Natural Tubular Halloysite as Drug Carrier: Effect of Organosilane Modification and Thermal Treatment

Naturally occurring tubular halloysite is a potential drug carrier because of the significant deposit, unique mesoscopic (2-50 nm) or even macroscopic (>50 nm) lumen, and excellent biocompatibility. The drugs loaded on halloysite exhibited slow release under the diffusion limitation by the halloysite nanotube. However, due to the weak interaction between halloysite and guest, the loading capacity of halloysite was relatively low. This drawback severely limits the application of halloysite as carrier in pharmaceutics. In this study, the performance of halloysite as carrier for ibuprofen (IBU) loading was investigated for the first time. The effects of 3-aminopropyltriethoxysilane (APTES) modification and thermal treatment of halloysite on the loading and release of IBU were also studied. The purified halloysites were heated at 120 ℃ and 400 ℃ (labeled as Hal/120 and Hal/400), and then modified with APTES (labeled as Hal/120-A and Hal/400-A). The loading of IBU was achieved by soaking method (labeled as IBU-Hal/120, IBU-Hal/400, IBU-Hal/120-A, and IBU-Hal/400-A.). The in vitro drug delivery assays were performed in phosphate buffer solution. IBU was loaded mainly into the lumen and partially on the external surface of halloysite. The order of IBU contents was as follows: IBU-Hal/400-A (14.8wt%) > IBU-Hal/120-A (12.7wt%) > IBU-Hal/400 (11.8wt%) > IBU-Hal/120 (11.7wt%). The IBU was initially anchored to the surface hydroxyl groups of halloysite by hydrogen bonding, followed by further bonding of IBU with the anchored IBU to form hydrogen-bonded aggregates. The APTES modification of halloysite promoted the loading of IBU by introducing a strong affinity through electrostatic attraction between the introduced aminopropyl groups of APTES and the carboxyl groups of IBU. Thermal treatment at 400°C did not destroy the tubular morphology or the crystal structure of halloysite and had little effect on IBU loading in unmodified halloysite. However, thermal treatment by reducing water content in halloysite restricted the grafting of APTES in the lumen space, and further increased IBU loading. All IBU-loaded samples exhibit a burst release with a following slow release. However, owing to the strong electrostatic attraction in modified samples, the burst release was much more suppressed and the release rate was also lower than that in unmodified ones. The in vitro release profiles of the IBU-loaded samples were well fitted with the modified Korsmeyer-Peppas model. The IBU release mechanism of the unmodified samples was Fickian diffusion; however it was non-Fickian diffusion for the modified samples. The findings are of significance for broadening the use of halloysite as carrier for drugs and other active molecules in the pharmaceutical, pesticides, and coating industries.     

埃洛石的命名、结构、形貌和卷曲机制

埃洛石作为一种典型的高岭石族矿物,大部分情况下呈现出管状形貌,近年来已被广泛用作缓释容器、催化剂载体、有机聚合物填充材料、储氢材料和纳米材料模板等,具有重要的应用价值。对埃洛石微观化学信息的研究,不仅有助于理解埃洛石地质成因、掌握埃洛石结构细节,还有助于提高埃洛石使用性能、拓宽其应用范围。本文针对埃洛石的结构、形貌和发生卷曲的机理等进行了详细介绍;此外,鉴于长期以来埃洛石名称的混乱状态,本文还对其命名历史进行必要综述。在此基础上,给出埃洛石的中文建议名称,提出目前结构研究中存在的一些问题,并对未来的研究方向进行了展望。     

云南西双版纳埃洛石特征研究

采用X射线衍射(XRD)、扫描电子显微镜(SEM)、傅里叶红外吸收光谱(FT-IR)、X荧光光谱分析(XRF)、电子探针,等现代测试手段,对西双版纳-2μm粒级埃洛石的矿物学特征进行了系统的研究。研究结果表明:该矿床中同时存在10?-埃洛石和7?-埃洛石,以10?-埃洛石为主。埃洛石管的平均长度为约1.25μm,平均外径约0.16μm,内径为15~40 nm,管状结构形态较好,具有天然纳米多孔晶体材料性质。加热后10?-埃洛石中结构水较容易脱除,导致10?-埃洛石转变为7?-埃洛石,但7?-埃洛石的结构水较难脱除,在400℃仍有残留。     

