Author's Accepted Manuscript

Synthesis of mesoporous nano-

hydroxyapatite by using zwitterions surfac-
tant
Walid Amer, Karima Abdelouahdi, Hugo Ro-
nald Ramananarivo, Mohamed Zahouily, Aziz
Fihri, Yannick Coppel, Rajender S. Varma,
Abderrahim Solhy

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PII: S0167-577X(13)00751-9
DOI: http://dx.doi.org/10.1016/j.matlet.2013.05.103
Reference: MLBLUE15345

To appear in: Materials Letters

Received date: 12 February 2013

Revised date: 7 May 2013
Accepted date: 20 May 2013

Cite this article as: Walid Amer, Karima Abdelouahdi, Hugo Ronald
Ramananarivo, Mohamed Zahouily, Aziz Fihri, Yannick Coppel, Rajender S.
Varma, Abderrahim Solhy, Synthesis of mesoporous nano-hydroxyapatite by
using zwitterions surfactant, Materials Letters, http://dx.doi.org/10.1016/j.mat-
let.2013.05.103

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 Synthesis of mesoporous nano-hydroxyapatite by using
zwitterions surfactant

Walid Amera,b, Karima Abdelouahdi c, Hugo Ronald Ramananarivoa,b, Mohamed Zahouilya,d,

Aziz Fihria, Yannick Coppele,f, Rajender S. Varmag, Abderrahim Solhya,*

a
MAScIRFoundation, VARENA Center, Rabat Design, Rue Mohamed El Jazouli, Madinat El Irfane 10100-
Rabat, Morocco.
b
Faculté des Sciences, Université Mohamed V-Agdal, 4 Avenue Ibn Battouta, B.P. 1014-Rabat, Morocco.
c
Centre National pour la Recherche Scientifique et Technique (CNRST), Division UATRS, Angle Allal
Fassi/FAR, B.P.8027, Hay Riad, 10000-Rabat, Morocco.
d
Laboratoire de Catalyse, Chimiométrie et Environnement, URAC 24, Faculté des Sciences et Techniques,
Université Hassan II, Mohammedia B. P. 146, 20650, Morocco.
e
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP 44099, F-31077 Toulouse
Cedex 4, France.
f
Université de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4, France.
g
U. S. Environmental Protection Agency. National Risk Management Research Laboratory. Sustainable
Technology Division. 26 West Martin Luther King Drive, MS 443. Cincinnati, Ohio 45268, USA.

Abstract
Mesoporous nano-hydroxyapatite (mn-HAP) was successfully synthesized via a novel

micelle-templating method using lauryl dimethylaminoacetic acid as zwitterionic surfactant.

The systematic use of such a surfactant in combination with microwave energy input enables

the precise control of pore size in a narrow-size distribution range (36 nm). The comparison

of the specific surfaces area of dried and calcined mn-HAP (87 and 55 m2g-1) illustrates the

fundamental role of zwitterionic surfactant in the synthesis of mn-HAP. The controlled growth

of hydroxyapatite is confirmed by means of thermogravimetric analyses (TGA), Fourier

transform infrared (FT-IR), Raman spectroscopy, powder x-ray diffraction (XRD), solid-state

NMR, N2 adsorption-desorption measurements (BET), and transmission electron microscopy

(TEM) techniques.

Keywords: Nano-hydroxyapatite, Mesoporous Structure, Sol-Gel, Zwitterionic Surfactant,

Microwave Irradiation.

                                                            
*
Corresponding author.Fax: +212 530279827.
Email address: [email protected] (A. Solhy).
1. Introduction

Since their discovery in the early 1990s, soft templating approaches have attracted

tremendous interest for the synthesis of many mesoporous and nanostructured materials [1-3].

This strategy opened the door for a large variety of materials featuring a narrow pore size

distribution and regular 2D or 3D arranged pore structures [4-5].

Synthesis of mesoporous nano-hydroxyapatite has attracted wide attention in the

chemistry and materials communities because of their its wide accessibility, low density, large

specific area and pore volume, small size, mechanical properties, thermal stabilities and

surface permeability [6]. In addition, mn-HAP has also a greater potential in a nanoscale-

based delivery system due to its promising high capacity [7]; HAP crystals have been widely

used in delivery systems for genes [8], proteins [9] and various drugs [10-12] due to their non

toxic and excellent biocompatibility attributes [13-15]. Alternately, this material has potential

application in heterogeneous catalysis field which must be attributed to their cation-exchange

ability and adsorption capability [16-17]. 

