Hollow capsules prepared from all block copolymer micelle multilayers

We introduce a novel and versatile approach for preparing hollow multilayer capsules containing functional hydrophobic components. Protonated polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and anionic polystyrene-block-poly(acrylic acid) (PS-b-PAA) block copolymer micelles (BCM) were used as building blocks for the layer-by-layer assembly of BCM multilayer films onto polystyrene (PS) colloids. After removing the PS colloids, the stabilities of the formed BCM hollow capsules were found to be strongly dependent on the charge density of the hydrophilic corona segments (i.e., P4VP and PAA block segments) as well as the relative molecular weight ratio of hydrophobic core (i.e., PS segments) blocks and hydrophilic corona shells. Furthermore, in the case of incorporating hydrophobic fluorescent dyes into the PS core blocks of micelles, the hairy/hairy BCM multilayers showed well-defined fluorescent images after colloidal template removal process. These phenomena are mainly caused by the relatively high degree of electrostatic interdigitation between the protonated and anionic corona block shells.     

Hollow spheres of silver synthesized using polyelectrolyte capsules as microreactors

Ag/polyelectrolyte (PE) hollow spheres were prepared using PE capsules as microreactors and electroless deposition of Ag. The external layer of the PE capsule was found to have a great effect on the morphology and permeability of the Ag shell. A positive surface charge will form compact and continuous Ag shells whereas a negative surface charge will form expanded and discontinuous shells. After removing the PE, hollow spheres of Ag with different morphologies were obtained.     

Hollow silica capsules with well-defined asymmetric windows in the shell

A straightforward and effective approach to fabricate porous silica capsules with well-defined asymmetric windows in the shell using raspberry-like templates has been developed. This process begins with the formation of a hierarchical template by chemically coupling a large polystyrene sphere to an ensemble of small, polystyrene latex spheres. The hierarchical template in conjunction with a hard templating method and spin-coating leads to silica capsules with well-defined, asymmetric pores (windows) in the outer shell. Proof-of-principle of this approach has been demonstrated using a 1500/110 nm hierarchical template. The silica capsules thus produced were characterized with scanning electron microscopy and STEM. The diameter of the capsules was ~1400 nm, and the outer opening of the windows was ~100 nm in size, consistent with the diameters of the core and satellite spheres considering the shrinkage due to the calcination. The inner opening was ~30 nm, which gives rise to an asymmetry factor, defined as the diameter of the outer window to the diameter of the inner window, of ~3. In another example, surface-bound capsules with an asymmetry factor of ~1 were made. Collectively, these windows can provide efficient pathways to connect the inside of the capsule to the outside and have potential for asymmetric diffusion and rectification.     

Sorption characteristics and mechanisms of organic contaminant to carbonaceous biosorbents in aqueous solution

A series of carbonaceous biosorbents was prepared by pyrolyzing pine needles,a model biomass,at various temperatures (100-700℃) under an oxygen-limited condition for 6h. The elemental composi-tions and the specific surface areas (BET-N2) of the biosorbents were analyzed. Sorption properties of 4-nitrotoluene to the biosorbents and their mechanisms were investigated,and then correlated with the structures of the biosorbents. The result shows that with the increase of the pyrolytic temperature,the aromaticity of the carbonaceous biosorbents increases dramatically and the polarity (the (N O)/C atomic ratio) decreases sharply. Correspondingly,conformations of the organic matter in the biosor-bents transform gradually from a "soft-state" to a "hard-state" and the specific surface areas of the resultant biosorbents extend rapidly. The sorption isotherms fit well with the Freundlich equation. The regression parameters (i.e.,N and lgKf) are linearly related to the aromaticity indices (the H/C atomic ratio). Contributions of adsorption and partition to total sorption of the carbonaceous biosorbents are quantified. The adsorption of the carbonaceous biosorbents increases quickly with the increase of the pyrolytic temperature. The saturated adsorption amounts (Qmax) increase linearly with the increase of the specific surface areas (SA) of the biosorbents. For the carbonaceous biosorbents with hard-state carbon,the calculated normalized-Qmax values by SA are comparable to the theoretical estimation (2.45 μmol/m2). In comparison,for the carbonaceous sorbents with soft-state carbon,the calculated nor-malized-Qmax values by SA are much higher than the theoretical estimation. The partition coefficients (Kom) increase with the decrease of the polarity of the biosorbents,reaching a maximum,and then de-crease sharply with further decreasing the polarity,suggesting that partition mechanism be dominated by the compatibility and accessibility of the sorbent medium with organic pollutant. These observations will provide a theoretical and practical reference to design a cost-effective and high-efficient sorbent,and to accurately predict sorption properties and mechanisms of a given sorbent.     

