Preparation of poly(methyl methacrylate) microcapsules by in situ polymerization on the surface of calcium carbonate particles

Poly(methyl methacrylate) (PMMA) microcapsules were prepared by the in situ polymerization of methyl methacrylate (MMA) and N,N′-methylenebisacrylamide on the surface of calcium carbonate (CaCO₃) particles, followed by the dissolution of the CaCO₃ core in ethylenediaminetetraacetic acid solution. The microcapsules were characterized using fluorescence microscopy, atomic force microscopy, scanning electron microscopy, and Fourier transform infrared spectroscopy. The average sizes of the CaCO₃ particles and PMMA capsules were 3.8 ± 0.6 and 4.0 ± 0.6 μm, respectively. A copolymer consisting of MMA and rhodamine B-bearing MMA was also used to prepare microcapsules for fluorescent microscopy observations. Fluorescein isothiocyanate-labeled bovine serum albumin was enclosed in the PMMA microcapsules and its release properties were studied.     

以手性两亲小分子为模板剂制备介孔二氧化硅纳米空心球

以L-亮氨酸为手性源合成了手性阳离子两亲性小分子化合物L-18Leu6NEtBr,用其自组装体作为模板,氢氧化钠为催化剂,经溶胶-凝胶过程制备出介孔二氧化硅纳米空心球;分析了介孔二氧化硅纳米空心球的尺寸和孔径.结果表明,所制备的二氧化硅空心球直径约100nm;其介孔孔道平行于壳表面,孔径为3.1nm.     

以手性两亲小分子自组装体为模板制备介孔二氧化硅空心球

合成了手性阳离子型两亲性小分子化合物,利用圆二色谱分析了其在水中形成的自组装体的结构;以该化合物的自组装体为模板,在正丙醇和氨水的混合溶剂中制备得到了介孔二氧化硅空心球;利用扫描电镜、透射电镜、X射线衍射仪以及氮气吸附-脱附试验装置分析了二氧化硅空心球的形貌及孔结构.结果表明,两亲性小分子在水中形成的自组装体呈现手性堆积;合成的介孔二氧化硅空心球的直径约为600~800nm,壁厚约为100~150nm,其孔道垂直于球的表面,孔径约为3.0nm,比表面积约为306m2·g-1.正丙醇作为模板控制二氧化硅空心球的空腔尺寸和形貌,而两亲性小分子的自组装体作为模板控制放射状孔道的形貌和尺寸.     

Differentiating calcium carbonate polymorphs by surface analysis techniques—an XPS and TOF‐SIMS study

Calcium carbonate has evoked interest owing to its use as a biomaterial, and for its potential in biomineralization. Three polymorphs of calcium carbonate, i.e. calcite, aragonite, and vaterite were synthesized. Three conventional bulk analysis techniques, Fourier transform infrared (FTIR), X‐ray diffraction (XRD), and SEM, were used to confirm the crystal phase of each polymorphic calcium carbonate. Two surface analysis techniques, X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectroscopy (TOF‐SIMS), were used to differentiate the surfaces of these three polymorphs of calcium carbonate. XPS results clearly demonstrate that the surfaces of these three polymorphs are different as seen in the Ca(2p) and O(1s) core‐level spectra. The different atomic arrangement in the crystal lattice, which provides for a different chemical environment, can explain this surface difference. Principal component analysis (PCA) was used to analyze the TOF‐SIMS data. Three polymorphs of calcium carbonate cluster into three different groups by PCA scores. This suggests that surface analysis techniques are as powerful as conventional bulk analysis to discriminate calcium carbonate polymorphs. Copyright © 2008 John Wiley & Sons, Ltd.     

Characterization,by inverse gas chromatography,of the surface properties of calcium carbonate before and after treatment with stearic acid

Summary The interaction of n-alkanes with stearyl chains chemically fixed on the surface of calcite particles is investigated using inverse gas chromatography. Free enthalpy, enthalpy, entropy of adsorption and dispersive component of the surface free energy are determined. Untreated and stearic acid treated calcites have comparable affinities for the alkanes. However, the differences in adsorption entropies point to different interaction mechanisms: gas-solid adsorption for the untreated calcite and gasliquid interactions for the modified sample. Furthermore, for long chains probes, having more than 8 carbon atoms, the loss in entropy is smaller than for shorter chains. Possibly, long chains are only partially inserted in between the stearyl grafts, thus keeping a higher degree of freedom.     