Thus, nanostructured hydroxyapatite with organized mesoporosity (mn-HAP) and

controllable morphologies like spheres, needles, rods, fibers, plates, and tunable wall

structures can be of particular interest for catalysis, adsorption, biomedicine, and hosts for

nanomaterials synthesis [18]. The needle or rod-like morphology of HAP is especially

preferred for biomedical applications [19]. However, it’s very difficult to obtain mn-HAP with

the nanoscale dimensionality and controlled morphology through traditional methods, such as

dry processes [20], spray pyrolysis [21], and sonochemical synthesis [22].

Other techniques have been deployed to control the mesoporous structures of this

material, the most significant being emulsion system [23-24] and sol-gel [25-26]. Thus, the

template-directed nucleation-growth process by surfactants can produce nanostructured HAP

with organized mesoporosity [27-28]. The cooperative self-assembling of inorganic phases

and surfactants produce a mesophase structure, and the subsequent removal of the organic

component can generate well organized porous structures. A series of surfactants, including

pluronic P123 [29-30], sodium dodecyl sulfate [31], polyethylene glycol [32-33], citric acid

[34], polyvinyl alcohol [35], and cetyltrimethylammonium bromide [36-38], have been used

as templates for the synthesis of mesoporous HAP. These techniques are promising especially

when used in conjunction with a non-conventional alternative heating mode such as the

microwave irradiation [39-40].

The surfactant molecule consists of two parts having different properties: a ‘head-group’

(hydrophilic) with a strong affinity for the solvent and a ‘tail’ (hydrophobic) with less affinity

for the solvent [41]. The head group may carry a negative or positive charge, giving rise to

anionic or cationic surfactants, respectively. Besides, there is the class of ‘zwitterionic’

surfactants which alter their ionic behaviour according to pH-value of the solvent [42].

Depending on the molecular structure and type, a balance between hydrophilicity and

hydrophobicity co-existin the surfactant molecule. This is called hydrophilic-lipophilic

balance, which is important in categorizing surfactants as emulsifiers, detergents, wetting

agents, and micelle forming types [43-44]. Zwitterionic surfactants are soluble and effective

in the presence of high concentrations of electrolytes, acids and alkalies and they exhibit

cationic behaviour near or below their isoelectric points and anionic behaviour at higher pH.

The isoelectric point depends on the structure of the surfactant. These surfactants may contain

two charged groups of different sign. Whereas the positive charge is invariably ammonium,

the source of the negative charge may vary such as carboxylate, sulphate, or sulphonate

groups. These surfactants have excellent dermatological properties and they are frequently

used in shampoos and other cosmetic products, and also in hand dishwashing liquids because

of their high foaming properties [45].

 To the best of our knowledge, no study has been published using a zwitterionic surfactant

for the synthesis of hydroxyapatite. In this report, mesoporous nano-structured hydroxyapatite

was successfully produced via zwitterionic template-sequential nucleation-growth route using

lauryl dimethylaminoacetic acid (See Supporting Information), assisted by microwave

irradiation. The effect of surfactant addition on the morphology, size, crystallinity, surface

area, and porosity of crystals of the mn-HAP are discussed.

2. Experimental section

2.1. Materials and apparatus

The lauryl dimethylaminoacetic acid (LB) surfactant was purchased from O.L.A.C. (local

company in Casablanca Morocco). All other commercial reagents were purchased from

Aldrich Chemical Company and were used without further purification. The microwave oven

from Strat-Synth (Milestone S.r.l.) and Sorvall WX Ultra Series centrifuge from Thermo

Scientific was used in these studies. For drying materials, a thermostatic vacuum dryer

Vacuo-Temp was deployed.

