Comparison of DOPA and DPPA liposome templates for the synthesis of calcium phosphate nanoshells

The aim of this paper is to synthesise calcium phosphate (CaP) nanoshells by controlling their particle size and shape using negatively charged liposomes (1,2 dioleoyl-sn-glycero-3 phosphate sodium salt (DOPA) and 1,2-dipalmitoyl-sn-glycero-3-phosphate sodium salt (DPPA)) as a template. The morphology, particle size, size distribution and zeta potential properties of DOPA and DPPA liposome templates were determined. The results showed that both DOPA and DPPA formed spherical nanoshell structures to be used as templates for the synthesis of CaP nanoshells. By using the DOPA template, spherical CaPs structures with a mean particle size of 197.5 ± 5.8 nm were successfully formed. In contrast, needle or irregularly shaped CaP particles were observed when using the DPPA template.     

Synthesis of mesoporous alumina by using a cost-effective template

A salt of stearic acid, i.e., magnesium stearate [(C₁₇H₃₅COO)₂Mg], can be used as a chemical template for the formation of mesoporous alumina, and is a less expensive reagent than stearic acid. Mesoporous alumina prepared using this cost-effective surfactant shows similar pore properties with respect to pore size (3.5 nm) and surface area (above 300 m²Vg) to that prepared using stearic acid. In addition, textural porosity, arising from non-crystalline intraaggregate voids and spaces, was effectively removed by the addition of magnesium nitrate. The entire transformation from aluminum hydroxide to active alumina was performed at 550 °C, and the crystallinity of the product was confirmed by powder XRD analysis.²⁷A1 MAS NMR result shows the phase of mesoporous alumina is the γ-alumina form.     

有序介孔磷酸锆的研究进展

简要阐述了磷酸锆材料的特点和应用发展现状,重点探索了有序介孔磷酸锆的制备方法及表征技术,对于磷酸锆材料研究及制备中存在的问题进行了归纳。     

Highly dispersed zinc phosphate microdomains in mesoporous silica

In situ immobilization of crystalline zinc phosphate nuclei in the mesoporous silica material resulted in a highly ordered 2D-hexagonal mesoporous material with evenly dispersed crystalline NaZnPO₄ microdomains in its matrix using the self-assembly of cationic surfactant under hydrothermal synthesis condition. Four samples with different Si:Zn:P:Na mole ratios have been prepared. X-ray diffraction (XRD) patterns of the as-synthesized as well as template-free samples indicated the presence of mesophase in each case. N₂ adsorption data indicated mesoporosity in the samples together with the existence of crystalline NaZnPO₄ phase for the materials synthesized with Si/Zn mole ratio 5-12. ²⁹Si MAS NMR results showed high value of the Q⁴/Q³ ratio in these materials suggesting highly crosslinked structure.     

Inorganic cements for biomedical application: calcium phosphate,calcium sulphate and calcium silicate

Inorganic cements have found utility in tissue replacement since the late nineteenth century, one of the first examples being calcium sulphates in the augmentation of bone defects. In the intervening period of time countless formulations of calcium phosphate, sulphate and silicate cement have been researched and as a result, many are now commercially available for a variety of biomedical applications. This review summarises the applications, formulations, advantages and drawbacks of such inorganic cements, suggesting future work that will drive progress in this area into the future of biomaterials research.     

Soluble phosphate salts as setting aids for premixed calcium phosphate bone cement pastes

Recently, premixed calcium phosphate cement pastes have been proposed as biomaterials for bone tissue repair and regeneration. Use of premixed pastes saves the time and removes an extra step during a medical operation. α-Tricalcium phosphate (α-TCP) based cements set to form calcium deficient hydroxyapatite which has a moderate bioresorbtion speed. α-TCP cements require a setting aid, usually a sodium or potassium phosphate salt, to speed up the setting process. Within the current research we investigated which setting aid has significant advantage, if α-TCP is used in form of non-aqueous premixed paste. This approach offers the application of simple ingredients to produce a premixed calcium phosphate cement. The following properties of cement formulations were evaluated: cohesion, phase composition, microstructure, pH value of the liquid surrounding the cement, and compressive strength.Compositions using mixture of basic and acidic potassium phosphate salts (KH₂PO₄ and K₂HPO₄) in sufficient amounts give the best overall results (adequate cohesion and pH of the surrounding liquid, hydrolysis of starting materials within 48 h, and compressive strength of 12 ± 3 MPa). Cement prepared with basic sodium phosphate salt (Na₂HPO₄) as setting aid had considerably higher compressive strength 22 ± 1 MPa, but the pH of the surrounding liquid was basic (9.0).     

