Pore wall thickness and interpore influence on adsorption of alkanes in carbons using explicit pore models

In modeling of activated carbons, the pores are often assumed to be slit-shaped formed of a constant number of graphene layers. X-ray diffraction studies show that micropores are formed between stacks of different numbers of graphene layers. In this study, we investigate, through the grand canonical Monte Carlo method, the influence on the adsorbed alkanes densities of pore walls with different graphene layers thickness and the related interpore adsorbate interaction when the pore wall has only one graphene layer. All studies of thickness and interpore interaction to date were performed using the Steele 10-4-3 potential model. Instead of Steele model, we propose explicit models made up of graphene layers of discrete carbon atoms. We also investigated the sensitivity of the system to the cut-off and solid-fluid parameter. With our explicit model we found that the influence of the number of carbon layers is not significant for n>2 as previously observed by Steele model??DFT studies. The system was also insensitive to cut-off and well deep parameter variations. A new pore model with an extra dummy graphene wall was proposed to investigate the interpore interaction. The interpore interaction study with the alkanes series C1 to C4 shows that the retention capacity of heavier alkanes is the same whether for activated carbons with few layers (stronger interpore interaction) as for carbons with two or more layers (stronger solid-fluid interaction) assuming negligible surface mediation. The explicit models proposed can be successfully used in the elaboration of virtual porous carbon models to reproduce wall thickness and interpore adsorbate interactions phenomena.     

Novel patterns by focused ion beam guided anodization

Focused ion beam patterning is a powerful technique for guiding the growth of ordered hexagonal porous anodic alumina. This study shows that, with the guidance of the focused ion beam patterning, hexagonal porous anodic alumina with interpore distances from 200 to 425 nm can be fabricated at 140 V in 0.3 M phosphoric acid. When the interpore distance is increased to 500 nm, alternating diameter nanopore arrays are synthesized with the creation and growth of new small pores at the junctions of three large neighboring pores. Moreover, alternating diameter nanopore arrays in hexagonal arrangement are fabricated by focused ion beam patterning guided anodization. Interpore distance is an important parameter affecting the arrangement of alternating diameter nanopore arrays. Different types of novel patterns are obtained by designing different focused ion beam concave arrays. The fundamental understanding of the process is discussed.     

Moiré pattern nanopore and nanorod arrays by focused ion beam guided anodization and nanoimprint molding

Nanoporous anodic aluminum oxide has been intensively studied as templates in the fabrication of various nanomaterials. Most of the research focuses on highly ordered hexagonal nanopore arrangement with homogeneous area-specific pore density. Anodic aluminum oxide with alternating area-specific nanopore densities has seldom been addressed. In this study, focused ion beam patterned concave arrays created by overlapping two periodic patterns show the exceptional ability of guiding the subsequent anodization and fabricating porous anodic aluminum oxide with Moire? patterns, which have a wide range of interpore distances and area-specific pore densities. The periodicity of the Moire? patterns can be predicted by the interpore distance of the initial patterns and the rotation angle. The depth of the nanopores of these Moire? patterns is around 1 μm. Vertically aligned and high aspect ratio h-PDMS nanorod arrays with Moire? pattern arrangements have been successfully synthesized using the patterned porous anodic aluminum oxide as templates.     

Self-assembly of chiral molecular honeycomb networks on Au(111)

Self-assembly of the specifically designed 3-fold symmetric 1,3,5-trikis(4'-carboxylphenyl)-2,4,6-trikis(4'-tert-butylphenyl)-benzene molecule on a Au(111) surface is investigated by means of in situ ultrahigh vacuum scanning tunneling microscopy. A variety of chiral honeycomb networks with increasing interpore distance is observed. Experiments and force field calculations reveal that the formation of the two-dimensional hexagonal porous networks is driven by a balance of molecular close-packing within half-unit cells and cyclic hydrogen bonding dimerization between half-unit cells. The honeycomb networks are shown to be chiral owing to asymmetric molecular close-packing within the half-unit cells.     

