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New approaches to stimuli-responsive polymeric micelles and hollow spheres
Zhang Youwei, Jiang Ming
Frontiers of Chemistry in China. 2006, 1 (4): 364-368.
https://doi.org/10.1007/s11458-006-0049-2
This article briefly describes some new approaches to stimuli-sensitive polymeric micelles and hollow spheres, which were developed in the authors laboratory in recent years. (1) Self-assembly of component polymers to non-covalently connected micelles (NCCM) driven by specific interactions. For example, in water, PCL and PAA formed core-shell nanospheres due to interpolymer hydrogen bonding. After crosslinking the PAA shell and removing PCL core, nanocages made of PAA network were obtained. This hollow structure shows perfect reversible size-pH dependence. (2) Simultaneous in-situ polymerization of monomers and self-assembly of the polymers. In this approach, PNIPAM network was formed by radical polymerization covering PCL particles. Hollow spheres of PNIPAM network were then obtained by biodegradation of PCL core. Both the core-shell spheres and hollow spheres show reversible size dependence on temperature change because of the phase transition of PNIPAM around 32ºC. (3) Complexation-induced micellization and transition between the micelles and hollow spheres. Graft copolymers hydroxylethyl cellulose (HEC) and PAA were prepared free radical polymerization. The copolymers showed pH dependent micellization, i.e., micelles formed when pH of graft copolymer solution decreased to around 3. The micellar structure could be locked by crosslinking the PAA grafts. The resultant cross-linked micelles undergo pH-dependent transition between the micelles and hollow spheres, which accompanies a remarkable particle size change. Both the micellization and the structure transition were found to be reversible and associated with H-bonding complexation between the main chain and grafts.
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Synthesis and characterization of rare earth complexes with Phthalaldehyde-lysine Schiff base
Hu Meixian, Li Ning, Yao Kemin
Frontiers of Chemistry in China. 2006, 1 (4): 369-373.
https://doi.org/10.1007/s11458-006-0058-1
Ten new rare earth complexes with Schiff base (HL) derived from phthalaldehyde with two CHO groups and lysine, which has unsymmetrical α-and ε- -NH2 groups, were synthesized and characterized by elemental analysis, TG-DTA analysis, UV Vis, IR, and 1H NMR spectra. They were confirmed to be as LnL2(NO3)•4H2O (Ln=La, Pr, Nd, Sm, Y) and LnL2(NO3)•3H2O (Ln=Gd, Tb, Dy, Er, Yb), respectively. Furthermore, their coordination mechanism, spectral properties and probable molecular structures were also discussed.
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Solid-state synthesis and properties of SmCoO3
Liu Runru, Xu Dapeng, Li Shuang, Lv Zhe, Xue Yanfeng, Wang Deyong, Su Wenhui
Frontiers of Chemistry in China. 2006, 1 (4): 398-401.
https://doi.org/10.1007/s11458-006-0065-2
In this paper, perovskite oxide SmCoO3 was prepared by the solid-state reaction method using Co2O3 and Sm2O3 as raw materials. The structure and properties of the samples were investigated by XRD, Raman spectral techniques, and DC measurements and so on. The results of XRD and Raman spectra showed that the mixtures of Co2O3 and Sm2O3 can react to produce a single phase perovskite oxide SmCoO3 around 1353 K. The single-phase SmCoO3 changes from an insulator to a semi-conductor and transition occurs around 470 K. The thermal expansion coefficient (2.17?10-5 K-1) of the single-phase SmCoO3 is approximately equal to that of doped LaGaO3, but much bigger than that of SDC(Ce0.85Sm0.15O2) above 873 K.
