Periodic mesoporous organosilicas with multiple bridging groups and spherical morphology

Bi- and trifunctional periodic mesoporous organosilicas (PMOs) with phenylene, thiophene, and ethane bridging groups were synthesized using 1,2-bis(triethoxysilyl)ethane (BTEE), 1,4-bis(triethoxysilyl)benzene (BTEB), and 2,5-bis(triethoxysilyl)thiophene (BTET) organosilica precursors and a poly(ethylene oxide)-poly(D,L-lactic acid-co-glycolic acid)-poly(ethylene oxide) (PEO-PLGA-PEO) triblock copolymer template under low acidic conditions. The PMO samples with different concentrations of organic bridging groups were obtained in the form of spherical particles having average diameters of 2-3 mum and 2D hexagonal (p6m) mesostructure with pore diameters of 7.3-8.4 nm. The particle morphology and chemistry of pore walls were tailored using different mixtures of organosilica precursors. Adsorption and structural properties of the aforementioned PMOs have been studied by nitrogen adsorption and small-angle X-ray scattering, whereas their framework chemistry was quantitatively analyzed by solid-state 13C and 29Si MAS NMR.     

Adsorption of gas on ion exchangers. III. The pore structure of m-aminophenol–formaldehyde condensation resins

m-Aminophenol was condensed with formaldehyde in an acid medium in the presence of a water-soluble inorganic salt (NaCl, CaCl₂ etc) and/or poly(ethylene glycol). The pore structure characteristics of the condensation products were investigated by measurements of average pore size, pore size distribution of channels, total pore volume, surface area, and electron microscopic observation. The type and concentration of inorganic salts appeared to be a significant variable for the resulting pore structure, while poly(ethylene glycol) had a little effect. The nongel interstices of products were channels between many agglomerates of minute spherical gel particles with narrow pore size distribution. The diameters of these spherical gel particles were 3–10 × 10^?1µ from the scanning electron microscopic observation. Apparent dissociation constants of functional groups of resin, pK_a and pK_b, estimated by using the Henderson-Hasselbach equation, were 10.94 and 10.99, respectively. The resin had an ion-exchange capacity of 1.0 meq/g for base and 4.8 meq/g for acid.     

Synthesis and characterization of nanostructural polymer-silica composite: positron annihilation lifetime spectroscopy study

The swelling of poly(TRIM) spherical particles in TEOS is assessed as a potential way for obtaining polymer-silica nanocomposite materials. Silica deposition was achieved by simply stirring of swollen polymer particles in acidic hydrochloric-water solution. This procedure leads to spherical composite particles with dispersed silica gel within the polymer matrix. The resulting material exhibits the same morphology as the initial polymer. Nanocomposite particles are silica rich (about 17 wt.%). Characterization of the nanocomposites was performed using scanning electron microscopy, FT-IR spectroscopy, (29)Si CP MAS NMR spectroscopy and thermogravimetry. Moreover, the use of positron annihilation lifetime spectroscopy PALS to characterize the structural properties of the nanocomposites is presented. This technique gave more realistic pieces of information about the pore structure of the investigated samples in contrast to nitrogen adsorption studies.     

Formation mechanism of nonspherical gold nanoparticles during seeding growth: roles of anion adsorption and reduction rate

A small section of nonspherical particles can be observed in the further growth of spherical gold colloids exposed to a mixture of NH2OH and HAuCl4. The concentration ratio of [NH2OH]:[HAuCl4] is critical for the formation of nonspherical particles as higher ratios produce lower yields and smaller of such particles. These concentrations also affect the reaction kinetics; the reaction rate increases with [NH2OH], while independent of [HAuCl4], which we believe is due to the specific adsorption of AuCl4- onto gold surface. These nonspherical particles come from the preferential growth of {111} facets as indicated by their TEM images and electron diffraction patterns. We propose this preferential growth is ascribed to the preferential adsorption of AuCl4- on {111} facets, and some competition which determines the yield of nonspherical particles exists between the AuCl4- adsorption and the AuCl4- reduction, faster reduction counteracting the effect of this preferential adsorption and thus suppressing nonspherical particle. This result probably provides some guidance to develop a shape-controlled synthesis of gold particles without any additives.     