Preparation of uniform silica/polypyrrole core/shell microspheres and polypyrrole hollow microspheres by the template of modified silica particles using different modified agents

Silica/polypyrrole (PPY) core/shell microspheres and PPY hollow microspheres were prepared by the template of silica particles whose surface character was modified with different modified agents. The morphology and structure of the particles were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Elemental analysis and X-ray photoelectron spectroscopy (XPS) were carried out to characterize the structure of PPY hollow microspheres. We investigated the effect of different modified agents on the surface character of silica particles and the effect of surface character of silica particles on the morphology of PPY hollow microspheres. The effect of reaction conditions on the size of core/shell particles and hollow particles was also studied.     

Synthesis of silica particles with lamellar and wormhole-like bi-modal mesopores using anionic surfactant as the template

Silica particles with lamellar and wormhole-like bi-modal mesopores have been synthesized using anionic surfactant (N-lauroylsarcosine sodium) as the template. The particles with diameters of 300―500 nm possess bi-modal mesopores with pore sizes of 3 nm and 12 nm, which were ascribed to the disordered wormhole-like mesophase and lamellar mesophase, respectively. The BET surface area of the particles was 536 m2/g and the pore volume was 0.83 cm3/g. The lamellar mesophase and cylindrical mesophase were formed...     

Preparation of anhydrochymotrypsin diol silica as selective adsorbent for affinity chromatography of peptides with aromatic amino acids at C-termini

Summary Anhydrochymotrypsin (AHC), a catalytically inert derivative of chymotrypsin in which the serine-residue active site has been converted chemically to a dehydroalanine residue, was immobilized on diol silica by activation with trifluoroethanesulfonyl chloride. A AHC-diol-silica column was used for high-performance affinity chromatographic separation of peptides with aromatic amino acids at their C-termini from other peptides. Faster separations were achieved.     

Synthesis of highly pure poly(aryleneethnylene)s using palladium supported on calcium carbonate as an eco‐friendly heterogeneous catalyst

Metal catalyst contamination is a major concern in the preparation of polymeric materials. For conjugate polymers, trace amount of metal catalyst is detrimental to the optoelectronic properties. In this work, a method for synthesizing highly pure fluorescent polymers, poly(aryleneethynylene)s (PAEs), was developed using heterogeneous Pd/CaCO₃ catalytic system. Polymerization between a variety of aryl diethynes and aryl diiodides or dibromides were achieved using a catalytic amount of Pd/CaCO₃, CuI, and PPh₃ at 80 °C in good to excellent yields (79–100%). Resulting polymers possess degree of polymerization ranging from 8 to 50 with polydispersity index of 1.5–3.6. Importantly, PAEs from Pd/CaCO₃ catalytic system contain considerably lower level of Pd and Cu contamination (1.9 and 3.4 ppm, respectively) than those obtained from classical homogeneous catalyst, Pd(PPh₃)₄ and PdCl₂(PPh₃)₂ or heterogeneous catalyst Pd/C. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1556–1563     

Modification of fumed silica surface with different sulfonamides via a postsynthesis method and their application as antibacterial agents

The surface of nanosized fumed silica (FSi) was modified with different amine groups by the use of silylating agents. The obtained propylamine, propylpiperazine, and propyl-p-phenylenediamine–modified FSi were treated with different sulfonyl chlorides to gain sulfonamide-modified FSi compounds. These compounds were characterized by various techniques including Fourier transform infrared spectroscopy, thermogravimetric analysis, differential thermal analysis, scanning electron microscopy, and energy-dispersive X-ray spectroscopy (EDX), confirming the grafted sulfonamides on the FSi surface. Sulfonamide-modified surfaces are efficient catalysts for the Michael addition-based syntheses and coupling reactions. Furthermore, the antibacterial tests showed that these modified FSi compounds have antibacterial activities and thus are useful materials for preparing antibacterial silicone-based compounds such as silicone glue and oil.     