2.2. Synthesis of mesoporousnano-HAP

Calcium nitrate tetrahydrate (Ca(NO3)2.4H2O) and diammonium hydrogen phosphate

((NH4)2HPO4) were used as calcium and phosphorous sources respectively for the synthesis

of mn-HAP. The zwitterionic surfactant, LB, was utilized as the templating agent. Two

mixtures were prepared (designated S1 and S2). For S1: 0.1 mol (11.8 g) of Ca(NO3)2.4H2O

was dissolved into 75 mL of deionized water and then 0.01 M of LB was added. This mixture

was stirred for 30 min at room temperature to form micelles. For S2: 0.06 mol (3.96 g) of

(NH4)2HPO4 was dissolved into 125 mL of deionized water. The pH of this solution was

maintained higher than 10 by adding ammonium hydroxide. The two solutions, S1 and S2,
were mixed and then placed in a microwave reactor for 30 minutes at a temperature of 80 °C.

After the reaction time, the resulting white precipitate was separated by centrifuging at 8000

rpm for 10 min. The separated product was washed with deionized water and ethanol three

times and then driedat 80 °C overnight in hot vacuum desiccator.

2.3. Thermal and structural characterization techniques

Elemental analysis was determined by inductively coupled plasma-optical emission

spectroscopy (ICP-OES) from Yvan Jobin (Ultimate 2). TGA was conducted under air in a

TA Instrument Q500 apparatus with a 10°C/min ramp between 25 and 1000°C. Fourier

transforms infrared spectra of samples in KBr pellets were measured on a Bruker Vector 22

spectrometer. Raman spectra were recorded for powder samples on a Perkin Elmer Raman

spectrometer with 785 nm red laser irradiation. NMR solid-state experiments were recorded

on a Bruker Avance 400 (9.4 T) spectrometer equipped with a 4 mm probe. For 1H MAS and
31
P MAS single pulse experiments, small flip angle (~30°) were used with recycle delays of

5s and 20s, respectively.31P-NMR spectra were recorded under high-power proton decoupling

conditions. X-ray diffraction patterns of the samples were obtained at room temperature on a

Bruker AXS D-8 diffractometer using Cu-Kα radiation in Bragg-Brentano geometry (θ-2θ).

The crystal size was calculated using the Scherrer’s equation. TEM micrographs were

obtained on a Tecnai G2 microscope at 120 kV.

2.4. Textural characteristics

The specific surface areas were determined from the nitrogen adsorption/desorption

isotherms at -196 °C, and estimated in relation to the masses of the out gassed samples and

calculated from the BET equation. Pore size distributions were calculated from the N2

adsorption isotherms with the ‘‘classic theory model’’ of Barret, Joyney and Halenda (BJH)
[46]. The gas adsorption was performed on a Quantachrome Autosorb-1 automatic analyzer

using N2 (molecule cross-sectional area of 0.162 nm2) as the adsorptive gas. Prior to N2

sorption, all samples were degassed at 100 °C overnight.

3. Results and discussion

Mesoporous nano-hydroxyapatite has been synthesized via template-directed nucleation-

growth reactions from zwitterionic surfactant under microwave irradiation heating conditions.

Elemental analysis of mn-HAP by inductively coupled plasma-optical emission spectroscopy

reveals that the Ca/P ratio matched the expected ratio for hydroxyapatite (~1.66).

In order to determine the thermal behaviour of this material, the dried powder of the

mn-HAP was analysed by TGA (Fig. S2). Two major stages mass loss were observed: i) the

first one at 280°C≥ T ≥ Troom, is due to water evaporation, ethanol and after the template

combustion, and ii) the secondat 500 °C ≥ T ≥ 280 °C corresponds to the crystallization of

mn-HAP. Thus, we have adopted 500 °C as calcination temperature for all samples.

The FT-IR analysis of mn-HAP sample, prepared by this route is shown in Fig. 1A which

indicates that all bands correspond to mn-HAP. The band at 3572 is characteristic of OH

stretching of mn-HAP lattice [50]. The bending modes appeared at 602,566 and 472 cm-1 are

assigned respectively to ν4(PO43-), ν4(PO43-), ν2(PO43-) [49] and the absorption at 1027 cm-1 is

attributed to ν3(PO43-) [51]. In addition, the broad band centred approximately at 3400 cm-1

and the band at 1617 cm-1 show the presence of adsorbed water [50]. The bands

corresponding to 1420 and 1470 cm-1 indicate the presence of carbonate ions in the resultant

mn-HAP [51].