Hydrocarbon dispersions of acrylic microspheres with polar surface functionality

Submicron and micron sized particles containing a crosslinked core and a polar shell were prepared by 3-stage nonaqueous dispersion [NAD] polymerization in an aliphatic hydrocarbon medium. When a poly (12-hydroxystearic acid) [PHS] comb stabilizer was used in all three stages, the particles produced were spherical, submicron in size, and had a relatively broad size distribution. If the monomer mixture in the third stage contained relatively large amounts of butyl acrylate, stable dispersions of sponge-like aggregates, 3–5 μm in size, were obtained. When butyl rubber was employed as a stabilizer precursor in the seed formation step, the shape of the final particles depended upon whether a crosslinker was employed in the second stage polymerization. When a crosslinker was present, the second-stage particles and the subsequent third-stage particles had a shrunken, raisin-like appearance. When no crosslinker was present, spherical particles were obtained. In both cases, the resulting third-stage particles were easily dispersed in water containing a small amount of amine base, indicating that ? COOH and ? OH groups are located at the surface (or in a shell at the surface) in these NAD particles. © 1994 John Wiley & Sons, Inc.     

Monodisperse porous poly(vinyl acetate-co-divinylbenzene) particles by single-stage seeded polymerization: a packing material for reversed phase HPLC

A single-stage swelling and polymerization method was proposed for the synthesis of monodisperse porous poly(vinyl acetate-co-divinylbenzene) [poly(VAc-co-DVB)] particles with different VAc/DVB feed ratios. The particles obtained with the VAc/DVB feed ratio of 50:50 v/v had a narrow pore size distribution exhibiting a sharp peak at 30 nm. Based on this distribution the mean pore size and the specific volume were determined as 12 nm and 1.39 mL/g, respectively. The specific surface area of poly(VAc-co-DVB) particles was found to be 470 m2/g. These properties make poly(VAc-co-DVB) particles a promising support for potential HPLC applications. Poly(vinyl alcohol-co-divinylbenzene) [poly(VA-co-DVB)] particles were then obtained by the basic hydrolysis of poly(VAc-co-DVB) particles. The hydroxyl groups on poly(VA-co-DVB) particles have a suitably reactive functionality for surface grafting or derivatization protocols aiming at synthesizing various HPLC packings. The examination of poly(VA-co-DVB) particles by confocal laser scanning microscopy showed the homogeneous distribution of hydroxyl functionality in the particle interior. As a starting point, the chromatographic performance of plain material, poly(VAc-co-DVB) particles produced with VAc/DVB feed ratio of 50:50 (v/v) was tested by a commonly utilized chromatographic mode, reversed phase chromatography. Poly(VAc-co-DVB) particles were successfully used as packing material in the RP separation of alkylbenzenes with resolutions higher than 1.5. Theoretical plate numbers up to 17 500 plates/m were achieved. No significant change both in the chromatographic resolution and column efficiency was observed with increasing flow rate. The chromatography showed that poly(VAc-co-DVB) particles were a suitable starting material for the synthesis of chromatographic packings for different modes of HPLC.     

Adsorption of bovine serum albumin on template-polymerized chitosan/poly(methacrylic acid) complexes

Particulate systems composed of polyelectrolyte complexes (PEC) based on chitosan and poly(methacrylic acid) were obtained via template polymerization. The resultant particles were characterized as having regions with different charge densities: chitosan predominating in the core and poly(methacrylic acid) at the surface, the particles being negatively charged, as a consequence. Albumin was adsorbed on these particles (after cross-linking with glutardialdehyde), and pH was controlled to obtain two conditions: (i) adsorption of positively charged albumin and (ii) adsorption of albumin at its isoelectric point. Adsorption isotherms and zeta-potential measurements showed that albumin adsorption was controlled by hydrogen bonding/van der Waals interactions and that brush-like structures may enhance the adsorption of albumin on these particles. It was also found that shearing can induce desorption of albumin from the PEC surface, depending on the continuous phase albumin concentration.     

Synthesis of hollow spherical silica with MCM-41 mesoporous structure

Hollow spherical mesoporous silica was synthesized by using sodium silicate as a precursor and a low concentration of cetyltrimethylammonium bromide (CTAB) (0.154 mol dm^–3). The resulting hollow spherical particles were characterized with scanning electron microcopy (SEM), small-angle X-ray diffraction (SXRD), transmission electron microscopy (TEM), and N₂ gas adsorption and desorption techniques. The results showed that regular spherical mesoporous silica could be obtained only if the molar ratio of propanol to CTAB was in the range of approximately 8:1–9:1. The spherical particles were hollow (inside), and the shell consisted of smaller particles with a pore structure of hexagonal symmetry. With an increase of the molar ratio of propanol to CTAB, the distance (a value) between centers of two adjacent pores increased, and the pore structure of mesoporous silica became less ordered. N₂ adsorption–desorption curves revealed type IV isotherms and H1 hysteresis loops; with an increase of the molar ratio of propanol to CTAB, the pore size with Barrett–Joyner–Halenda (BJH) diameter of the most probable distribution decreased, but the half peak width of the pore size distribution peak increased     

