See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/308667801

Nanostructured Samarium Doped Fluorapatites and Their Catalytic Activity

towards Synthesis of 1,2,4-Triazoles

Article  in  Molecules · September 2016

DOI: 10.3390/molecules21101281

CITATIONS READS

3 52

4 authors, including:

Sreekantha Babu Jonnalagadda

University of KwaZulu-Natal
289 PUBLICATIONS   2,941 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Analytical and biochemical of studies of selected seaweeds obtained from the eastern coast of South Africa`s Indian Ocean in
KwaZulu-Natal. View project

Both of them and total i have published 31 articles in international reputed journals. View project

All content following this page was uploaded by Sreekantha Babu Jonnalagadda on 19 October 2016.

The user has requested enhancement of the downloaded file.

 molecules
Article
Nanostructured Samarium Doped Fluorapatites
and Their Catalytic Activity towards Synthesis
of 1,2,4-Triazoles
Kranthi Kumar Gangu, Suresh Maddila, Surya Narayana Maddila
and Sreekantha B. Jonnalagadda *
School of Chemistry & Physics, University of KwaZulu-Natal, Westville Campus, Chiltern Hills, Durban-4000,
South Africa; kkgangu@ymail.com (K.K.G.); sureshmskt@gmail.com (S.M.); maddilasurya@gmail.com (S.N.M.)
* Correspondence: jonnalagaddas@ukzn.ac.za; Tel.: +27-31-260-7325

Academic Editor: Arnaud Gautier

Received: 29 July 2016; Accepted: 20 September 2016; Published: 24 September 2016

Abstract: An investigation was conducted into the influence of the amino acids as organic
modifiers in the facile synthesis of metal incorporated fluorapatites (FAp) and their properties.
The nanostructured Sm doped fluorapatites (Sm-FAp) were prepared by a co-precipitation method
using four different amino acids, namely glutamic acid, aspartic acid, glycine and histidine. The
materials were characterized by various techniques including X-ray diffraction (XRD), Fourier
transform infra-red spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM),
energy-dispersive X-ray spectroscopy (EDX), high resolution transmission electron microscopy
(HR-TEM), N2 -adsorption/desorption isotherm, temperature programmed desorption (TPD) and
fluorescence spectrophotometry. Under similar conditions, Sm-FAp prepared using different amino
acids exhibited distinctly different morphological structures, surface area and pore properties.
Their activity as catalysts was assessed and Sm-FAp/Glycine displayed excellent efficiency in the
synthesis of 1,2,4-triazole catalyzing the reaction between 2-nitrobenzaldehyde and thiosemicarbazide
with exceptional selectivity and 98% yield in a short time interval (10 min). The study provides an
insight into the role of organic modifiers as controllers of nucleation, growth and aggregation which
significantly influence the nature and activity of the catalytic sites on Sm-FAp. Sm-FAp could also
have potential as photoactive material.

Keywords: Sm-fluorapatite; nanostructured catalysts; 1,2,4-traizole; organic modifiers; textural

properties; amino acids

1. Introduction
In recent years, due to their exceptional properties the application of calcium apatites,
Ca10 (PO4 )6 (OH)2 (HAp), particularly fluorapatites, Ca10 (PO4 )6 F2 (FAp) has become far-reaching
in the fields of biomedicine, bioactive implant surfaces, dental implants, catalysis, drug delivery
and environment engineering [1–6]. FAp crystallizes in a hexagonal crystal system with space
group P6/m (175) having lattice parameters a = 9.3684 Å and c = 6.8841 Å in which the calcium
and phosphate ions are arranged around the fluoride ions in the [001] direction (along c-axis) [7,8].
Tuning the composition and surface properties of FAp imparts flexibility with respect to behavior
as catalysts or as supports for several catalytic centers which accelerate many value-added organic
transformations [9–11]. Studies have demonstrated that apatites can be utilized in the development of
sustainable, green and reliable heterogeneous catalysts in the organic transformations such as Michael
addition, Knoevenagel condensation, oxidation, hydroformylation, cyclic additions and epoxidation
reactions [12–16]. The ability of FAp to adsorb organic, inorganic and metal salt substrates on their
surfaces make them ideal for several catalytic applications. Due to the presence of both Brønsted/Lewis

Molecules 2016, 21, 1281; doi:10.3390/molecules21101281 www.mdpi.com/journal/molecules