Synthesis of weakly crystallized hydroxyapatite with Zn substitution and its effect on the calcium phosphate and calcium sulfate cements

Zn is an essential trace element in the normal growth and loading Zn into biomaterials for biomedical applications has always been a hot topic due to its immune regulation. The preparation and characterization of Zn-substituted weakly crystallized hydroxyapatite (WCH) are studied in this work, and Zn-substituted WCH was added to calcium phosphate and calcium sulfate cements (CPC and CSC) to address the effect of Zn²⁺ on the hydration crystallization behavior of calcium phosphate and calcium sulfate. Our results demonstrate that Zn²⁺ will inhibit the transformation of α-TCP to HA during the hydration reaction of CPC. And the adding of Zn²⁺ in CSC changed the crystallization morphology of calcium sulfate. The regulation of Zn on the crystallization behavior of calcium phosphate and calcium sulfate resulted in the different in vitro degradation behaviors of CPC and CSC. With the purpose of improving the biological effects of materials, the polarization of Zn²⁺ released from cements on macrophages was also characterized in this work, and the results showed that appropriate concentrations of Zn²⁺ can inhibit inflammation after stimulating RAW264.7 cells for an appropriate period of time. The presented results may be useful guidelines for the preparation and design of composite bone cement with specific Zn content.     

Eggshell derived mesoporous biphasic calcium phosphate for biomedical applications using rapid thermal processing

Biphasic calcium phosphate (BCP) has received much interest for making various bone substitutes since its physicochemical properties can be easily tailored by tuning its phase composition. Due to high temperature processing, it is hard to prepare BCP with nanoscale characteristics. In the present study, we have made an attempt to optimize the heat treatment parameters for the synthesis of BCP with nanoscale characteristics from eggshell derived hydroxyapatite (HA) through rapid thermal processing (RTP). To accomplish this, eggshell derived HA was prepared by wet precipitation method and subjected to RTP at 750°C and 1150°C for 3 and 10 minutes. For comparison we have also studied conventional calcination at 750°C and 1150°C for 3 hours. XRD, FTIR, SEM, EDX, HRTEM, and BET analyses were used to understand the effect of RTP and conventional calcination on eggshell derived HA. Our results indicate that eggshell derived HA on RTP at 1150°C for 3 minutes and 10 minutes can offer nanoscale BCP with good dissolution, bioactivity, cytocompatibility, and mesoporous nature. Hence, RTP can be a potential method to prepare BCP with nanoscale features for biomedical applications.     

Synthesis and electronic property of platinum nanowire and nanoparticle in mesoporous silica template

Platinum nanowires and nanoparticles were selectively synthesized in mesoporous silicas FSM-16 and HMM-1. The nanowires are 3 nm in diameter and several hundred nm to μm in length with high crystallinity. Pt nanowires and nanoparticles can be isolated by dissolving silica matrix with HF. The Pt wires extracted from organosilica HMM-1 have a nanonecklace structure, while the wires from siliceous FSM-16 have a nanorod structure. The extracted Pt nanoparticles (3 nm in size) on HOPG show the Coulomb staircase phenomena in STM/STS analysis. The mechanism for formation of the Pt nanowires is based on the migration of Pt ions in the mesoporous channels.     