Using paramagnetic particles as repulsive templates for the preparation of membranes of controlled porosity

Using mixtures of repulsive superparamagnetic polystyrene particles and a photopolymerizable organic liquid (trimethylolpropane trimethacrylate) that are applied to a water surface, it is possible to prepare porous membranes with controlled porosity. The particles were polarized by applying a magnetic field H perpendicular to the interface and spread out over the interface making use of the induced repulsive magnetic dipole interactions. As a consequence, the organic liquid in which the particles were embedded covered the water surface uniformly. Subsequent photo cross linking of the organic liquid and dissolution of the embedded particles gave rise to membranes whose porosities were controlled mainly by the chosen areas per particle. The spatial distribution of the pores and the deviation from a crystalline arrangement were characterized in terms of the 2D pair-correlation function and the mean nearest-neighbor interpore distance.     

The effect of anode surface area on nanoporous oxide formation during anodizing of low purity aluminum (AA1050 alloy)

Porous anodic alumina layers were obtained by a simple two-step anodization of low purity aluminum (99.5 % Al, AA1050 alloy) in a 0.3 M oxalic acid electrolyte at 45 V and 20 °C. The effect of anode surface area on structural features of nanoporous oxide and process of oxide formation was investigated. An ordered structure composed of nanostripes or nanopores was formed on the Al surface during electrochemical polishing in a mixture of perchloric acid and ethanol. This nanopattern is then replicated during the anodic oxide formation. It was found that the pore diameter, interpore distance, and porosity increase slightly with increasing surface area of the aluminum sample exposed to the anodizing electrolyte. On the other hand, a slight decrease in pore density and cell wall thickness was observed with increasing surface area of the sample. The detailed inspection of current density vs. time curves was also performed. The obtained results revealed that the higher surface area of the anode, the local current density minimum, was reached faster during first step of anodization and the increase in current density corresponding to the pore rearrangement process was observed earlier. Finally, a dense array of Pd nanowires (～90 nm in diameter) was synthesized by simple electrodeposition of metal inside the channels of through-hole nanoporous anodic alumina templates with relatively large surface areas (4 cm²).     

Synthesis, morphology, and magnetic characterization of iron oxide nanowires and nanotubes

We have explored the synthesis of iron oxide particles, tubes, and fibrils within the pores of nanoporous polycarbonate and alumina membranes. The membranes contain uniformly distributed cylindrical pores with monodispersed diameters (varying between 20 and 200 nm) and thicknesses of 6 and 60 microm, respectively. By hydrolysis and polymerization of iron salts, particles of different sizes and phases were formed in the pores, building iron oxide particle nanowires. Alternatively, by the sol-gel technique, using as reagents metalloorganic compounds, fibrils and tubes of different iron oxide phases were prepared. Structural and morphological investigations performed using scanning electron microscopy and transmission electron microscopy revealed ordered iron oxide particle wires, tubes, and fibrils formed inside the membrane nanopores. Magnetic characterization was accomplished with a vibrating sample magnetometer. Below the blocking temperature (T(B)), the magnetic behavior of the nanowires was governed by dipolar interaction between nearest-neighbor nanoparticles inside the pore, whereas the energy barrier, and therefore the T(B) value, was mainly governed by dipolar interaction between magnetic moments over larger (interpore) distances. As expected, crystalline iron oxide nanotubes exhibited magnetic perpendicular anisotropy due to their magnetocrystalline and shape anisotropy.     

