron microscopy (TEM) and the crystal symmetries were determined using the convergent-beam electron diffraction (CBED) technique. Samples sintered at 1200°C contain a mixture of cubic (C-), tetragonal (T-) and rhombohedral (R-) phases at a ratio of C/T/R?=?56.6: 28.4: 15.0?wt%. Two types of grains are produced: one characterized by a featureless contrast consisting of nano-scale T-domains dispersed in a C-phase matrix; the other a core-shell structure with a shell containing twin and anti-phase-boundary (APB) domains coexisting with a (C?+?T)-phase mixture core. The T- and R-twin boundaries are determined to {111}_T and {110}_R, respectively, and the fault vector for T-APB to R?=?1/2?110]_T. The characteristic microstructure is discussed in terms of the reduction in the point group symmetry and changes in the unit cell volume or the Bravais lattice upon phase transformation among the C-, T- and R-phases. The twin and the APB domains are induced and explained.     

Recovering the Sturm-Liouville Operator with Singular Potential Using Nodal Data

The paper deals with the Sturm-Liouville operator with singular potential. We assume that the potential is a sum of an a priori known distribution from a certain class and an unknown sufficiently smooth function. The inverse problem is to recover the operator using zeros of eigenfunctions (nodes) as an input data. For this inverse problem we obtain a procedure for constructing the solution.     

The unusual paramagnetic mixed-metal carbonyl chalcogenide clusters: [E(2)Cr(2)Fe(CO)(10)](2-) (E = Te,Se)

The rare examples of electron-rich mixed-metal carbonyl telluride and selenide clusters [E(2)Cr(2)Fe(CO)(10)](2-) (E = Te, Se) have been demonstrated. These two novel carbonyl complexes exhibit the unusual paramagnetic behavior.     

A Convenient Synthesis of 3, 4′-Bipyridine

3, 4′-Bipyridine was synthesized from 6-methoxy-3, 4′-bipyridine or 6-benzyloxy-3, 4′-bipyridine via 6-chloro-3, 4′-bipyridine. The chloro derivative was catalytically dechlorinated into the corresponding 3, 4′ -bipyridine.     

Syntheses of chromium pentacarbonyl derivatives of arsenic(V) and antimony(V). contrasting chemical reactivity with organic halogen derivatives

We have synthesized a new series of chromium-group 15 dihydride and hydride complexes [H(2)As(Cr(CO)(5))(2)](-) (1) and [HE(Cr(CO)(5))(3)](2)(-) (E = As, 2a; E = Sb, 2b), which represent the first examples of group 6 complexes containing E-H fragments. The contrasting chemical reactivity of 2a and 2b with organic halogen derivatives is demonstrated. The reaction of 2a with RBr (R = PhCH(2), HC triple bond CCH(2)) produces the RX addition products [(R)(Br)As(Cr(CO)(5))(2)](-) (R = PhCH(2), 3; R = C(3)H(3), 4), while the treatment of 2b with RX (RX = PhCH(2)Br or HC triple bond CCH(2)Br, CH(3)(CH(2))(5)C(O)Cl) forms the halo-substituted complexes [XSb(Cr(CO)(5))(3)](2-) (X = Br, 5; X = Cl, 6). Moreover, the dihaloantimony complexes [XX'Sb(Cr(CO)(5))(2)](-) can be obtained from the reaction of 2b with the appropriate organic halides. In this study, a series of organoarsenic and antimony chromium carbonyl complexes have been synthesized and structurally characterized and the role of the main group on the formation of the resultant complexes is also discussed.     

N-Doped, porous TiO2 with rutile phase and visible light sensitive photocatalytic activity

Nitrogen-doped, porous rutile has been prepared by hydrothermal reaction of TiN in nitric acid, with the nitrogen atoms present in the interstitial sites and in the form of adsorbed nitrate ions. The N-rutile powder exhibits outstanding photocatalytic activity toward degradation of adsorbed methylene blue under visible light irradiation.