Molecules 2016, 21, 1281 2 of 15

acidic and basic sites on its surface, FAp provides multiple active sites for catalysis [17]. The acidic sites
are generated from the Ca2+ and phosphorous of PO4 group, whereas the basic sites are obtained from
the F− and oxygen of PO4 group. The electron rich Lewis basic sites (P-O− and F− ) and acidic sites
(M2+ , PO2 H2+ ) which are closely packed in different locations in the FAp surfaces can facilitate the
organic transformations through the acid-base catalyzed processes [18–20]. Gruselle et al. in their study
have reported that the hydroxyl groups present on the surfaces of calcium hydroxyapatite played a
key role in the Michael C-C bond formation [21]. In order to improve FAp as a heterogeneous catalyst,
it can be modified by the partial replacement of Ca2+ with other divalent or trivalent ions, which lead
to the creation of well-defined Lewis acidic active sites on the surfaces. Rare earth elements from La to
Lu possess ionic radii comparable to Ca2+ making such replacement much easier [22–24]. In addition,
the incorporation of rare earth elements, particularly samarium, into the FAp structure increases
wide ranging catalytic properties [25–28]. The catalytic efficiency of FAp also relies on its physical
features. Thus, synthesis of such well-crafted materials with specific size, controlled morphology
and hierarchical architecture is of real significance [29–31]. The synthesis of such materials can be
influenced by various factors including the nature of, surfactants, capping agents, chelating agents or
organic compounds employed [32,33]. Polymers-assisted synthesis can lead to varied morphologies,
restriction of nucleation and confiscation of crystal growth [34,35]. Amino acids as crystal growth
modifiers are an attractive option in the preparation of modified fluorapatites, in terms of green
principles and biocompatibility as they are eco-friendly, sustainable and cost-effective. They possess
functional groups (–NH2 & –COOH) with capability to tune the size and dimensions of optimistic
materials, while their side chains (-R group) remain intact [36–39]. The literature has few reports on
the scope and role of crystal growth modifiers in the synthesis of fluorapatites [40].
The efficacy of the nanostructured Sm loaded FAp as catalysts for the synthesis of 1,2,4-triazoles
was assessed. Triazoles have plentiful applications in the biological and pharmaceutical fields [41–43].
Appropriate intrusion of the 1,2,4-triazole nucleus in biologically active compounds is known to
create anti-tubercular, anti-malarial, anti-microbial, anti-inflammatory, anti-tumor and anti-convulsant
activities [44,45]. In addition to their pharmaceutical importance, high nitrogen containing compounds
like 1,2,4-triazoles are extensively used as energetic materials due to their valuable ballistic
properties [46]. The above applications highlight the importance of a facile synthetic route for triazoles
to surmount the hindrances such as elaborate reaction conditions, high temperature maintenance,
long work-up procedures and low yields. In the earlier studies, we have reported the synthesis and
characterization of diverse metal (Fe Co, Pt, Sr, Ir, and V) substituted hydroxyapatites and their scope
as heterogeneous catalysts in value-added organic transformations such as selective oxidation of
n-pentanes and in Knoevenagel condensation reactions with excellent yields [47–50]. We have also
reported the scope of Sm(III) based coordination polymer as a viable yellow light emitter [51].
In this paper, we report the amino acids-assisted synthesis of nanoparticles of fluorapatites
impregnated with Sm through co-precipitation methods with examination of the changes in the
physical characteristics such as size, morphology, surface area, pore properties and fluorescence
activity of the products by using four different amino acids as crystal growth modifiers. The activities
of the materials as catalysts for the reaction between 2-nitro-benzaldehyde and thiosemicarbazide to
yield thio-triazole moiety are compared.

2. Results and Discussion

2.1. XRD Analysis

To investigate the crystalline phases of Sm-FAp, X-ray diffraction measurements were performed
and the results are illustrated in Figure 1. The diffraction patterns of the six samples are well matched
with the fluorapatite standard (JCPDS # 15-0876). No significant variation is observed in the diffraction
pattern of samples prepared with different amino acids and no characteristic peaks of impurities
are observed, which confirms that the present experimental conditions used are suitable for the
Molecules 2016, 21, 1281 3 of 15