Preparation of block copolymer of poly(trimethylene carbonate) with oligo(ethylene glycol) and the surface properties of the dip coated film

To persuade the stent coating materials for the better sustainable development, a block copolymer composed of hydrophobicity of poly(trimethylene carbonate) (PTMC) and hydrophilicity of PTMC bearing ethylene glycol chains was synthesized as a potential candidate. The result of thermal stability of the polymer was analyzed which reached up to 206 °C (T₁₀) and it is considered that sufficient for sterilization during the treatment. Moreover, the dip coated films of polymer were coated on polyethylene (PE) and stainless steel (SS) substrates in order to stimulate the stability upon the physiological environment. In addition, the preliminary in vitro test of the films were evaluated by protein adsorption and blood platelet adhesion tests. Hence, this study tends to convince that the synthetic block copolymer based on PTMC derivatives were approached for stent coating materials.     

Oxidative carbonylation of phenol to diphenyl carbonate catalyzed by palladium complexes bridged with N,N‐ligands over functionalized silica

Heterogeneous palladium catalysts anchored on functionalized silica were prepared by sol–gel methods and their catalytic properties for the oxidative carbonylation of phenol to diphenyl carbonate (DPC) were investigated. The catalysts were characterized by means of IR, XPS, EA and BET. The Pd loading in the heterogeneous catalysts and leaching in solution were detected by atomic absorption. The effects of different reaction parameters such as temperature, solvent and inorganic cocatalyst on the yield of DPC and Pd leaching were also studied. It was found that Cu₂O and tetrahydrofuran (THF) were the best partners with these heterogeneous catalysts. In the presence of 3 Å molecular sieves as dehydrating agent, the heterogeneous palladium catalyst prepared from 2‐acylpyridine revealed excellent catalytic performance and stability at 110 °C for 5 h, giving 13.7% yield of DPC based on phenol and 4.0% Pd loss in solution. The heterogeneous catalyst was more active and stable compared with traditional supported Pd? C catalyst under the same reaction conditions. Copyright © 2005 John Wiley & Sons, Ltd.     

Polymers of carbonic acid. XIV. High molecular weight poly(trimethylene carbonate) by ring-opening polymerization with butyltin chlorides as initiators

Numerous BuSnCl, Bu₂SnCl, and Bu₃SnCl-initiated polymerizations of cyclo(tri-methylene carbonate) (TMC) were conducted in bulk. In addition to the initiator, reaction time, temperature, and monomer/initiator (M/I) ratio were varied. Yields above 90% were obtained with all three initiators, but their reactivities decrease in the order BuSnCl₃ > Bu₂SnCl₂ > Bu₃SnCl. The maximum molecular weights decrease in the same order. With BuSnCl₃ M_ws up to 250,000 were obtained. These molecular weights were determined by GPC on the basis of the universal calibration method. In this connection Mark-Houwink equations for two solvents, tetrahydrofuran (THF) and CH₂Cl₂ were determined and compared with literature data. Furthermore, mechanistic aspects were studied. ¹H- and ¹³C- NMR spectra revealed that BuSnCl₃ forms complexes with the CO-group of TMC, whereas Bu₂SnCl₃ do not cause NMR spectroscopic effects. Kinetic studies in chloroform and nitrobenzene and a comparison with Bu₃SnOMe suggest that at least BuSnCl₃ initiates a cationic mechanism. However, in contrast to SnCl₄ (or SnBr₄), BuSnCl₃ does not cause decarboxylation. Regardless of the initiator ¹H-NMR spectroscopy revealed CH₂OH and CH₂CI endgroups in all cases. © 1995 John Wiley & Sons, Inc.     

Fused silica capillaries with two segments of different internal diameters and inner surface roughnesses prepared by etching with supercritical water and used for volume coupling electrophoresis

In this work, single‐piece fused silica capillaries with two different internal diameter segments featuring different inner surface roughness were prepared by new etching technology with supercritical water and used for volume coupling electrophoresis. The concept of separation and online pre‐concentration of analytes in high conductivity matrix is based on the online large‐volume sample pre‐concentration by the combination of transient isotachophoretic stacking and sweeping of charged proteins in micellar electrokinetic chromatography using non‐ionogenic surfactant. The modified surface roughness step helped to the significant narrowing of the zones of examined analytes. The sweeping and separating steps were accomplished simultaneously by the use of phosphate buffer (pH 7) containing ethanol, non‐ionogenic surfactant Brij 35, and polyethylene glycol (PEG 10000) after sample injection. Sample solution of a large volume (maximum 3.7 μL) dissolved in physiological saline solution was injected into the wider end of capillary with inlet inner diameter from 150, 185 or 218 μm. The calibration plots were linear (R ² ∼ 0.9993) over a 0.060–1 μg/mL range for the proteins used, albumin and cytochrome c. The peak area RSDs from at least 20 independent measuremens were below 3.2%. This online pre‐concentration technique produced a more than 196‐fold increase in sensitivity, and it can be applied for detection of, e.g . the presence of albumin in urine (0.060 μg/mL).     