海泡石应用于调湿材料的研究

为寻找合适的湿度调节材料,本文对海泡石及海泡石复合样品进行了吸湿能力和放湿能力测试。与坡缕石比较,10g200目海泡石样品可以将10L密闭容器的湿度从70%降至4%,吸湿能力强于同样条件下的坡缕石。海泡石(10g)的吸、放湿能力经过3次吸、放湿实验后有所减弱,最后一次吸湿量达0.4g,放湿量达0.15g。实验还发现,30g海泡石和白水泥复合样品可以使10L容器内部的湿度稳定在40%～50%,因此,海泡石可以用作室内湿度调节的建筑材料。     

Experimental Study on Adsorption of Rare Earth Elements on Kaolinite and Halloysite

<正>1 Introduction The weathered crust rare earth deposits is one of the most significant rare earth deposits,which are mostly distributed in southern China,especially in the south of Jiangxi province(Chi et al.,2007).The compositions of these deposits,which are weathered from igneous rocks such as granite through biological,physical or chemical     

Identification and characterization of the encrusting materials in a coastal liquefied petroleum gas storage cavern

An examination was carried out of the encrusting materials on the seepage removal pumps in a bottom sump of an undersea liquefied petroleum gas (LPG) cavern. The studied cavern, constructed at 8 km off the western coast of Korea, facing the Yellow Sea, is at 130–150 m below the seabed. Since the first filling of the LPG into the cavern, it has suffered from the unexpected problem of a thick encrustation of unknown materials on the seepage removal pumps of the cavern. The XRD and XRF analyses revealed that the encrustation materials were mainly iron (hydro)oxides and carbonate mineral (aragonite). Based on the geological setting below the cavern site, it was inferred that iron oxides found in the Pleistocene sandy sediment and the Precambrian gneiss might be supplying ferrous iron to the cavern waters under an anaerobic condition, evidenced by low dissolved oxygen and negative redox potential in the cavern water. A significant change in the hydraulic condition near the pump intake and mixing the cavern water with oxic waters supplied through re-circulated seawater and terrestrial groundwater discharge, would precipitate the dissolved iron. Precipitation of the carbonate mineral is thought to have occurred due to over-saturation of calcium and bicarbonate, which may have resulted from the dissolution of cement grouting materials used during the undersea cavern construction and submarine groundwater discharge (SGD). This study reports the iron and carbonate precipitation in the man-made undersea cavern, which is affected by the surrounding hydrogeological condition and the SGD.     

Vein arrays as kinematic indicators in kinked anisotropic materials

Vein arrays associated with natural kink bands have been, even recently, used by some workers as kinematic markers to distinguish between the migration and the rotation models of kink band mechanics.In an outcrop of schistose meta-agglomerate, conjugate kinks and synthetic sinistral shears are associated with a component of sinistral slip along the foliation. Discordant scalariform vein arrays form in association with the shears, but not the kinks. Tension gash elements of the arrays form by combined layer-parallel slip and layer-parallel extension along the rotated schistosity. They are only kinematically significant at the scale of the length of the rotated segment anisotropy.Applying this analysis to kink bands elsewhere, it is concluded that discordant vein arrays are not diagnostic of the rotational kink band model, or of high resolved shear stress on kink boundaries.     

Arch in granular materials as a free surface problem

This paper discusses the formation of stable arches in frictional soils. A series of laboratory tests are performed to explore the formation of arches in granular materials, either cohesionless or with small apparent cohesion. By considering the stable soil arch as a stress‐free surface, the analysis in the framework of continuum mechanics reveals that such an arch can only form in cohesive frictional materials. The shape of the arch mainly depends on the material's friction angle, while the critical width of the arch is primarily dominated by cohesion. The formation of stable arches in cohesionless materials is interpreted by taking into account the discrete nature of the material, with the failure of the arch being considered as buckling of particle columns. It is shown that the width of stable arches in cohesionless materials is generally five to seven times of the particle size. Copyright © 2012 John Wiley & Sons, Ltd.     