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Synthesis of Eu(Ⅲ) and Tb(Ⅲ) complexes with novel pyridine dicarboxylic acid derivatives and their fluorescence properties
Tang Ruiren, Yan Zi′er, Luo Yiming, Guo Cancheng
Frontiers of Chemistry in China. 2006, 1 (4): 408-413.
https://doi.org/10.1007/s11458-006-0056-3
Starting from pyridine-2,6-dicarboxylic acid (DPA), a series of novel pyridine-2,6-dicarboxylic acid derivatives were synthesized. In these compounds, 4-(hydroxymethyl) pyridine-2,6-dicarboxylate (4-HMDPA) and 4-[(bis-carboxymethyl-amino)-methyl]-pyridine-2,6-dicarboxylic acid (4-BMDPA) were used as multifunctional ligands to coordinate with Tb(!b) and Eu(!b) and the complexes were prepared. The fluorescence properties of the solid complexes and their solutions were investigated in detail. The results indicated that the weak election-withdrawing group 4-hydroxymethyl in 4-position of pyridine in 4-HMDPA could weaken the fluorescence intensity of the lanthanide complexes. The contradistinctive experimental results showed that the fluorescence intensities of these complexes are related to pH values of the aqueous solutions and the dipole moments of solvent molecules: in the neutral aqueous solutions, the fluorescence intensities of these complexes were strongest, while the dipole moments were lower when the fluorescence intensities were stronger. 4-BMDPA is the better sensitizer and may be used as time-resolved fluoroimmunoassay.
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Preparation and characterization of silver colloids with different morphologies under ultrasonic field
Cheng Jingquan, Yao Suwei, Zhang Weiguo, Zou Yi
Frontiers of Chemistry in China. 2006, 1 (4): 418-422.
https://doi.org/10.1007/s11458-006-0067-0
In the ultrasonic field, stable silver colloids were produced by the reduction of AgNO3 with the protection of PVP using KBH4 or N2H4•H2O as reductant. The main factors affecting the morphology of silver nanoparticles, such as distribution of the ultrasonic field, ultrasonic time, ultrasonic power, and the species of reductant, were studied. The silver colloids were identified by TEM and spectrophotometry. The results indicate that the factors such as distribution of the ultrasonic field, ultrasonic time, ultrasonic power, and the species of reductant have a great impact on the morphology of the silver nanoparticles. The size of the silver nanoparticles decreases with the ultrasonic power and ultrasonic time increasing. Ag nanoparticles prepared in standing wave field preferentially grow in a certain direction, which is propitious for forming hexagonal- and spherical-like silver nanoparticles. Monodispersed spherical silver nanoparticles are easily synthesized in the diffusion field. The stability of silver colloid becomes improved by ultrasonic treatment. For example, precipitate is not found after several weeks for the silver colloid prepared with an ultrasonic treatment time of 180 min. The silver nanoparticles prepared without ultrasonic treatment are large spherical-like and hexagonal. Well-dispersed spherical silver particles with a mean size of about 20 nm have been prepared under ultrasonic treatment. Spherical, spherical-like, and hexagonal silver nanoparticles can be obtained by changing the reductants.
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Synthesis of fulleropyrrolidine dicarboxylic acid and its scavenging activity to superoxide radicals $(O_2 ^{\bar \cdot } )$
Liu Xufeng, Liu Xufeng, Chen Zhengxian, Chen Zhengxian, Guan Wenchao, Guan Wenchao
Frontiers of Chemistry in China. 2006, 1 (4): 423-426.
https://doi.org/10.1007/s11458-006-0061-6
Photochemical reaction of C60 with iminodiacetic ester (NH(CH 2COOR) 2, R=Me, Et, t-Bu) produced fulleropyrrolidine derivatives fulleropyrrolidine derivatives 2 in a 55%-36% yield (based on consumed C60). The reaction activity correlated with the steric hindrance of R groups. The order of the reaction rates decreased from Me to t-Bu (R=Me>Et> t-Bu). Fulleropyrrolidine derivative 2 (R=Me) were hydrolyzed with NaH and methanol in toluene, and then acidified with HCl to result in the corresponding fulleropyrrolidine dicarboxylic acid 3 in a 65% yield (relative to fulleropyrrolidine derivative 2). C60 derivatives 2 and 3 were structurally characterized by 1H NMR, 13C NMR, IR, and elementary analysis, MS. A chemiluminescence technique was applied to study the effects of their scavenging superoxide radicals (  ) generated by pyrogallol autoxidation. The results show fulleropyrrolidine dicarboxylic acid 3 had scavenging activity and the efficiencies were dependent on their concentrations. At the concentration of 3.0×10 -4 mol·L -1, fulleropyrrolidine dicarboxylic acid 3 showed a radical scavenging efficiency of approximately 70%. Finally, the influence of structure factor on the scavenging activity was discussed. The results show that the monoadduct of C60, owing to keeping almost intact double bands in C60 moiety, had obvious scavenging activity for superoxide radicals (  ).