Fig. 1B shows the Raman spectra of mn-HAP synthesized in the presence of LB calcined at

500°C for 10 hrs. Apart from the hydroxyl bands, all the modes associated to the phosphate
were observed (ν1(PO4), ν2(PO4), ν3(PO4), and ν4(PO4) bands) [47]. The phosphate modes

1072 cm-1 (ν3(PO4),1046 cm-1 (ν3(PO4), 959 cm-1 (ν1(PO4), 608 cm-1 (ν4(PO4), 590 cm-1

(ν4(PO4)), 577 cm-1 (ν4(PO4)), 445 cm-1 and 432 cm-1 (ν2(PO4) are observed. We note that the

ν1(PO4) band at 959 cm-1 is very intense and characteristic of hydroxyapatite. This mode is

associated to the totally symmetric stretching mode of the ‘free’ tetrahedral phosphate ligand.

Fig. 1.

Fig. 1C illustrated the XRD patterns of the before and after calcination of mn-HAP

respectively. All the diffraction peaks corresponded to the standard characteristic peaks of

hexagonal symmetry (space group P63/m) indicating that the phase of the samples was highly

pure HAP, and this is expected since we have synthesized the mn-HAP at a pH higher than 10.

The both diagrams are identical in terms of existing phase. Moreover, in the case of the

calcined sample, the diffraction peaks are thinner (see (300) and (211) peaks), indicating an

increase in the crystallite size.

The lattice parameters are presented in Table 1 which is in good agreement with data of the

JCPDS card no74-566. The Average crystallite size estimated by the Scherrer equation is

about 19 nm for the dried sample and 22 nm for calcined sample at 500 °C.
31
The PMAS NMR spectrum of the mn-HAP reveals the presence of a single isotropic

signal at 2.6ppm (Fig. 1D), which proves the existence of only one type of phosphorus (PO43-)

in the apatite structure. The 1HMAS-NMR spectrum of the mn-HAP presents two signals (Fig.

1D, inset). The first peak at 0.10 ppm is characteristic of the proton of the hydroxyapatite,

while the second peak at 5.45 ppm corresponds to the water molecule physisorbed on the

surface. The results of both NMR spectra are consistent with previous results and confirm the

purity of the prepared mn-HAP.

 The size and the morphology of the prepared sample were examined by TEM (Fig. 2). The

images show rod-like mn-HAP crystallites with a uniform diameter and length of about 19 nm

and 69 nm, respectively (Table 1). Observing the SAED patterns (Fig. 2), spacing and angles

of the lattice fringes, can consistently be assigned to the structure of hydroxyapatite. We can

also, see that the spots corresponding to the (002) faces of mn-HAP were notably brighter than

the others, suggesting a preferred orientation of the mn-HAP nanoparticles according to the

[001] direction. This explains the high intensity of the (002) reflection in the XRD diagram.

The preferential orientation along the axis (002) of these nanocrystallites of mn-HAP may be

due to the high energy offered by the microwave system. Indeed, reduction of specific surface

energy is the principal driving force for crystal growth and morphology development [48].

Microwave irradiation provides a rapidly changing electric field, which cause the movement

and the polarisation of water molecules and PO43- ions. When the crystallites acquire the

energy needed, they are moving according to the plans of lower energy which are in this case

the (001) planes.

Fig. 2.

The pores are formed by the removal of the intermediate assemblies of the charged

surfactant molecules. The nitrogen adsorption/desorption isotherms of the dried and calcined

mn-HAP samples can be categorized as type IV, with a distinct hysteresis loop. The BET

surface area is calculated to be 87 and 55m2g-1 for dried and calcined samples respectively.