Sterols as source indicators of organic materials in sediments

The sterol contents of plankton and sediment samples have been determined. Cholesterol, 22-dehydrocholesterol, brassicasterol, campesterol, 24-methylenecholesterol, stigmasterol, and β-sitosterol are the major sterols in these samples. Systematic variations have been observed in the compositions of the sterols from bay and Gulf of Mexico plankton and from sediments collected in the mouth of the Aransas River, Capano Bay, Aransas Bay, Corpus Christi Bay and the Gulf near Port Aransas. The concentration of cholesterol increases as the concentration of β-sitosterol decreases in the sample sequence of river inlet sediments-bay sediments-Gulf sediments-bay and Gulf plankton. Calculations based on either the cholesterol or the β-sitosterol contents of the sterol fractions of the fresh water sediments and the Gulf plankton and sediments suggest that 34% of the sterols in the Gulf sediments are derived from terrigenous sources.     

Geomechanical evaluation of Pliocene natural aggregates as pavement materials

Asphaltic roads and constructions in Egypt annually consume a huge amount of aggregates. The physical and geomechanical properties of these aggregates have controlled their performance in which they are used. All road pavements require the efficient use of locally available materials if economically constructed roads are to be built. More than 650 million m³ of fine and coarse aggregates are herein selected to be the tonnage of the present study. The studied Pliocene aggregates have smoothed grading curves and neither a deficiency nor excess of any one particle size, generally produce good mixtures with fewer voids between particles. The litho-particles of coarse aggregates are composed mainly of granites, gneisses, granodiorite, gabbro, and quartz particles. The sand equivalent value of fine aggregates varies from 95 to 97 %. The specific gravity values of the studied aggregates vary from 2.72 to 2.74 gm/cm³ for coarse aggregate and range from 2.51 to 2.54 gm/cm³ for fine aggregate. The Los Angles abrasion value varies from 19 to 24 %. Both coarse and fine aggregates meet the international standards which are suitable for usage as subbase and surface course aggregates, respectively.     

Experimental reduction of aqueous sulphate by hydrogen under hydrothermal conditions: Implication for the nuclear waste storage

Sulphate reduction by hydrogen, likely to occur in deep geological nuclear waste storage sites, was studied experimentally in a two-phase system (water + gas) at 250-300 °C and under 4-16 bars H₂ partial pressure in hydrothermal-vessels. The calculated activation energy is 131 kJ/mol and the half-life of aqueous sulphate in the presence of hydrogen and elemental sulphur ranges from 210,000 to 2.7 × 10⁹ years at respective temperatures of 90 °C, the thermal peak in the site and 25 °C, the ambient temperature far from the site. The features and rate of the sulphate reduction by H₂ are close to those established for TSR in oil fields. The experiments also show that the rate of sulphate reduction is not significantly affected in the H₂ pressure range of 4-16 bars and in the pH range of 2-5, whereas a strong increase is measured at pH below 2. We suggest that the condition for the reaction to occur is the speciation of sulphate dominated by non symmetric species ( at low pH), and we propose a three steps reaction, one for each intermediate-valence sulphur species, the first one requiring H₂S as electron donor rather than H₂. We distinguish two possible reaction pathways for the first step, depending on pH: reduction of sulphate into sulphur dioxide below pH 2 or into thiosulphate or sulphite + elemental sulphur in the pH range 2-5.     

Recharge characteristics of a phreatic aquifer as determined by storage accumulation

The cumulative storage accumulation curve (CSAC) is a tool for saturated-volume fluctuation (SVF) analysis of transient recharge to shallow phreatic aquifers discharging only to springs. The method assumes that little underflow or phreatic evapotranspiration occurs. The CSAC is a modified water-table hydrograph that distinguishes storage increase caused by recharge from loss due to springflow-induced recession. Required for the analysis are water-table fluctuations at a single representative location within the catchment of a single spring and either direct measurements or robust interpolations of springflows at different aquifer stages. The method employs empirical manipulation of head observations, varying spring catchment area to minimize CSAC water-level changes in late portions of long recessions. Results include volumetric estimates of recharge integrated over individual events and instantaneous rates of recharge to the water table, at the temporal resolution of the water-level sampling interval. The analysis may also yield physically realistic information on spring catchment and recharge focusing. In a test case in West Virginia, USA, recharge estimates by this technique were consistent with integrated springflow time series but greater than estimates based on potential evapotranspiration. Results give insight into dynamic recharge behavior over time as well as an indication of recharge catchment size. Electronic Publication     