of impurities
Molecules 2016, 21, are
1281 observed,
which confirms that the present experimental conditions used3 ofare 15
suitable for the preparation of Sm-FAp. The peaks (211), (300) and (202) have high intensities with
glutamic acid (Figure 1c) and aspartic acid (Figure 1d), but those peaks are missing with the other
preparation of Sm-FAp. The peaks (211), (300) and (202) have high intensities with glutamic acid
two amino acids, glycine and histidine. This is ascribed to the variance in the texture due to different
(Figure 1c) and aspartic acid (Figure 1d), but those peaks are missing with the other two amino acids,
amino acids used and preferred orientation of those planes which probably have not allowed
glycine and histidine. This is ascribed to the variance in the texture due to different amino acids used
appropriate diffraction to occur. No additional phases are found in the patterns indicating that the
and preferred orientation of those planes which probably have not allowed appropriate diffraction to
doped substrate is effectively built into the host lattice. When compared with the FAp sample
occur. No additional phases are found in the patterns indicating that the doped substrate is effectively
without amino acid, the peaks of remaining samples appear to be broadened, suggesting a relative
built into the host lattice. When compared with the FAp sample without amino acid, the peaks of
decrease in the crystallite size, which is confirmed by the crystallite size calculated by Scherrer’s
remaining samples appear to be broadened, suggesting a relative decrease in the crystallite size,
formula using (211) reflection of each XRD pattern. The average crystallite size of all samples are
which is confirmed by the crystallite size calculated by Scherrer’s formula using (211) reflection of
summarised in Table 1. The amino acid introduction during the synthesis was observed to induce a
each XRD pattern. The average crystallite size of all samples are summarised in Table 1. The amino
notable modification in the crystallite size by its surface capping ability. The similar observation was
acid introduction during the synthesis was observed to induce a notable modification in the crystallite
made by Pallazzo et al. when varied amino acids were used in the preparation of hydroxyapatite
size by its surface capping ability. The similar observation was made by Pallazzo et al. when varied
nanaocrystals, where amino acid altered the morphology of crystals as well as functionalization the
amino acids were used in the preparation of hydroxyapatite nanaocrystals, where amino acid altered
hydroxyapatite surface [52]. The degree of crystallinity of the samples in the current study was
the morphology of crystals as well as functionalization the hydroxyapatite surface [52]. The degree of
examined after successive profile fit processes using High-score plus software and the results reveals
crystallinity of the samples in the current study was examined after successive profile fit processes using
that when compared with un-calcined XRD patterns, the crystallinity percentage was improved after
High-score plus software and the results reveals that when compared with un-calcined XRD patterns,
calcination (Figure S1). Furthermore, the degree of crystallinity for the un-doped FAp (65% ± 2%)
the crystallinity percentage was improved after calcination (Figure S1). Furthermore, the degree of
and Sm-FAp (63% ± 2%) in absence of amino acid were slightly higher than the amino acid assisted
crystallinity for the un-doped FAp (65% ± 2%) and Sm-FAp (63% ± 2%) in absence of amino acid
Sm-FAp (55%–60% ± 5%), which indicates that the presence of amorphous amino acid decrease the
were slightly higher than the amino acid assisted Sm-FAp (55%–60% ± 5%), which indicates that the
crystallinity in amino acid assisted Sm-FAp.
presence of amorphous amino acid decrease the crystallinity in amino acid assisted Sm-FAp.