Preparation and characterization of single phase,biphasic and triphasic calcium phosphate whisker-like fibers by homogenous precipitation using urea

Whisker-like calcium phosphate fibers were prepared by a homogenous precipitation method under refluxing conditions in solutions with a Ca/P molar ratio of 1.67 at 90 °C and pH 3.0 using urea as additive. The precipitates were characterized by XRD, FTIR, SEM, and FE-SEM. The ICP spectroscopy and elemental analyzer were used to determine Ca/P ratio and carbonate content of products, respectively. The results indicate that the morphology and structural characteristics of the precipitates depend on the urea concentration and reaction time. Whisker-like biphasic monetite/hydroxyapatite (HA) fibers with a mean length of 60 µm and a mean width of 1.0 µm were obtained with the use of a low concentration of urea. Calcination of the biphasic calcium phosphate at 800 °C led to the formation of a triphasic mixture of HA/whitlockite (β-TCP)/calcium pyrophosphate (CPP) with a whisker-like morphology. The use of a higher concentration of urea was caused to form a mixed morphology of spherulites/whisker-like fibers consisting of octacalcium phosphate (OCP) and HA phases. When the reaction time was increased to 10 days, both the above biphasic calcium phosphates transformed to a single phase HA which its morphology and growth pattern were similar to those of a whisker, according to FE-SEM images. The HA whiskers produced by a lower amount of urea had a lower carbonate content compared to those obtained using a higher urea concentration.     

Solvent-free infiltration method for mesoporous SnO2 using mesoporous silica templates

Mesoporous tin oxide (SnO₂) materials, exhibiting high surface areas, crystalline frameworks and various mesostructures, were successfully obtained by a facile solvent-free infiltration method from mesoporous silica templates. Various kinds of mesoporous silica materials, such as KIT-6 (bicontinuous 3-D cubic, Ia3d), SBA-15 (2-D hexagonal, p6mm), SBA-16 (3-D cubic with cage-like pores, Im3m) and spherical mesoporous silica (disordered), were utilized as the hard templates. Tin precursor (SnCl₂ · 2H₂O, m.p. 310–311 K) was infiltrated spontaneously within the mesopores of silica templates by melting the precursor at 353 K without using any solvent. The heat-treatment of SnCl₂-infiltrated composite materials at 973 K under static air conditions and subsequent removal of silica templates by using HF result in the successful preparation of mesoporous SnO₂ materials. The mesostructures as well as the morphologies of mesoporous SnO₂ materials thus obtained were very similar with those of the mesoporous silica templates. The mesoporous SnO₂ materials exhibit high surface areas of 84–121 m²/g as well as high pore volumes in the range of 0.22–0.35 cm³/g. The present solvent-free infiltration method is believed to be a simple and facile way for the preparation of mesoporous materials via nano-replication from mesoporous silica templates.     

Template synthesis of large pore ordered mesoporous carbon

Nanocast carbon (NCC-1) with large pores and ordered structure was synthesized via a nanocasting process using aluminum-containing SBA-15 as template and furfuryl alcohol (FA) as carbon precursor. This carbon has several interesting features, such as two steps with distinguished hystereses in the nitrogen sorption isotherm, high surface area of 2000 m²/g and large pore volumes of 3.0 cm³/g. It was found that the key factors in the synthesis of such carbons are the aging temperature of the SBA-15 template, the concentration of furfuryl alcohol (dissolved in trimethylbenzene), and the carbonization temperature. The optimal conditions for materials with high surface area and pore volumes are SBA-15 starting materials aged at 140 °C, 25 vol% of FA solution and 850–1100 °C carbonization temperatures. Moreover, it has been demonstrated that such nanocast carbon can be synthesized in a more facile way than previously reported. Purely siliceous SBA-15 without the need of Al³⁺-incorporation can be directly used as template. In this case, the polymerization catalyst—oxalic acid and FA were simultaneously introduced into the pore space of SBA-15.     

Synthesis and characterization of hybrid nano-crystallites inside self-ordered mesoporous carbon

The design and construction of nano-crystallites inside ordered mesoporous carbon is of great interest for potential applications in many fields. One of the main challenges is how to control hybrid nano-crystallites formed inside the pores. We describe a synthesis strategy of impregnation/hydrothermal method for incorporation of hybrid nano-crystallites Ru_0.3Cr_0.7O₂ inside CMK-3 with the average size of the nano-crystallites around 2.8–3.05 nm. The texture/structures of the resultant materials have been characterized by X-ray diffraction, transmission electron microscope, and nitrogen adsorption/desorption measurements. No nano-crystallites are observed to be generated on the external surface of CMK-3. The resultant material exhibits a high specific capacitance of approximately 226 F g⁻¹. This approach is expected to be applied to other hybrid metals oxides synthesized inside CMK-3 with specific structures and properties. Furthermore, it provides a versatile route for expanding the application of ordered mesoporous carbon with diverse pore arrangements.     