Sedimentary humic acid and fulvic acid as fluorescent organic materials

Fluorescence and absorption spectra of sedimentary humic acid (HA) and fulvic acid (FA), with molecular weights ranging from < 10,000 to >300,000, were measured at 20°C and pH 8. The maximum excitation and emission wavelengths of HA were longer than those of FA, being independent of molecular weight. The excitation and emission maxima can be utilized to differentiate between sedimentary HA and FA. It is suggested that the fluorophors in HA are of a higher molecular weight aromatic groups than those in FA.Smaller molecules were found to have a greater fluorescence than larger ones for sedimentary humic substances and this phenomenon is similar to those obtained for humic substances of terrestrial origin. The absorption coefficient (1/g/cm) of HA decreased, while that of FA increased with the increase in molecular weight. It was shown that fluorescence intensity per weight concentration unit of HA increases and that of FA decreases with increasing absorption coefficient.     

A review of materials used as carrier agents in pesticide formulations

Development of environmentally-friendly pesticides for sustainable agriculture is a key focus in the agrochemical industry. Identifying novel active ingredients and improving the delivery system of a pesticide are the main challenges in developing new pesticides. Strategies for the control of delivery systems for slow and sustained release of agrochemicals are of great interest to environmental scientists. In this context, the selection of materials to be used as carrier agents in pesticide formulations is crucial. In recent years, the efficacy of several materials for agrochemical formulations has been evaluated by researchers. These materials have unique properties, such as being biodegradable and biocompatible, and having low toxicity and involving a simple preparation process. This review summarises recent applications of various materials in pesticide formulations. The application of the materials can effectively encapsulate or bind the pesticide’s active ingredients in the material’s matrix with a sustained release profile and slow mobility in soil. This review also discusses some issues and concerns that are faced in formulating pesticide products.     

固化疏浚淤泥做堤防填筑材料的试验研究

固化疏浚淤泥作为堤防填筑材料,既解决淤泥的处置,又可解决堤防建设中填土的缺乏。用灰渣胶凝材料（HAS）固化淤泥并测试固化淤泥土的主要物理力学性质,发现掺6 %灰渣胶凝材料固化后的淤泥土,在自然堆积28 d后的液塑限达到60 %,有机质含量降低到2 %,淤泥由原来的有机质高液限黏土（CHO）变成高液限粉质黏土（MH）,其28 d的无侧限抗压强度普遍大于1.4 MPa,凝聚力c≥100 kPa,内摩擦角?＞35°,渗透系数小于10-6 cm/s,远高于提防填筑材料的标准,表明灰渣胶凝材料固化改性淤泥成为堤防填土是可行的。     

Microstructure and Photocatalytic Decomposition of Methylene Blue by TiO2-Mounted Halloysite, a Natural Tubular Mineral

On the basis of analysis of structure and properties, halloysite, a natural tubular mineral, was developed for an environmental treatment. TiO2 was mounted into halloysite by using hydrolysis of tetrabutyl titanate at room temperature. The adsorption and photocatalytic performance of halloysite and TiO2-mounted halloysite have been examined in methylene blue aqueous solution in the dark and under ultraviolet ray irradiation, respectively. Their performance of adsorption and photodecomposition was evaluated from the adsorbed and degraded amounts of methylene blue （MB）. Due to the mixture of adsorption and photodecomposition, the concentration of MB, organic pollution, in water decreased rapidly with TiO2-mounted halloysite powder, which is a faster reaction than that with halloysite-only adsorption. This new use of halloysite is leading to many interesting applications in the decomposition and elimination of various pollutants in air and water.     

Spring and conduit sediments as storage reservoirs for heavy metals in karst aquifers

Sediment samples were collected from six springs draining the karst aquifer at Fort Campbell, Kentucky/Tennessee. These were analyzed by ICP-MS following an extraction procedure that separates the metals into exchangeable, carbonate, oxide, organic and residual fractions. Aluminum and iron are primarily present in the residual fraction while manganese may be dominantly in either the oxide or carbonate fraction. The redox-sensitive metals (Fe and Mn) have the greatest fractional distribution in the spring with the thickest sediments. Trace metals detected include Cr, Cd, Ni, Pb, and Zn in the range of a few to 200 mg/kg. In Beaver Spring, nickel is distributed between the exchangeable, carbonate and organic fractions, while in Gordon Spring, nickel is largely residual. Chromium is almost entirely associated with the organic fraction in Beaver Spring while it is largely residual in Gordon Spring.