Pushing the size limits in the replication of nanopores in anodized aluminum oxide via the layer-by-layer deposition of polyelectrolytes

We report on the successful replication of the smallest pores in anodized aluminum oxide (AAO) via the layer-by-layer (LBL) deposition of polyelectrolytes to date to yield free-standing, open nanotubes with inner and outer diameters (±2σ) down to 37 ± 4 and 52 ± 19 nm, respectively. This work is based on the fabrication of defined arrays of highly regular nanopores by anodic oxidation of aluminum. Pores with pore diameters between 53 ± 9 and 356 ± 14 nm and interpore distances between 110 ± 3 and 500 ± 17 nm were obtained using an optimized two-step anodization procedure. 3-(Ethoxydimethylsilyl)propylamine-coated pores were replicated by alternating LBL deposition of poly(styrenesulfonate) and poly(allylamine). The detrimental adsorption of polyelectrolyte on the top surface of the template that typically results in partial pore blocking was eliminated by controlling the surface energy of the top surface via deposition of an ultrathin gold layer. The thickness of the deposited LBL multilayer assembly at the pore orifice agreed to within the experimental error with the thicknesses measured by variable angle spectroscopic ellipsometry and atomic force microscopy (AFM) for layers assembled on flat substrates. The selective dissolution of the alumina template afforded free-standing, open polymer nanotubes that were stable without any cross-linking procedure. The nanotubes thus obtained possessed mean outer diameters as small as 52 nm, limited by the size of the AAO template.     

聚酯多孔支架降解液对骨髓基质干细胞活力和成骨分化的影响

通过室温模压/粒子浸出方法制备得到聚乙交酯丙交酯(PLGA)多孔支架,每个质量50 mg、孔径200～300μm、孔隙率略大于90%的PLGA85/15多孔支架在10 mL磷酸盐缓冲液(PBS)中37℃体外降解24周.降解液每周换一次,不同时间点的降解液被收集、并加入骨髓基质干细胞(MSC)的培养液或者成骨诱导液中,利用胞外乳酸脱氢酶含量检测、细胞死活染色、四唑盐检测、碱性磷酸酶染色和定量检测的方法考察降解液对MSC的活力和成骨分化能力的影响.实验结果表明,PLGA多孔支架材料在PBS中逐渐降解,其质量、尺寸、孔径、孔与孔的连通性、分子量有不同程度的降低;其降解液在本研究的实验条件下未发现对MSC有明显的细胞毒性,对MSC的活力、增殖以及成骨分化均无显著的负面影响.     

A novel controllable synthesis of silica nanotube arrays with ultraviolet photoluminescence

The synthesis of large-scale one-dimensional silica nanotube (SNT) arrays embedded in Si substrate is demonstrated by using the combination of AAO template mask and Ar ion milling technique. The geometry of the SNTs could be precisely controlled by the process parameters, which included that the SNT diameter and the interpore distance were controlled by AAO anodization voltage and H₃PO₄ pore widening time, while the length of SNT was controlled by ion milling time and AAO aspect ratio. Also, the SNT fabrication parameters could be related to their photoluminescence (PL) emitting properties, when anodized at 40 V, pore widening in H₃PO₄ acid for 70 min and ion milled for 5 min, a strong intensity and stable ultraviolet (UV) light of 3.25 eV (381 nm) emitted from the SNTs under the excitation of 266 nm laser, which could be assumed arising from twofold coordinated silicon lone pair centers in the oxygen deficiency SNTs. The present fabrication of SNT arrays presents a novel method for intensity and frequency adjustable ultraviolet optoelectronic devices.     

Effect of continuous magnetic field on the growth mechanism of nanoporous anodic alumina films on different substrates

The effects induced by an external homogeneous magnetic field on the oxide film growth on aluminum in aqueous solutions of oxalic and sulfuric acid and on surface morphology of the alumina films were studied. Aluminum films of 100 nm thickness were prepared by thermal evaporation on SiO₂/Si and glass-ceramic substrates. The pore diameter for oxalic acid alumina films on the SiO₂/Si substrate decreased by 0.8 nm, the interpore distance by 5.9 nm, and cell diameter by 6.9 nm if a magnetic field of 0.5 T was applied. When aluminum was anodized in sulfuric acid on the same substrate, the significant changes in parameters of porous structure of alumina, which were similar to the ones in oxalic acid, are firstly observed in stronger magnetic fields (of 0.7 T). On the basis of data obtained in this study and of previous investigation on the negative space charge and thermally activated defects in anodic alumina, we concluded that the intensity of the magnetic field is associated with energy of electron traps and that the changes of cell diameter characterize the trap concentration. The energy of electron traps in oxalic acid alumina films was proved to be smaller than the one in films formed in sulfuric acid, but the concentration of traps was of the same order of magnitude. When the substrate was replaced with the glass-ceramic one, the pore diameter in oxalic acid alumina films increased to ca. 17.6 nm.     