The decrease of the specific surface area can be explained by the effect of heat treatment on

the pore network. The typical H1 hysteresis loop for two samples (Fig. 3A) indicated that

there were a great amount of cylinder-like open-ended pores inside the mn-HAP

nanoparticles, which corroborate the TEM results. The BJH pore size distribution of dried and

calcined samples, are analogous, they were centred approximately at 36 nm (Table 1). To
confirm the role of the template, we have also synthesized this material without using any

surfactant. The formation of small pores was observed, giving a low surface area not

exceeding 30 m2g-1 after heat treatment. Additional concentrations were also evaluated but the

results obtained are similar to the one discussed here. Similarly, the synthesis of this material

in the presence of surfactant but by conventional heating gives rise to mn-HAP powder with

low surface area, about 20 m2g-1. This demonstrates the definitive advantage of microwave

heating and its synergistic effect with surfactants to generate the organized mesoporosity.

Indeed, this study outlines the precise effect of this technique to control growth of mn-HAP.

Fig. 3.

Table 2

4. Conclusions

In this present work, we have developed a novel microwave process for the synthesis of

mn-HAP via a template-directed nucleation-growth reaction using zwitterionic surfactant. The

elemental analysis by ICP-OES confirms that powders mn-HAP is stoichiometric. The

31
structural characterizations by FT-IR, Raman, XRD and P and 1H MAS NMR analysis

confirms that the synthesized material have a pure crystal structure corresponding to

hydroxyapatite. TEM observations illustrate the rod-like structure assemblies and the mean

size that varied between: 19/69 nm (diameter/length). However, the exploitation of the

adsorption/desorption isotherms via BET equation reveal that mn-HAP powders are

meso-structured in nature. The specific surfaces areas are 87 and 55 m2g-1corresponding to the

pore volume 0.886 and 0.963 cm3/g, respectively, for the dried and calcined mn-HAP. The

BJH isotherm shows the powder has a broad pore size distribution with average sizes toward

36 nm. These observations demonstrate the crucial role of the use of zwitterionic surfactant to
generate the calibrated pores, and then the nano-structuration of hydroxyapatite. The precise

control over the particle and narrow-size pore distribution broadens the scope of this material

for future applications.

Acknowledgement

The financial assistance of the Office Chérifien des Phosphates in the Moroccan Kingdom

(OCP Group): Industrial pole, Department of the R&D towards this research is hereby

acknowledged. We acknowledge also the financial assistance of the CNRST. We also thank

the technical support teams of the MAScIR Foundation.

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Table 1. Lattice parameter, crystallite size, mean diameter and length, BET surface area, pore
volume and pore diameter for dried and calcined mn-HAP.

Lattice
Particle
parameter
Crystallite size[c]/nm SBET[d]/ Vmeso[d]/ Pore
Material (Å) diameter
size[a]/nm m2g-1 mL g-1 (nm)[d]
a b Mean Mean
diameter Length
M1 87 0.886
9.399 6.865 22 19 69 36
M2 55 0.963
M1: Dried mn-HAP at 80 °C, M2: Calcined mn-HAP at 500 °C. [a] Calculated by Debye-Scherer equation. [b]
Mean diameter and length determined by TEM. [d] From nitrogen sorption analysis.
Fig. 1. (A) FT-IR spectrum of dried mn-HAP at 80 °C overnight. (B) Raman spectrum of

dried mn-HAP at 80 °C overnight. (C) XRD patterns of dried mn-HAP at 80 °C overnight and

calcined mn-HAP at 500°C for 10 hrs. (D) 31P MAS NMR spectrum of calcined mn-HAP at

500 °C for 10 hrs and (inset) the 1H MAS NMR spectrum of calcined mn-HAP at 500 °C for

10 hrs.
 Fig. 2. TEM micrograph and SAED pattern of calcined mn-HAP at 500 °C for 10 hrs.

Fig. 3. (A) Nitrogen adsorption isotherms on mn-HAP powders: dried at 80 °C overnight (a),

and calcined at 500 °C for 10 hrs (b). (B) BJH pore size distribution for mn-HAP by action of

0.01M of LB surfactant: (a) dried material at 80 °C overnight, and (b) calcined material at 500

°C for 10 hrs.
Highlights

► Mesoporous nano-hydroxyapatite (nm-HAP) was expeditiously synthesized using sol-gel

protocol assisted by microwave.

► A zwitterionic template: lauryl dimethylaminoacetic acid has been tested.

► This way enables the precise control of pore size in a narrow-size distribution range (36
nm).

► The controlled growth of hydroxyapatite is confirmed by several techniques.