Figure 1. X-ray diffraction pattern of (a) FAp/without amino acid; (b) Sm-FAp/without amino acid;
Figure 1. X-ray diffraction pattern of (a) FAp/without amino acid; (b) Sm-FAp/without amino acid;
(c) Sm-FAp/Glutamic acid; (d) Sm-FAp/Aspartic acid; (e) Sm-FAp/Glycine; (f) Sm-FAp/Histidine.
(c) Sm-FAp/Glutamic acid; (d) Sm-FAp/Aspartic acid; (e) Sm-FAp/Glycine; (f) Sm-FAp/Histidine.
Table 1. BET-Surface area, pore properties and TPD data of catalysts.
Table 1. BET-Surface area, pore properties and TPD data of catalysts.
BET-Surface Pore Volume Pore Size Average Crystallite
Average Size Acidity (mmol
Sample
Area (m2 /g)
BET-Surface (cm 3 Volume
Pore/g) Pore Size from XRD (nm)
(nm) Acidity
NH 3 /g)
Sample Crystallite Size
± 1.3(m /g)
Area 2
0.13 ±(cm
0.02 /g)
3 (nm)
11.5 ± 0.2 (mmol
205 ± NH
6.7 3/g)
FAp/without amino acid 32 from±XRD
17.52 0.4 (nm)
Sm-FAp/without amino acid 39 ± 3.1 0.21 ± 0.02 12.6 ± 0.3 15.58 ± 0.4 271 ± 6.2
FAp/without amino
Sm-FAp/Glutamic acidacid 321.1
43 ± ± 1.3 0.22 0.13 ± 0.02
± 0.02 13.1 ±11.5
0.2 ± 0.2 9.817.52
± 0.3 ± 0.4 205
349 ± ±12.6
6.7
Sm-FAp/without amino
Sm-FAp/Aspartic acid acid 94 ±
391.5
± 3.1 ± 0.03
0.44 0.21 ± 0.02 18.4 ±12.6
0.3 ± 0.3 ± 0.4 ± 0.4
6.215.58 ± ±11.4
271
412 6.2
Sm-FAp/Glycine 106 ± 1.3 0.38 ± 0.01 14.1 ± 0.3 5.7 ± 0.4 607 ± 14.4
Sm-FAp/Glutamic acid 43 ± 1.1 0.22 ± 0.02 13.1 ± 0.2 9.8 ± 0.3 349 ± 12.6
Sm-FAp/Histidine 76 ± 1.3 0.27 ± 0.01 16.6 ± 0.3 10.6 ± 0.4 375 ± 11.5
Sm-FAp/Aspartic acid 94 ± 1.5 0.44 ± 0.03 18.4 ± 0.3 6.2 ± 0.4 412 ± 11.4
Sm-FAp/Glycine 106 ± 1.3 0.38 ± 0.01 14.1 ± 0.3 5.7 ± 0.4 607 ± 14.4
2.2. FT-IR Analysis
Sm-FAp/Histidine 76 ± 1.3 0.27 ± 0.01 16.6 ± 0.3 10.6 ± 0.4 375 ± 11.5

Figure 2 illustrates the FT-IR spectra for the formation of Sm-FAp in the presence of different
amino acids. No changes are observed in the spectra of Sm-FAp prepared using different amino
Molecules 2016, 21, 1281 4 of 15

2.2. FT-IR Analysis

Molecules 21,illustrates
2016, 2
Figure 1281 4 of 15
the FT-IR spectra for the formation of Sm-FAp in the presence of different
amino acids. No changes are observed in the spectra of Sm-FAp prepared using different amino
acids. This plainly suggests that amino acids contribute to the modification of structural features
acids. This plainly suggests that amino acids contribute to the modification of structural features
without major changes in the final product. The amino acids played a role in the crystal growth and
without major changes in the final product. The amino acids played a role in the crystal growth and
surface modification throughout the reaction. The major absorption peaks at 1064 cm−1,−601 cm−1 and
surface−1modification throughout the reaction. The major absorption peaks at 1064 cm , 601 cm− 1
1
561 cm indicate the phosphate group’s stretching and bending vibrations. The peaks at 601 and 561
and−1561 cm− 1 indicate the phosphate group’s stretching and bending vibrations. The peaks at 601
cm are from the bending asymmetric modes of triply degenerated O–P–O bonds of phosphate
and 561 cm− 1 are from the bending asymmetric modes of triply degenerated O–P–O bonds of
group, whereas the band at 1064 cm−1 is assigned to P–O asymmetric stretching vibrational mode of
phosphate group, whereas the band at 1064 cm− 1 is assigned to P–O−1asymmetric stretching vibrational
phosphate group [53]. The observed bands at 1656 and 1452 cm respectively correspond to C=O
mode of phosphate group [53]. The observed bands at 1656 and 1452 cm−1 respectively correspond
stretching and COO– asymmetric vibrations of carboxylic acid group present in the amino acid. The
to C=O stretching and COO– asymmetric vibrations of carboxylic acid group present in the amino
peaks at 3382 and 1420 cm−1 respectively are related to the N–H and NH2–H+ symmetric stretching
acid. The peaks at 3382 and 1420 cm− 1 respectively are related to the N–H and NH2 –H+ symmetric
vibrations of amino group. No peaks at 1452 and 1420 cm were observed for the glutamic acid
−1
stretching vibrations of amino group. No peaks at 1452 and−11420 cm− 1 were observed for the glutamic
assisted Sm-FAp and the weak peaks appeared at 1656 cm and − 3382 cm−1 indicate minimal presence
acid assisted Sm-FAp and the weak peaks appeared at 1656 cm and 3382 cm− 1 indicate minimal
1
of amino acid on the surface (Figure 2a). The absorption bands reflecting the presence of amino acid
presence of amino acid on the surface (Figure 2a). The absorption bands reflecting the presence of
suggest that it binds to the Sm-FAp surface effectively.
amino acid suggest that it binds to the Sm-FAp surface effectively.