Properties of a new alkaline proteinase from Aspergillus niger

A. niger LCF 9 synthesizes a new aspergillopeptidase of potential interest in therapeutics. The properties and operating range of the enzyme were determined. It is a semi-alkaline aspergillopeptidase (EC 3.4.23.4) with one endopeptidase activity. Its pI is 4.10, its molecular weight is 21000 Da and its A1%(1 cm) at 280 nm is 9.75. It rapidly hydrolyzes casein and hemoglobin. Its optimal pH is 7.8 and optimal temperature is 45 degrees C. It is thermally labile above 40 degrees C but can be stabilized by adding calcium ions. It is inhibited by phenylmethylsulfonyl fluoride (PMSF), by ethylenediaminetetraacetic acid (EDTA) and by certain metals ions, e.g. copper, manganese and cobalt ions. It has no dipeptidase or tripeptidase activity and its esterase activity is weak. It has a high collagenase activity and is to our knowledge the only aspergillopeptidase that is active towards benzoyl-arginine p-nitroanilide (BAPNA).     

Some thermodynamic peculiarities of the nonexchange sorption of phenylalanine on dissimilar anion exchangers

It is shown that the nonexchange sorption of phenylalanine on dissimilar anion exchangers occurs by the same mechanism, determined by the structure of the amino acid, while the absorbed amount of substance depends on the sorbent structure. It is established that the micelle formation and the phenylalanineanion exchanger sorption equilibrium depend on the amount and nature of functional groups in anion exchangers. It is shown that, in the systems under investigation, the nonexchange sorption constant is determined by the constant of phenylalanine micelle formation.     

Piperidone synthesis using amino acid: A promising scope for green chemistry

Piperidone is a family of organic chemicals characterized by a 6-carbon ring substituted with nitrogen and a double-bonded oxygen atom. Piperidones are named by the location of the nitrogen or amine group on the ring. It differs from piperidine by the presence of oxygen molecule (from ketone). It is used in pharmaceutical companies and chemical manufacturers as intermediates having anti microbial activity. It is usually synthesized using ammonia both in laboratory and industry. In present study, amino acid namely aspartic acid is used instead of ammonia. The amino acid incorporated piperidones is purified and analyzed using NMR spectroscopy. It has antimicrobial activity against Pseudomonas aeruginosa and Salmonella aboni.     

Electrochemical synthesis of substituted trialkyl phosphates

The process of synthesis of tryalkyl phosphates, i.e., derivatives of methanol, butanol, and diethylene glycol, by anodic oxidation of dimethyl phosphite in the corresponding alcohol is studied. It is found that three alkyl phosphates corresponding to the three possible combinations of substituents bound to phosphorus in phosphate are formed. It is established that the cause for formation of two of the three oxidation products is reesterification of the initial dimethyl phosphite by the alcohol in the course of electrolysis. It is assumed that the process of reesterification is catalyzed by the acid formed in the anode layer.     