Super Absorbent Hydrogel Based on Poly[acrylamide/maleic acid/2-methacryloxy ethyl trimethylammonium chloride]: Synthesis,Characterization and their Application in the Removal of Chromium (VI) from Aqueous Solution

New poly[acrylamide/maleic acid/2-methacryloxy ethyl trimethylammonium chloride], poly[AAm/MA/METAC], super absorbent hydrogels (M1-M4) were prepared via microwave irradiated free radical solution polymerization using different compositions. According to swelling experiments, hydrogel M1 with higher METAC content gave relatively higher swelling percentage compared to other hydrogels. The hydrogel M1 was characterized by FT-IR, TGA, and SEM analysis. The influence of the uptake conditions such as pH, time, adsorbent dose and initial feed concentration on the metal ion binding capacity of hydrogel was also tested. Furthermore, the Langmuir and Freundlich adsorption isotherms were applied and they showed a good fit to the experimental data.     

新型吸附剂——球形碳化树脂的研究Ⅳ

将粒径为0.8-1.2mm的大孔聚丙烯腈小球在氧气氛下热处理后,于高纯氮保护下,进行高温裂解,得到粒径为0.40—0.63mm的球形碳化吸附树脂。该树脂比表面为588m~2/g,对肌酸酐、尿酸及维生素B_12的吸附量可达98％以上。碳化聚丙烯腈(下称碳化球)收率为20％。降低裂解温度或未经活化处理,碳化球收率可达50％,对尿酸及锥生素B_12仍有优异的吸附性能,但对肌酸酐的吸附率很低。     

锆-铝复合氧化物的制备及酸腐蚀对其表面性质的影响

利用溶胶－凝胶技术制备了ZrO2-Al2O3复合氧化物,考察了不同的投料比时复合氧化物的物理化学性质,比较了不同浓度酸腐蚀前后氧化物微球的比表面积、孔径、表面酸碱性及复合氧化物中氧化锆、氧化铝摩尔比等物理化学参数的变化。     

三维大孔TiO2光催化剂的制备及其催化性能

 以聚甲基丙烯酸甲酯微球为模板,以钛酸正丁酯为原料,采用溶胶-凝胶法制备了具有三维结构的大孔TiO2. 采用差示扫描量热、热重-微分热重、X射线衍射、红外光谱、扫描电子显微镜和氮气吸附等手段对样品进行了表征. 结果表明,高温热处理后得到的三维大孔TiO2光催化剂的孔径为200 nm左右,孔径分布均匀, TiO2纳米晶粒中锐钛矿相和金红石相的含量分别为82%和18%. 光催化氧化实验表明,此种三维结构的TiO2对甲基橙溶液具有较好的光催化氧化性能.     

Precipitation polymerization in acetic acid: synthesis of monodisperse cross-linked poly(divinylbenzene) microspheres

This paper reports two important results with cross-linked precipitation polymerization. (1) Acetonitrile, a substance harmful to human health, is the most commonly used solvent for the synthesis of cross-linked polymeric microspheres by precipitation polymerization. Here, the much safer acetic acid replaced acetonitrile as a solvent in the precipitation polymerization of monodisperse cross-linked poly(divinylbenzene) (PDVB-55) microspheres. Pumpkin-like particles and microspheres were obtained. XPS results displayed a significant amount of double bonds on the surface of the particles. The effect of monomer content, temperature, and initiator amount on the formed particles were studied. For a DVB loading below 1 vol % at 70 degrees C, monodisperse microspheres with smooth surfaces and narrow diameters were successfully obtained. With a DVB loading of 2 vol % and by observing the shapes of particles obtained with three different temperature(60, 70, and 80 degrees C), we found that more spherical particles were obtained at higher temperatures and pumpkin-like particles were obtained at lower temperatures. No significant differences in morphology or the coefficient of variation (CV) of the particles were obtained for different initiator loadings, whereas the particle diameters could be increased with increased initiator concentrations. (2) In order to obtain a better understanding of the formation mechanism of these particles, time-dependent experiments, for the first time, were conducted in a hydrophobic monomer system. By tracing the whole polymerization process, some important results were found. First, with the polymerization time at 70 degrees C, the particle diameters were found to increase from 800 nm to 3.0 microm, the CV displayed a decrease, and the amount of spheres and the spherical evenness of the particle surfaces improved. Second, by quantitatively calculating the particle number from the yields and diameters data, it is found that starting from 3.1% yield or two hours reaction time the total amount of particles in the system is almost a constant (about 9.6 x 10 (8)/L), which means that no homocoagulation occurred and no new particles were generated after nucleation, and there is a linear relation between cubic diameters and yields. These two results give us a distinct impression that particle growth almost comes from capturing of newly formed oligomers. Based on the above results, a scheme for the particle formation is proposed, which shows that that pumpkin-like particles are caused by a prolonged nucleation including the homocoagulation of primary nuclei. The growth of the particles includes two modes, an in situ surface polymerization of monomer and the adsorption of PDVB-55 oligomers. The differences between results in acetonitrile and in acetic acid (higher yields, smaller size, not spherical but pumpkin-like particles in acetic acid) were due to the lower solubilizability of acetic acid which is the so-called proton-containing solvent with the hydrogen bonding structure.     