Figure 2. FT-IR spectra of (a) Sm-FAp/Glutamic acid; (b) Sm-FAp/Aspartic acid; (c) Sm-FAp/Glycine
Figure 2. FT-IR spectra of (a) Sm-FAp/Glutamic acid; (b) Sm-FAp/Aspartic acid; (c) Sm-FAp/Glycine
(d) Sm-FAp/Histidine.
(d) Sm-FAp/Histidine.

2.3. SEM and

2.3. SEM and TEM
TEM Analysis
Analysis of
of Sm-FAp
Sm-FAp and
and the
the Influence
Influence of
of Amino
AminoAcids
Acids
The
The morphology,
morphology, size size and
and shape
shape of of the
the particle
particle characteristics
characteristics were
were obtained
obtained from from FE-SEM
FE-SEM and and
HR-TEM
HR-TEM micrographs.
micrographs.FigureFigure3 shows
3 shows thetheSEM andand
SEM TEMTEMmicrographs
micrographs of Sm-FAp
of Sm-FApwith various amino
with various
acids.
aminoSEM and SEM
acids. TEM micrographs reflect the effect
and TEM micrographs of amino
reflect the acids on of
effect change
aminoof morphological
acids on change featuresof
and size of the particles.
morphological When
features and glutamic
size acid was used
of the particles. Whenasglutamic
crystal growth
acid was modifier,
used as thecrystal
crystals have
growth
amodifier,
flower bud-like
the crystalsshape
have(Figure 3a)bud-like
a flower attainingshape
dimensions
(Figure of
3a)30–40 nm in
attaining length and
dimensions of 20–25
30–40 nm nm inin
diameter. The TEM micrograph (Figure 3c) show the particles are in bunches
length and 20–25 nm in diameter. The TEM micrograph (Figure 3c) show the particles are in buncheswith sharp ended edges.
In thesharp
with case of aspartic
ended acid,
edges. In unlike
the caseglutamic acid,acid,
of aspartic the particles are widely
unlike glutamic acid,dispersed
the particleswitharesmoother
widely
surfaces (Figure 3d) and 40–60 nm in length with 20–40 nm diameters as shown
dispersed with smoother surfaces (Figure 3d) and 40–60 nm in length with 20–40 nm diameters as in TEM micrograph
(Figure
shown 3f). The TEM
in TEM micrograph
micrograph also reveals
(Figure 3f). Thethat
TEMparticles are wellalso
micrograph dispersed.
revealsWith thatglycine
particlesalsoare
similar
well
features
dispersed.areWith
observed,
glycinebut thesimilar
also particles had rough
features and compact
are observed, morphological
but the particles hadsurfaces
rough and (Figure
compact3g).
A perusal of TEM micrograph indicates that the particles are 14–35 nm in length
morphological surfaces (Figure 3g). A perusal of TEM micrograph indicates that the particles are 14– and 8–10 nm in
diameter
35 nm in(Figure
length3i). In the
and 8–10presence
nm inofdiameter
histidine,(Figure
the size3i).
distribution of discreteofnanoparticles
In the presence histidine, the is very
size
similar to that with the aspartic acid and exhibit similar surface morphology (Figure
distribution of discrete nanoparticles is very similar to that with the aspartic acid and exhibit similar 3j), but particle
dimensions are different.
surface morphology The TEM
(Figure micrograph
3j), but of Sm-FAp with
particle dimensions histidine (Figure
are different. The TEM 3l) shows particles
micrograph of
100–160
Sm-FApnm within histidine
length and 35–50 nm
(Figure in diameter.
3l) shows Figure
particles 3b,e,h,k
100–160 nmshows the EDX
in length spectranm
and 35–50 of in
all diameter.
products,
which endorses the existence of doped samarium and also confirms the formation of nanostructures of
Sm-FAp together with the presence of Sm, Ca, P and F in the specimen. The existence of fluorine and
Molecules 2016, 21, 1281 5 of 15

Molecules 2016, 21, 1281 5 of 15

Figure 3b,e,h,k shows the EDX spectra of all products, which endorses the existence of doped
samarium and also confirms the formation of nanostructures of Sm-FAp together with the presence
of Sm, Ca,
doping P and was
samarium F infurther
the specimen. The
confirmed byexistence of fluorine
the ICP-OES analysis and
and doping samarium
the correlated was
results further
with EDX
confirmed
are by in
tabulated theTable
ICP-OES
S1. analysis and the correlated results with EDX are tabulated in Table S1.