过氧化苯甲酰的光敏电荷转移分解反应及引发甲基丙烯酸甲酯的聚合

过氧化苯甲酰(BPO)的光诱导分解曾为许多工作者所注意。Walling和Gibian认为:以二苯酮为敏化剂时,BPO的敏化光解是通过三重态的能量转移过程。Encinas和Lissi则认为敏化是通过单重激发态使激发能转移至过氧化物基态的热振动态,从而导致过氧化物的分解。Tokumarur是最早提出过氧化苯甲酰光敏化诱导分解过程中存在着激基复合物(Exciplex)的可能性。最近他们又进一步研究以BPO为猝灭剂去猝     

On chemical reactions in the laser-induced breakdown of a liquid

It is shown experimentally that a laser-induced breakdown of a liquid is accompanied by chemical reactions initiated by radicals and excited species formed in the spark. It is found that, in water, the laser-induced breakdown is accompanied by the dissociation of water and dissolved nitrogen molecules with the formation of HNO₂ and HNO₃, while, in a FeSO₄ aqueous solution, by the Fe²⁺ → Fe³⁺ oxidation reaction. It is assumed that the mechanism of the process is analogous to that of the action of ionizing radiations and the chemical action of ultrasonically induced cavitation (it is proposed that this mechanism of chemical action of a laser-induced spark proposed be termed indirect). Energy yields of these reactions are found to be of the same order of magnitude as for sonochemical redox reactions. It is shown that the laser-induced breakdown of an aqueous solution of maleic acid is accompanied by its stereoisomerization into fumaric acid, a process catalyzed by small amounts of an alkyl bromide. It is established that, for the formation of fumaric acid in a laser-induced spark, the energy yield is about five orders of magnitude higher than that typical of the above-mentioned redox reactions in the laser-induced spark.     

通过等离子体表面处理提高聚乙炔稳定性

用等离子体方法对聚乙炔膜进行表面处理发现,其碘掺杂室温电导率与未处理的PA膜相当,但电导在空气中的稳定性及膜自身的抗氧化能力都有了较大提高。ESCA谱证实了在空气等离子体处理后的PA膜表面上接入了O和N原子。另外,IR光谱结果也表明,随着等离子体处理功率的增加,PA膜反式食量逐渐增加,顺式含量相应减少。     

Concentration dependence of the structure of aqueous solutions of lutetium nitrate according to X-ray diffraction

Aqueous solutions of lutetium nitrate over a wide range of concentrations are studied by X-ray diffraction under standard temperature and pressure. The low-angle peaks in experimental scattering intensity curves are interpreted. It is shown that the structure of these solutions can be of two types. It is found that a saturated solution and solutions concentrated to a molar ratio of 1: 20 have a quasi-crystalline structure resulting from interionic interactions. It is determined that dilute solutions form a water-like structure characterized by a tetrahedral network of hydrogen bonds between the water molecules. It is found that low-angle peaks also appear in the intensity curves of dilute solutions; this proves that the so-called “long-range” order is preserved in these solutions. It is revealed that in all the studied systems, the contributions to the total scattering pattern that are responsible for the occurrence of pre-peaks are intercationic interactions.     

Fullerene-containing phases obtained from aqueous dispersions of carbon nanoparticles

The hydration of fullerenes and shungite carbon nanoclusters in aqueous dispersions at various carbon concentrations is studied on frozen samples by EPR with spin probes. It is found that, for stable dispersions of both substances (at carbon concentrations of 0.1 mg/ml), the probe rotation frequency versus 1/T dependences exhibit a plateau in the range 243–257 K, which is probably associated with the peculiarities of freezing of water localized near hydrophobic structures of carbon nanoclusters. Solid phases isolated from supersaturated aqueous dispersions of fullerenes and shungites by slow evaporation of water at temperatures higher than 0°C are examines by electron diffraction and electron microscopy. It is established that obtained films of fullerenes contain at least two phases: fullerite with a face-centered cubic lattice and a phase similar in interplanar spacing and radically different in distribution of intensities of diffraction peaks. It is concluded that this phase is formed by the interaction of fullerenes and water (an analogous phase is found in shungite carbon films). It is found that the morphology of the new crystal phase is characterized by globules of size 20 to 70 nm, for fullerenes, and 10 to 400 nm for shungites. It is established that processes of crystallization of fullerites and fullerene-containing phases are very sensitive to temperature: a decrease in the temperature (within the range from 40 to 1°C) is accompanied by an increase in the new phase content.