Fabrication of highly porous poly (ɛ-caprolactone) fibers for novel tissue scaffold via water-bath electrospinning

A non-toxic route was used for the preparation of silver nanoparticles using tryptophan (Trp) as reducing/stabilizing agent in the presence of cetyltrimethyl ammonium bromide (CTAB). Role of water soluble neutral polymer poly(vinylpyrrolidone) (PVP) has been studied on the growth of yellow colour silver nanoparticle formation. The synthesized nanostructures were characterized by UV–Visible absorption spectroscopy, transmission electron microscopy (TEM) by observing the size and distribution of silver nanoparticles. As the reaction proceeded, particles grew up to about 10 and 20 nm in the presence and absence of PVP, respectively, as determined by TEM. The formed nanoparticles showed the highest absorption plasmon band at 425 nm. Rate of silver sol formation increases with the [Trp], [CTAB] and [PVP], reaching a limiting value and then decreases with the increase in concentrations of these reagents. It was observed that nanoparticles are spherical, aggregated and poly dispersed in the absence and presence of PVP, respectively. On the basis of kinetic data, a suitable mechanism is proposed and discussed for the silver sol formation.     

Preparation of MCM-41 silica using the cationic surfactant blend

A series of samples of MCM-41 silica was synthesized using surfactant blends of 1-alkyl-3-methylimidazolium and alkyltrimethylammonium salts or blends of two different 1-alkyl-3-methylimidazolium salts (alkyl denotes octyl or hexadecyl) as structure-directing agents. The precipitation of solid particles from a homogeneous water solution of sodium metasilicate and surfactant blend was achieved by lowering the pH due to the hydrolysis of ethyl acetate added. The molecular sieves were characterized by scanning as well as transmission electron microscopy, X-ray powder diffraction, and nitrogen adsorption using a proper nonlocal density functional theory approach for calculations of the textural parameters. All the prepared silicas were of MCM-41-type; they differ in the integral breadth of the pore size distribution curve and the presence of secondary mesopores. The best quality MCM-41 silica of spherical particle morphology was synthesized by using of optimized blend of hexadecyltrimethylammonium bromide and 1-methyl-3-octylimidazolium chloride. The results obtained showed that spherical particles are composed of domains of perfectly ordered hexagonal porous structure. Some samples prepared by using 1-alkyl-3-methylimidazolium salts featured a narrow pore size distribution. However, they contained a small volume of secondary mesopores.     

Click-chemistry for surface modification of monodisperse-macroporous particles

In this study, click chemistry was proposed as a tool for tuning the surface hydrophilicity of monodisperse-macroporous particles in micron-size range. The monodisperse-porous particles carrying hydrophobic or hydrophilic molecular brushes on their surfaces were obtained by the proposed modification. Hydrophilic poly(glycidyl methacrylate-co-ethylene dimethacrylate), poly(GMA-co-EDM) particles were hydrophobized by the covalent attachment of poly(octadecyl acrylate-co-propargyl acrylate), poly(ODA-co-PA) copolymer onto the particle surface via triazole formation by click chemistry. In the second part, Hydrophobic poly(4-chloromethylstyrene-co-divinylbenzene), poly(CMS-co-DVB) particles were hydrophilized by the covalent attachment of poly(vinyl alcohol), PVA onto their surface also via triazole formation by click chemistry. The presence of PVA and poly(ODA-co-PA) copolymer on the corresponding particles was shown by FTIR-DRS. After click-coupling reactions applied for both hydrophobic poly(CMS-co-DVB) and hydrophilic poly(GMA-co-EDM) particles, the marked changes in surface polarity were shown by contact angle measurements. Protein adsorption characteristics of plain and modified particles were investigated for both materials. In the isoelectric point of albumin, the non-specific albumin adsorption decreased from 225 to 80 mg/g by grafting PVA onto the poly(CMS-co-DVB) beads. On the other hand, the non-specific albumin adsorption onto the plain poly(GMA-co-EDM) beads increased from 50 to 400 mg/g by the covalent attachment of poly(ODA-co-PA) copolymer onto the bead-surface via click chemistry. The protein adsorption behavior was efficiently regulated by the covalent attachment of appropriate molecular brushes onto the surfaces of selected particles. The results indicated that "click chemistry" was an efficient tool for controlling the polarity of monodisperse-macroporous particles.     

