Polymer nanoparticles with a sensitive CO2‐responsive hydrophilic/hydrophobic surface

Poly(methyl methacrylate) (PMMA) nanoparticles with a sensitive CO₂‐responsive hydrophilic/hydrophobic surface that confers controlled dispersion and aggregation in water were prepared by emulsion polymerization at 50 °C under CO₂ bubbling using amphiphilic diblock copolymers of 2‐dimethylaminoethyl methacrylate (DMAEMA) and N‐isopropyl acrylamide (NIPAAm) as an emulsifier. The amphiphilicity of the hydrophobic–hydrophilic diblock copolymer at 50 °C was triggered by CO₂ bubbling in water and enabled the copolymer to serve as an emulsifier. The resulting PMMA nanoparticles were spherical, approximately 100 nm in diameter and exhibited sensitive CO₂/N₂‐responsive dispersion/aggregation in water. Using copolymers with a longer PNIPAAm block length as an emulsifier resulted in smaller particles. A higher concentration of copolymer emulsifier led to particles with a stickier surface. Given its simple preparation and reversible CO₂‐triggered amphiphilic behavior, this newly developed block copolymer emulsifier offers a highly efficient route toward the fabrication of sensitive CO₂‐stimuli responsive polymeric nanoparticle dispersions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2149–2156     

New organoruthenium metallates containing ferrocenecarboxalidine thiosemicarbazones and their nucleic acid/albumin binding and in vitro cytotoxicity

A string of four new hetero binuclear Ru(III) complexes of ferrocenecarboxaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized by various spectral (infrared, ultraviolet–visible, Electron Paramagnetic Resonance (EPR) and High Resolution Mass Spectrometry (HR-MS) techniques. The binding abilities of the ligands/complexes with nucleic acid (calf thymus DNA, CT-DNA) and bovine serum albumin (BSA) were analyzed by absorption and emission titration methods. The complexes exhibited better DNA binding affinity than their parent ligands. The interaction with CT-DNA was found to be intercalative and with BSA static quenching mechanism was observed. All the synthesized Ru(III) complexes were subjected to study their in vitro cytotoxicity against MCF-7 (human breast cancer) and HT-29 (human colon cancer) cell lines. Among the four complexes, complex 3 [RuCp (FF-etsc)PPh₃]Cl exhibited the highest cytotoxicity in MCF-7 cells and complex 4 [RuCp (FF-ptsc)PPh₃]Cl was the most active on HT-29 cells.     

Temperature effects on surface activity and application in oxidation of toluene derivatives of CTAB-SDS with KMnO4

The γ_cmc values of CTAB-SDS decrease from 63.67 mN/m at 10‡C to 36.38 mN/m at 90‡C, slightly lower than those of either CTAB or SDS. Correspondingly, the CMC of CTAB-SDS decreases almost by half. The increase of surface activity of CTAB-SDS can be attributed to the relatively weak electrostatic interaction at high temperature, which is supported by the increase of solubility of CTAB-SDS with rise in temperature. Catalytic effect on oxidation of toluene derivatives with potassium permanganate follows the order CTAB-SDS > SDS > CTAB. This is not caused by the dissociative effect of CTAB-SDS with low surface activity at low temperature, as seen from the fact that almost all oxidative products can be retrieved for different toluene derivatives and surfactants by mimicking the conditions of reaction. In the emulsifications of toluene derivatives at 90‡C, the time that turbid water layers of surfactant solutions take to become clear is the same as that of the catalytic effect on oxidation of toluene derivatives. Thus, it can be inferred that surfactants can improve the oxidation yields of toluene derivatives by increasing the contact between two reacting phases.     

Conjugate addition of pyrroles to α,β-unsaturated ketones using copper bromide as a catalyst

Copper bromide was used as a catalyst for the addition of pyrroles to enones. When both the reactants were used in equimolar amounts, mono and dialkylated products were obtained. However, the use of excess enone furnished only dialkylated products. Thus, copper bromide was shown to be an efficient catalyst for the dialkylation of pyrroles.     

Efficient microwave induced direct α-halogenation of carbonyl compounds

A novel and direct method for the synthesis of α-halocarbonyl compounds using sequential treatment of carbonyl compounds with [hydroxy(tosyloxy)iodo]benzene followed by magnesium halides under solvent-free microwave irradiation conditions is described.     

Synthesis and Structure of Novel Organocycloborates

A series of α,ω‐boryl(bromo)alkanes of the general formula R₂B? (CH₂)_n? Br (n=3, 4, 5, 6) was obtained in high yield following a standard hydroboration protocol. Upon treatment with Mg turnings and formation of the respective Grignard species, all alkanes with n=4 to 6 underwent an unprecedented boron‐centered cyclisation reaction with formation of boratacyclopentanes, ‐hexanes, and ‐heptanes, respectively. All new compounds were isolated in high yields as colourless, crystalline materials and characterised in solution by multinuclear NMR spectroscopy. Four representative examples were chosen for X‐ray diffraction studies, thus providing the first structurally characterised ring systems of that size at a tetraalkyl borate centre.     

Synthesis and crystal structure of the octahedral cluster complex [Th(DMSO)8Cl][Re6Se7Cl7]

A cluster complex of the composition [Th(DMSO)₈Cl][Re₆Se₇Cl₇] has been obtained by interaction of ThCl₄ solution in DMSO with a water solution of K₃[Re₆Se₇Cl₇] and KCl. The compound crystallizes in the rhombic space group Pbcm with unit cell parameters a = 12.262(2) Å, b = 19.653(6) Å, c = 23.603(6) Å, V = 5688(2) ų, Z = 4, d _calc = 3.282 g/cm³. The structure is built from centrosymmetric cluster anions [Re₆Se₇Cl₇]^3? and complex cations [Th(DMSO)₈Cl]³⁺ possessing mirror-plane symmetry, half of the DMSO ligands being doubly disordered.     

MgO在Mg-hBN体系中对合成cBN晶体的影响

 以金属镁粉为触媒，以六角氮化硼为原料，其中加入适量比例的氧化镁，在国产六面顶压机上，在约5.0 GPa压力、1 500～1 800 K温度条件下，合成出了颜色均匀、晶形完整的黄色立方氮化硼单晶体。实验结果表明，在Mg-hBN体系中，氧化镁对合成cBN晶体的颜色及合成温度有很大的影响。     

Diagramme polythermique du systeme ternaire H2O—Al(NO3)3—Mg(NO3)2

The solid—liquid equilibria of the ternary system H₂O—Al(NO₃)₃—Mg(NO₃)₂ were studied at –30, –20, –10 and 0°C by using a synthetic method which allows to detemine all the characteristic points of isothermal sections. The stable solid phases which appear are respectively: ice, Al(NO₃)₃·9H₂O, Mg(NO₃)₂·9H₂O and Mg(NO₃)₂·6H₂O. Neither double salts nor mixed crystals are observed in the temperature and composition field studied. Polytherm diagram layout show two invariant transformations correspond with an eutectic point and a peritectic point.This revised version was published online in November 2005 with corrections to the Cover Date.     

不同溶剂体系中改性氢氧化镁的分散行为

研究了不同的表面改性剂对超细氢氧化镁的表面改性.并分别以水和乙醇为溶剂,研究了表面改性后氢氧化镁的分散行为.实验结果表明,以水为溶剂的体系,六偏磷酸钠分散性能最好,而以乙醇为溶剂,硅烷偶联剂KH-550分散性能最好,其用量为基体量的5%左右,可使制备的超细氢氧化镁粒径达到0.2 μm尺度以下.试验结果对进一步认识超细氢氧化镁的性质及其应用具有重要意义.