Preparation of ion exchange resins from carbonaceous adsorbents

Carbonaceous adsorbents are obtained by thermolysis of sulfonated macroreticular polystyrene ion exchange resins at 300-500°C. The hard, spherical, carbonaceous particles react exothermally with elemental chlorine to form products containing up to 38% Cl. The chlorinated particles react readily with polyamines to form anion exchange resins with capacities of up to 2.2 meq/g dry resin. Less than 60% of the nitrogen atoms in the particles are utilized as ion exchange sites. The carbonaceous particles can also be chloromethylated with chloromethyl methyl ether or chlorinated with sulfuryl chloride and then aminated with polyamines to form anion exchange resins, sulfonated with sulfuric acid or chlorosulfonic acid to form strongly acidic cation exchange resins, or chlorosulfonated and then aminated with polyamines to form anion exchange resins. Model structures of the thermolyzed resins containing polycyclic aromatic hydrocarbon fragments are proposed to explain their chemical reactivities.     

Sorption study of uranium on carbon spheres hydrothermal synthesized with glucose from aqueous solution

The ability of oxygen-rich carbon spheres (CSs) produced by hydrothermal carbonization with the glucose has been explored for the removal and recovery of uranium from aqueous solutions. The micro-morphology and structure of CSs were characterized by FT-IR and SEM. The influences of different experimental parameters such as solution pH, initial concentration, contact time, ionic strength and temperature on adsorption were investigated. The CSs showed the highest uranium sorption capacity at initial pH of 6.0 and contact time of 25 min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, △G°(298 K), △H° and △S° were determined to be ?16.88, 12.09 kJ mol^?1 and 197.87 J mol^?1 K^?1, respectively, which demonstrated the sorption process of CSs towards U(VI) was feasible, spontaneous and endothermic in nature. The adsorbed CSs could be effectively regenerated by 0.05 mol/L HCl solution for the removal and recovery of U(VI). Complete removal (99.9 %) of U(VI) from 1.0 L industry wastewater containing 15.0 mg U(VI) ions was possible with 3.0 g CSs.     

pH-responsive capsules derived from nanocrystal templating

In the current work we demonstrate a facile and versatile way to create hydrophilic polymeric capsules by integration of Au nanocrystal templating, surface-initiated atom-transfer radical polymerization, and selective chemical cross-linking of polymer shells. Capsules of the homopolymer of 2-(dimethylamino)ethyl methacrylate and its copolymers with 2-(diethylamino)ethyl methacrylate and poly(ethylene glycol) methyl ether methacrylate were constructed. They swell at low pH and shrink at high pH. On the basis of the pH sensitivity of the resulting capsules, encapsulation and release of a drug model, rhodamine 6G, were realized. Furthermore, by cleaving Au-S bonds between Au cores and polymer shells, capsules containing free Au cores were generated, paving a simple pathway to introduce more functionality to the polymeric capsules.     

Hollow gold and platinum nanoparticles by a transmetallation reaction in an organic solution

Transmetallation reaction between hydrophobized silver nanoparticles with hydrophobized chloroaurate and chloroplatinate ions in chloroform results in the formation of hollow gold and platinum shell nanoparticles respectively.     

Discrimination of guests encapsulation in large hexameric molecular capsules in solution: pyrogallol[4]arene versus resorcin[4]arene capsules

NMR experiments demonstrate that, although 2b and 3b form hexameric capsules in chloroform solutions and despite the very similar building units of these hexamers, 3b encapsulates only the noncharged trialkylamines while 2b can encapsulate both the noncharged trialkylamines and the respective ammonium salts obtained by the addition of DCl. In fact, it was found that protonation that forms in situ the ammonium salt ejects the guest from the hexameric capsule of 3b. This is a general observation as it was found for guests containing alkyl chains of four, five, six, and eight carbons.     

Supercritical fluid extraction of vapor-deposited pyrene from carbonaceous coal stack ash

The efficiencies of extraction of vapor-deposited pyrene from a high-carbon coal stack ash by Soxhlet extraction with methanol, ultrasonic extraction with toluene, acid pretreatment and subsequent ultrasonic extraction with toluene, batch extraction with toluene, and supercritical fluid extraction (SFE) are compared. SFE using CO(2) or isobutane yielded extraction recoveries virtually identical with those obtained using ultrasonic or Soxhlet extraction processes. Collection of the SFE extract was performed by expansion into a solvent or onto the head of a gas chromatography (GC) column. No loss of extracted pyrene was observed upon collection of methanol-modified CO(2) SFE by expansion into methanol. Also, no loss of pure CO(2) SFE extract was observed upon collection on the head of a GC column. However, use of a methanol or toluene modifier for CO(2) SFE directly coupled to GC effected complete loss of extracted pyrene.     