Synthesis,characterization, and applications of organic-inorganic hybrid mesoporous silica

Organic-inorganic hybrid mesoporous materials composed of homogeneously distributed ethane group in a silica framework were prepared by using 1,2 bis(trimethoxysilyl) ethane (BTME) as a precursor and alkyltrimethylammoniumchloride or -bromide surfactant as a structure directing agent with or without the presence of a swelling agent, mesitylene. Characterization of the materials was performed by XRD, TEM/SEM,^29Si-/^13C-solid state NMR, and N₂-adsorption. Testing of the hybrid material as a reversed phase HPLC column stationary phase after C18 surfacefunctionalization demonstrated a promising result, which closely approaches the performance of a commercial product. Mn-salen complex tethering on the hybrid material produced a catalyst with somewhat enhanced performance in liquid phase etherification with tert-butyl hydroperoxide as oxidant. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Synthesis of mesoporous MOR materials by varying temperature crystallizations and combining ternary organic templates

An approach, which involved perturbations of synthesis conditions in crystallization temperature and organic template composition, has been proposed for derivation of mesopores from bulk structural defects formed in mordenite (MOR) phases, based on the character of intrinsic crystal defects and tensional distortions of two compressed 8-membered rings in MOR framework. Consequently, hierarchically porous materials with MOR structures were prepared by varying temperature synthesis and using ternary organic micelles templates. The synthesized materials were characterized by powder X-ray diffraction, nitrogen adsorption at 77 K and transmission electron microscopy. These crystalline materials combined the advantages of both mordenites with the micropore system and mesoporous materials by featuring an additional intracrystalline mesopore system in MOR single crystals, resulting in a hierarchical pore distribution in range of 1.7-80.0 nm together with the significant specific surface areas. In particular, individual crystal morphologies of typical mesoporous MOR materials showed the defect-rich structures responding essentially to the mesoporosity; the mesoporous materials were substantiated matchable well to normal mordenites in acid capacity and acid strength distribution. Furthermore, several factors acting on intracrystalline mesopore formation were elucidated for explicating the perturbation synthesis approach, and whole reaction routes for synthesizing different solid products under related crystallization conditions were summarized coupling with a demonstration of part TEM micrographs. The overall results suggested that the investigative approach of perturbation imposed on crystal growth provides an alternative route for direct hydrothermal synthesis of mesoporous zeolite materials and implied that bulk structural defects within single crystals lead to the formation of intracrystalline mesopores in various sizes.     

Performance of templated mesoporous carbons in supercapacitors

By analogy with other types of carbons, templated mesoporous carbons (TMCs) can be used as supercapacitors. Their contribution arises essentially from the double layer capacity formed on their surface, which corresponds to 0.14 F m⁻² in aqueous electrolytes such as H₂SO₄ and KOH and 0.06 F m⁻² for the aprotic medium (C₂H₅)₄NBF₄ in CH₃CN. In the case of a series of 27 TMCs, it appears that the effective surface area determined by independent techniques can be as high as 1500-1600 m² g⁻¹, and therefore exceeds the value obtained for many activated carbons (typically 900-1300 m² g⁻¹). On the other hand, the relatively low amount of surface oxygen in the present TMCs, as opposed to activated carbons, reduces the contribution of pseudo-capacitance effects and limits the gravimetric capacitance to 200-220 F g⁻¹ for aqueous electrolytes. In the case of non-aqueous electrolyte, it rarely exceeds 100 F g⁻¹.It is also shown that the average mesopore diameter of these TMCs does not improve significantly the ionic mobility compared with typical activated carbons of pore-widths above 1.0-1.3 nm.This study suggests that activated carbons remain the more promising candidates for supercapacitors with high performances.     