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Synthesis of isoxazolidines by 1,3-dipolar cycloaddition and their bioactivity
Cheng Chunsheng, Li Zhinian, Shu Jinyan, Li Tao, Zhang Baoyan
Frontiers of Chemistry in China. 2006, 1 (4): 427-433.
https://doi.org/10.1007/s11458-006-0068-z
A series of new isoxazolidines was prepared by 1,3-dipolar cycloaddition of different mono-substituted styrenes with 1,3-dipolar compounds that were prepared by the reaction of N-methylhydroxylamine sulfate with aromatic carbonyl substances. This synthetic pathway for the preparation of isoxazolidines was an ideal process of green chemistry. The synthetic products were 5-substituted isoxazolidines and their structures were characterized by mass and NMR (1H-, 13C-, COSY, HSQC, and DEPT) spectrometry, and their bioactivity was investigated indicating that some new compounds inhibited Botrytis cinerea effectively.
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Self-assembly of cetyl trimethylammonium bromide in ethanol-water mixtures
Li Wei, Zhang Ming, Zhang Jinli, Han Yongcai
Frontiers of Chemistry in China. 2006, 1 (4): 438-442.
https://doi.org/10.1007/s11458-006-0069-y
The critical micelle concentration (CMC) of cetyl trimethylammonium bromide (CTAB) in both water and ethanol-water-mixed solvent was determined using steady- state fluorescence techniques in order to investigate the effect of the self-assembling properties of the surfactant on the template synthesis of porous inorganic materials. Results indicated that the CMC increased with the increase of ethanol concentration in the mixed solvent. The CMC of CTAB is 0.0009 mol/L in water, while it is 0.24 mol/L in ethanol. Furthermore, the dissipative particle dynamics (DPD) was adopted to simulate the aggregation of CTAB in water and ethanol/water mixtures, and the energy difference was calculated for the surfactant tail groups after mixing with the solvent. The simulation results reflected a regularity similar to the experimental data, i.e., tail groups of CTAB interacted more strongly with ethanol than with water, which elucidates the reason that the micelle is difficult to form in ethanol.
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Investigation on the acute biochemical effects of light rare earths on rat serum by NMR-based metabonomic approaches
Li Zhongfeng, Wu Huifeng, Zhang Xiaoyu, Li Xiaojing, Liao Peiqiu, Li Weisheng, Pei Fengkui
Frontiers of Chemistry in China. 2006, 1 (4): 443-447.
https://doi.org/10.1007/s11458-006-0060-7
1H-NMR spectroscopy and pattern recognition (PR) method were used to assess the acute biochemical effects of light rare earths. Male Wistar rats were treated with both La(NO3)3 and Ce(NO3)3 at doses of 2, 10, and 50 mg/kg body weight. Serum samples from the rats with the two kinds of doses of light rare earths were obtained after 48 h and analyzed by a 600 MHz 1H-NMR spectrometer. Each NMR spectra was data-processed to provide 238 intensity-related descriptors as input coordinates in a multidimensional space and analyzed by PR method. Many low-molecular weight metabolites were identified by 1H-NMR spectra of the rat serum. An increase in ketone bodies, creatinine, lactate, succinate, and various amino acids (valine, leucine, and glutamine) were found from the higher doses (10 and 50 mg/kg body weight) of rare earths-treated groups, together with a decrease of glucose in the serum from Ce(NO3)3-dosed groups. These findings may mean that high-dosage of La and Ce impair a specific region of liver. The similar toxicities with various mechanisms for La and Ce are implicated by NMR-based metabonomic approach. Ce(NO3)3 exhibited a higher toxicity than La(NO3)3 at the same doses.