Characterization of water adsorption onto carbonaceous materials produced from food wastes

The recycling of organic wastes has become very important and the development of technology for recycling organic wastes needs to sustain industrial development. In this study, techniques for producing carbonaceous materials from organic wastes are described and water adsorption is characterized. The organic wastes used are coffee grounds and oolong tea leaves carbonized at 673 to 1073 K. The iodine adsorption capacity of the carbonaceous materials increased with increased carbonization temperature. The amount of water adsorbed onto the carbonization materials produced from oolong tea leaves at 873 K for 2 h was the highest. The Freundlich constant 1/n and the differential heat of adsorption of the carbonaceous materials produced from oolong tea leaves were greater than that of the carbonaceous materials produced from coffee grounds. The ability to humidity control can be estimated by the difference between the amount of water adsorbed relative pressure 0.90 and that at relative pressure 0.55. The ability to humidity control was the greatest for the carbonaceous materials produced from the oolong tea leaves at 873 K for 2 h and did not depend upon the adsorption temperature. These results indicated that the carbonaceous materials produced from oolong tea leaves at 873 K for 2 h could have more humidity control.     

从三嵌段共聚物制备纳米空心纤维的研究

近年来 ,利用分子自组装技术制备纳米材料已引起人们越来越多的兴趣[1] ,而从三嵌段共聚物在选择性溶剂中形成可分散的纳米颗粒并通过化学改性的方法使其具有某种功能或用作功能化的载体更具有实际意义 [2 ] .本文从由阴离子聚合得到的窄分布三嵌段共聚物出发 ,成功地制备了纳米空心纤维 ,将有可能用于制备纳米导线及模板聚合等方面 .1　实验部分1 .1　样品制备　采用阴离子聚合方法制备三嵌段共聚物 ,用凝胶色谱测定分子量分布宽度 ,光散射测定重均分子量 ,NMR测定其化学组成比 .将共聚物的甲苯浓溶液 (质量分数 30 % )倒入培养皿中并密…     

Hollow fiber-liquid-phase microextraction of fungicides from orange juices

Liquid-phase microextraction (LPME) based on polypropylene hollow fibers was evaluated for the extraction of the post-harvest fungicides thiabendazole (TBZ), carbendazim (CBZ) and imazalil (IMZ) from orange juices. Direct LPME was performed without any sample pretreatment prior to the extraction, using a simple home-built equipment. A volume of 500 μL of 840 mM NaOH was added to 3 mL of orange juice in order to compensate the acidity of the samples and to adjust pH into the alkaline region. Analytes were extracted in their neutral state through a supported liquid membrane (SLM) of 2-octanone into 20 μL of a stagnant aqueous solution of 10 mM HCl inside the lumen of the hollow fiber. Subsequently, the acceptor solution was directly subjected to analysis. Capillary electrophoresis (CE) was used during the optimization of the extraction procedure. Working under the optimized extraction conditions, LPME effectively extracted the analytes from different orange juices, regardless of different pH or solid material (pulp) present in the sample, with recoveries that ranged between 17.0 and 33.7%. The analytical performance of the method was evaluated by liquid chromatography coupled with mass spectrometry (LC/MS). This technique provided better sensitivity than CE and permitted the detection below the μg L⁻¹ level. The relative standard deviations of the recoveries (RSDs) ranged between 3.4 and 10.6%, which are acceptable values for a manual microextraction technique without any previous sample treatment, using a home-built equipment and working under non-equilibrium conditions (30 min extraction). Linearity was obtained in the range 0.1–10.0 μg L⁻¹, with r = 0.999 and 0.998 for TBZ and IMZ, respectively. Limits of detection were below 0.1 μg L⁻¹ and are consistent with the maximum residue levels permitted for pesticides in drinking water, which is the most restrictive regulation applicable for these kinds of samples. It has been demonstrated the suitability of three-phase LPME for the extraction of pesticides from citrus juices, suppressing any pretreatment step such as filtration or removal of the solid material from the sample, that may potentially involve a loss of analyte.     

Very high-mass ions derived from carbonaceous samples in laser microprobe mass spectrometry

An extended series of positive ions occurring at regular intervals of 24 D is observed in the laser-induced ionization mass spectra of several solid carbonaceous materials. These ions occur with masses up to 3000 D, and can exceed the mass of the parent compound. This effect was found with some polynuclear aromatic hydrocarbons, coal and soots.