Improving mechanical properties of porous calcium phosphate scaffolds by constructing elongated gyroid structures using digital light processing

The present study reports the manufacturing of a novel type of porous calcium phosphate scaffolds with elongated gyroid structures using digital light processing (DLP), in order to offer significantly enhanced mechanical properties. In particular, solid camphor was employed as the diluent, in order to offer sufficiently low viscosity at high solid loading for conventional layer-by-layer DLP process. Four types of porous CaP scaffolds with different percent elongation (%EL = 0, 20, 40, and 60) were manufactured, and their porous structures and mechanical properties were characterized. All porous CaP scaffolds showed that CaP walls were elongated along the z-direction, while the degree of pore elongation increased with an increase in the designed %EL. Owing to the use of controlled processing parameters, such as layer thickness and exposure time for layer-by-layer photocuring process, and carefully designed debinding process, the photocured layers could be completely bonded together with high densification after sintering at 1,200 °C for 3 h. Such elongation of a gyroid structure offered significantly enhanced mechanical properties ? compressive strengths of 4.33 ± 0.26 MPa and 11.51 ± 1.75 MPa were obtained for the porous CaP scaffold with the %EL of 0 and 60, respectively.     

Computer simulation of proteins adsorption on hydroxyapatite surfaces with calcium phosphate ions

Protein adsorption plays a key role in determining the biological properties of calcium phosphate biomaterials. Calcium (Ca) and phosphate (P) ions are involved in the protein adsorption process and influence the protein adsorption behaviors. In this study, the proteins adsorption on hydroxyapatite (HA) (001), (100), (110), (010) surfaces with Ca, P ions in solution were investigated by Molecular Dynamics (MD) simulation. The results reveal that basic proteins were more favorable to adsorb on HA surface than acidic proteins. HA (110) surface absorbed more acidic proteins than HA (001) and (100). HA (010) surface adsorbed more basic protein. Basic residues play a more important role than acidic residues in the adsorption process, as the basic residues have shown higher absorption energy than acidic residues, and they were more likely to adsorb on HA surfaces than to bind P ions in solution. Most of the active sites of protein, especially for acidic residues, are prefer to interact with HA surface through water molecules. Basic residues are more likely to adsorb onto HA surfaces directly. The presence of Ca, P ions in solution can influence the adsorption behaviors of protein. The formation of Ca, P ion cluster may lead to desorption of proteins. And they can compete with water molecules to bond to HA surfaces, acting as a bridge of protein interacting with HA surfaces instead of water-bridge. This Ca, P ions bridge connection make the adsorption energy of protein weakened. The results of this study provided new information at atomic/molecular level to further interpret the mechanism of protein adsorption on calcium phosphate surfaces with Ca, P ions. It is also helpful for designing new calcium phosphate biomaterials with specific surface properties to adsorb target protein for biomedical applications.     

Synthesis and characterization of a series of mesoporous nanocrystalline lanthanides phosphate

A series of lanthanide (LA) phosphate were prepared by using N-(2-hydroxyethyl) ethylenediane-N,N′,N′-triacetic acid (H₃hedtra) as a chelating agent. The obtained samples were characterized by using X-ray diffraction (XRD), nitrogen adsorption-desorption isotherm, thermal analysis (TG-DTA), transmission electron microscope (TEM) and TPD-ammonia desorption. The results showed that samples prepared through chelating agent route possessed smaller particle size which led to higher specific surface area with increased acidic sites compared with the reference samples prepared free of H₃hedtra. It was also found that the acidic strength increased gradually from the light lanthanide phosphate to heavy lanthanide phosphate. Besides, pore size of the samples could be controlled by altering the mole ratio of the lanthanide(LA): H₃hedtra. Pore size distribution of the samples became narrower through synthesis in the presence of H₃hedtra. The precursor sol complex was investigated by FTIR and XRD and mesopore formation mechanism had been discussed.     

无水条件下导向剂法合成介孔磷酸铝

首次用微孔APO-5导向剂作为合成介孔磷酸铝的磷源铝源，将其引入到介孔磷酸铝的合成中，在无水体系中以正十八胺为模板剂，合成了具有弱酸中心的微观有序度较好介孔磷酸铝材料。材料在500℃下焙烧10h其介孔结构仍然保持，且酸性表征发现其有分布很窄的弱酸中心，说明其具有相对较好的短程有序性，很好的潜在的弱酸催化性。