Preparation of bi-layer-polymer coated silica using atom transfer radical polymerization and its application as restricted access phase for HPLC separation of hydrophobic molecules in biological fluids

A novel restricted access material was prepared by surface initiated atom transfer radical polymerization. The bi-layer-polymer structures were created on the surface of silica layer-by-layer. The inner layer was composed of poly(styrene-co-divinylbenzene), which was grafted first for binding small molecules based on hydrophobic and π-π interactions. The poly(styrene-co-divinylbenzene) bonded silica has good selectivity for aromatic hydrocarbons. It also has hydrophobicity and column efficiency similar to a C(18) bonded silica. The material has shown good ability of protein exclusion after grafting hydrophilic polymer on the external surface while its hydrophobicity and selectivity do not have obvious change. It demonstrated that the material is still qualified for hydrophobic extraction. In the study, the relations between the polymer structures and chromatographic properties of the materials were investigated. The synthetic conditions were optimized. The results have shown that the material prepared in the study has application potential in the HPLC analysis of hydrophobic molecules from biological samples by direct injection. It demonstrated that atom transfer radical polymerization can be used as a method in the preparation of restricted access material.     

Preparation of a polymeric ionic liquid-coated solid-phase microextraction fiber by surface radical chain-transfer polymerization with stainless steel wire as support

Polymeric 1-vinyl-3-octylimidazolium hexafluorophosphate was synthesized in situ on stainless steel wire by surface radical chain-transfer polymerization and used as sensitive coatings in solid-phase microextraction. The outer surface of the stainless steel wire was firstly coated with microstructured silver layer via silver mirror reaction and then functionalized with self-assembled monolayers of 1,8-octanedithiol, which acted as chain transfer agent in the polymerization. Coupled to gas chromatography, extraction performance of the fiber was studied with both headspace and direct-immersion modes using benzene, toluene, ethylbenzene and xylenes (BTEX), phenols and polycyclic aromatic hydrocarbon (PAHs) as model analytes. In combination with the microstructured silver layer, the PIL-coated fiber exhibited high extraction efficiency. Linear ranges for BTEX with headspace mode were in the range of 0.2-1000 μg L(-1) for benzene, and 0.1-1000 μg L(-1) for toluene, ethylbenzene and xylenes. Limits of detection (LODs) were from 0.02 to 0.05 μg L(-1). Wide linear ranges of direct-immersion mode for the extraction of several phenols and PAHs were also obtained with correlation coefficients (R) from 0.9943 to 0.9997. The proposed fiber showed good durability with long lifetime. RSDs of 56 times extraction were still in an acceptable range, from 8.85 to 22.8%.     

Preparation,characterization, and thermal properties of microPCMs containing <Emphasis Type="Italic">n</Emphasis>-dodecanol by using different types of styrene-maleic anhydride as emulsifier

Microcapsules containing polar phase change material (PCM) n-dodecanol were synthesized by in situ polymerization using melamine-formaldehyde resin as shell and styrene-maleic anhydride copolymer (SMA) as emulsifier. The effects of polarity of PCM and types and amounts of SMA emulsifier on the properties of microencapsulated PCMs (microPCMs) were studied and characterized by using Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and laser particle diameter analyzer. The results show that thermal properties of microPCMs are affected greatly by the types and amounts of SMA. Anionic SMA emulsifier is suitable for the encapsulation of n-dodecanol. The polarity of PCM leads to the higher adding amount of SMA emulsifier. When mass ratio of emulsifier to n-dodecanol is 4.8%, the phase change latent heat and encapsulation efficiency reach to the maximum value of 187.5 J/g and 93.1%, respectively. Irregular spherical microPCMs with mean diameter of 30.6 μm and phase change temperature of 21.5 °C are obtained and can be used for energy storage.