Figure 3.
Figure 3. FE-SEM,
FE-SEM,HR-TEM
HR-TEM micrographs andand
micrographs EDX spectra
EDX of (a–c)
spectra Sm-FAp/Glutamic
of (a–c) acid; (d–f)
Sm-FAp/Glutamic acid;
Sm-FAp/Aspartic acid; (g–i) Sm-FAp/Glycine; (j–l) Sm-FAp/Histidine.
(d–f) Sm-FAp/Aspartic acid; (g–i) Sm-FAp/Glycine; (j–l) Sm-FAp/Histidine.

2.4. Textural
2.4. Textural Properties
Properties of
of Sm-FAp
Sm-FApwith
withInfluence
InfluenceofofAmino
AminoAcids
Acids
The textural
The texturalproperties
properties pertaining
pertaining to a to a series
series of Sm-FAp
of Sm-FAp withamino
with various various amino
acids acids were
were determined
determined using adsorption/desorption isotherms of nitrogen under cryogenic
using adsorption/desorption isotherms of nitrogen under cryogenic conditions. The prime objective conditions. The
prime objective was to investigate the effect of varied amino acids in the synthesis
was to investigate the effect of varied amino acids in the synthesis of Sm-FAp on the BET-surface area, of Sm-FAp on the
BET-surface
pore volumearea, pore sizes.
and pore volume and
The pore sizes.
isotherms for The isotherms
all the samplesfor all the
match wellsamples
with TypematchIV well with
isotherm
Type IV isotherm (Figure 4) and the quantity of nitrogen adsorbed was found
(Figure 4) and the quantity of nitrogen adsorbed was found to be different for different products. to be different for
different products. Table 1 summarises the trends in BET-surface area, pore volume
Table 1 summarises the trends in BET-surface area, pore volume and pore sizes in presence of different and pore sizes
in presence
amino acids. of different
With glycine,amino acids. shows
the sample With glycine,
the highestthesurface
samplearea
shows the highest
of 106.96 m2 /g withsurface area of
decreasing
106.96 m 2/g with decreasing order as follows: aspartic acid > histidine > glutamic acid. Average pore
order as follows: aspartic acid > histidine > glutamic acid. Average pore volume was highest with
volume acid
aspartic was andhighest
lowestwith
withaspartic
glutamicacid and lowestsample.
acid-assisted with glutamic
While all acid-assisted
products show sample.
a meso While all
pore size
products show a meso pore size range of 13 to 18 nm and aspartic acid-assisted
range of 13 to 18 nm and aspartic acid-assisted sample displayed highest pore size. The lower surface sample displayed
highest
area pore size.
recorded withThe lower surface
un-doped FAp andarea recorded
Sm-FAp with un-doped
in absence of amino FAp and Sm-FAp
acid confirms in absence of
the importance of
amino acid
amino acidonconfirms the importance
their surface modifications. of The
amino acidproperties
textural on their surface
of samplesmodifications.
are related toThe textural
the physical
properties of samples are related to the physical parameters such as morphology,
parameters such as morphology, particle size etc. The lowest particle size of Sm-FAp/Glycine possessed particle size etc.
The lowest particle size of Sm-FAp/Glycine possessed the highest surface
the highest surface area, similar to that of Sm-FAp/Aspartic acid. Although Sm-FAp/Glutamic acid area, similar to that of
Sm-FAp/Aspartic
contained acid. Although
smaller particles Sm-FAp/Glutamic
to Sm-FAp/Histidine, acid contained
the later displayed smaller
higher surface area. particles
This may be to
Sm-FAp/Histidine, the later displayed higher surface area. This may be attributed
attributed to the wide distribution of particles with morphological structure and surfacial features of to the wide
distribution of particles
Sm-FAp/Histidine similarwith morphological structure
to Sm-FAp/Aspartic acid. and surfacial features of Sm-FAp/Histidine
similar to Sm-FAp/Aspartic acid.
Molecules 2016, 21, 1281 6 of 15
Molecules 2016, 21, 1281 6 of 15

Figure4.4.NN22 adsorption/desorption
Figure adsorption/desorption isotherm at 77 K.