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Identification and characterization of supercritical fluid extracts of Rhizoma Chuanxiong by high performance liquid chromatography ion trap mass spectrometry
Teng Jiuwei, Li Deliang, Chen Hongwei, Luo Andong
Frontiers of Chemistry in China. 2006, 1 (4): 454-458.
https://doi.org/10.1007/s11458-006-0070-5
The main constituents, senkyunolide A, Z-ligustilide, neocnidilide, 3-butylphthalide, and ligustilide dimers, in supercritical CO2 fluid extracts of Rhizoma Chuanxiong, a popular Chinese traditional medicine, have been identified and characterized by high performance liquid chromatography tandem mass spectrometry. Separations were carried out on an Agilent (ECLIPSE XDB) C18 analytical column by gradient elution with 0.25% acetic acid and methanol (containing 0.25% acetic acid). An Agilent 1100 series LC/MSD XCT system was operated under positive ESI and auto MS/MS modes for mass spectrometric analysis. Collision- induced dissociation (CID) fragmentations of these phthalides have been investigated and elucidated. Phthalides have primarily undergone two ESI CID pathways: side-chain cleavage with losses of alkenes and ring-opening with eliminations of H2O followed by losses of CO. Direct neutral loss of CO has not been observed. Sodium adduct ions have demonstrated completely different CID pathways.
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Preparation and properties of polymer and quantum dot composites
Tian Hongye, Shao Jun, He Rong, Gao Feng, Cui Daxiang, Gu Hongchen
Frontiers of Chemistry in China. 2006, 1 (4): 474-478.
https://doi.org/10.1007/s11458-006-0053-6
Quantum dots (QDs) were prepared in an organic system through a simple and low-cost wet chemistry method. Polymer beads with a diameter of 60 70 nm and specific functional groups were synthesized by a particular seeded emulsion polymerization technique. QDs were embedded in the polymer beads with the specific functional groups through dissolving and swelling method, which provided the condition for the conjunction of biomolecules and QDs as fluorescent probes. The prepared composites were characterized with UV-Vis, PL, TEM, FTIR, CLSM and conductance titration etc. The results show that QDs are successfully embedded in polymer beads, which breaks the limitation that the conjunction of biomolecules and QDs can be achieved only for those synthesized in aqueous system.
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Synthesis and properties of liquid crystalline polyurethanes
Xin Haobo, Zhang Yunfeng, Xing Zheng
Frontiers of Chemistry in China. 2006, 1 (4): 479-483.
https://doi.org/10.1007/s11458-006-0055-4
1,4-Bis(p-hydroxybenzoate)phenylene was prepared using 1,4-bis(trimethylsiloxy)benzene andp-hydroxybenzoyl chloride as starting materials. A series of novel 1,4-bis(p-hydroxyalkoxybenzoate)phenylene were synthesized by reaction of 1,4-bis (p-hydroxybenzoate) phenylene with 3-bromopropanol and 4-bromobutanol, respectively. The liquid crystal polyurethanes were prepared by 1,4-bis(p-hydroxyalkoxybenzoate)phenylene with MDI (p-methylene diphenylenediisocyanate) and 2,4-TDI(2,4-toluenediisocyanate), respectively. The thermotropic properties, the melting point (Tm) and the isotropization temperature (Ti) of the synthesized polyurethanes were characterized by DSC, IR and POM. It showed that all of the polyurethane polymers exhibited thermotropic liquid crystalline properties between 144ºC and 260ºC. The transition temperature (Tm and Ti) decreased with an increase in the length of the methylene spacer.
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