Correlative studies on the fabrication of poly(styrene-methyl-methacrylate-acrylic acid) colloidal crystal films

This research describes a one-step procedure for monodispersed poly(styrene-methyl-methacrylate-acrylic acid colloidal spheres [P(St-MMA-AA)] via soap-seeded emulsion polymerization. The effects ofreaction conditions such as temperature, stirring speed, initiation concentration, e.t.c. were examined. The results obtained showed that the spheres average particle diameter decreased with increase in initiator concentration, the reaction temperature and stirring speed and increased with an increase in monomer concentrations. The particles show stable mechanical properties within the transition and heating temperatures of 111.9?°C and 388?°C respectively. Zeta-potential values ranging from ?31.8?mV to ?36.5?mV which is indicative of stable dispersion of colloidal particles were obtained for all the prepared latexes. The assembled colloidal latex had periodic structures with mainly hexagonal three-dimensional structures with multi-facet arrangements. The latex also shows spherical shape of monodispersed core-shell particles.     

Structural characteristics of activated carbons and ibuprofen adsorption affected by bovine serum albumin

Structural characteristics of a series of MAST carbons were studied using scanning electron microscopy images and the nitrogen adsorption isotherms analyzed with several models of pores and different adsorption equations. A developed model of pores as a mixture of gaps between spherical nanoparticles and slitlike pores was found appropriate for MAST carbons. Adsorption of ibuprofen [2-(4-isobutylphenyl)propionic acid] on activated carbons possessing different pore size distributions in protein-free and bovine serum albumin (BSA)-containing aqueous solutions reveals the importance of the contribution of mesopores to the total porosity of adsorbents. The influence of the mesoporosity increases when considering the removal of the drug from the protein-containing solution. Cellulose-coated microporous carbon Norit RBX adsorbs significantly smaller amounts of ibuprofen than uncoated micro/mesoporous MAST carbons whose adsorption capability increases with increasing mesoporosity and specific surface area, burnoff dependent variable. A similar effect of broad pores is observed on adsorption of fibrinogen on the same carbons. Analysis of the ibuprofen adsorption data using Langmuir and D'Arcy-Watt equations as the kernel of the Fredholm integral equation shows that the nonuniformity of ibuprofen adsorption complexes diminishes with the presence of BSA. This effect may be explained by a partial adsorption of ibuprofen onto protein molecules immobilized on carbon particles and blocking of a portion of narrow pores.     

Addition of polyglycol to old culture of Phanerochaete chrysosporium

Polyglycols increased lignin peroxidase activity in shaken cultures of Phanerochaete chrysosporium even when they were added to an old fungus (5 or 10 d after inoculation). The effects depended on the polyglycol mol wts (10(2)-10(6) Daltons) as well as on the backbone structure (i.e., poly[ethylene glycol], poly[butylene glycol], poly[propylene glycol]) and terminal groups (i.e., poly[ethylene glycol], poly[ethylene glycol] methyl ether, poly[ethylene glycol] dimethyl ether). The residual quantity of polyglycol in the biomass and in the culture filtrate also varied among different polyglycols. The polyglycols act after being adsorbed to the cell membrane exaggerating the asymmetry of the membrane environment. In old fungus, the incompatibility of polyglycols and glycans decreases the adsorption and the effect of high mol wt polyglycols.     

Application of anomalous small‐angle X‐ray scattering to spherical polyelectrolyte brushes

The analysis of spherical polyelectrolyte brushes by anomalous small‐angle X‐ray scattering (ASAXS) is considered. The particles under consideration consist of a solid poly(styrene) core onto which chains of poly(acrylic acid) are grafted. If Rubidium ions are chosen as counterions, ASAXS can be applied to the study of these systems because the absorption edge of Rb (15199.6eV) can be reached by synchrotron radiation. Here we discuss the results to be obtained by the application of ASAXS to spherical polyelectrolyte brushes.