2.5. Fluorescence
2.5. Fluorescence Activity
Activity of
of Sm-FAp
Sm-FApwith
withAmino
AminoAcids
Acids
Lanthanides are
Lanthanides are well-known
well-known fluorescents,
fluorescents, but but their
their fluorescence
fluorescence efficacyefficacy purely
purely depends
depends on on the
the
selection of plausible host matrix [54]. Fluorapatites are promising supporting
selection of plausible host matrix [54]. Fluorapatites are promising supporting materials and possess materials and possess
capability to
capability to host
host the
thevaried
variedlanthanides.
lanthanides.The Thepresence
presenceofofCa Ca2+2+,, FFand
andPO PO4433−− ions
ions in FAp could
in FAp could notnot
initiate any luminescence, since no defect/impurity-related color centers were
initiate any luminescence, since no defect/impurity-related color centers were stabilized in its lattice. stabilized in its lattice.
FApdoped
FAp dopedwith withrarerareearth
earth(RE)
(RE)orortransition
transitionmetal
metal ions
ions have
have thethe ability
ability to to
causecause luminescence
luminescence duedue to
to electronic transitions existing between the doping metal orbital [55].
electronic transitions existing between the doping metal orbital [55]. Samarium impregnation into FAp Samarium impregnation into
FAp showed
showed a fairly a fairly widestrong
wide and and strong
emissionemission
bandsbands in visible
in visible regionregion upon excitation
upon excitation at 254 nm at 254
andnm and
it was
it was attributed
attributed to 4f-orbital
to 4f-orbital transitions
transitions of samarium
of samarium entity [56–58].
entity [56–58]. In this emission
In this study, study, emissionpeaks ofpeaksamino of
acid-assisted synthesis of Sm-doped FAp nanostructures have predominantly showed a change in thea
amino acid-assisted synthesis of Sm-doped FAp nanostructures have predominantly showed
change inwith
intensity the theintensity
amino with the amino
acid used (Figureacid usedmaximum
5). The (Figure 5). The maximum
emission wavelength emission
(λmax )wavelength
of Sm-FAp
(λmax
in the) presence
of Sm-FAp in the presence
of glutamic acid and of aspartic
glutamicacid acidwas
andassigned
aspartictoacid 490was assigned
nm with to 490
intensity of nm
642 with
and
intensity of 642 and 615 units, respectively. In the case of glycine, λ shifted
615 units, respectively. In the case of glycine, λmax shifted slightly towards the higher wavelength side
max slightly towards the
higher
at 496 nmwavelength
with highside at 496intensity
emission nm withofhigh >735emission
units. Onintensity
the other ofhand,
>735 units. On the other
histidine-assisted hand,
sample
histidine-assisted sample exhibited wavelength maximum at shorter
exhibited wavelength maximum at shorter wavelength 485 nm, but with lower intensity with 582 units. wavelength 485 nm, but with
Ultimately, the results demonstrate that the change in size, shape and textural traits occur dueand
lower intensity with 582 units. Ultimately, the results demonstrate that the change in size, shape to
textural
amino traits
acids occur synthesis
assisted due to amino acids assisted
also influence synthesis
fluorescence also influence
activity. This could fluorescence
lead to newactivity.
applicationsThis
could lead
through to new applications
modulating the physical through modulating
characteristics the physical
of samples. Figure characteristics
6 illustrates the of samples.
impact ofFigureamino6
illustrates the impact of amino acids as crystal growth modifiers
acids as crystal growth modifiers in the synthesis of Sm-FAp. The change in emission intensities in the synthesis of Sm-FAp. The
change
with in emission
respect to amino intensities
acid used with
hasrespect to amino acid
direct relationship toused has direct
the particle sizerelationship
attained bytothe theSm-FAp.
particle
size attained by the Sm-FAp. The emission intensity is inversely proportional
The emission intensity is inversely proportional to the particle size of Sm-FAp. The highest emission to the particle size of
Sm-FAp.from
intensity The samples
highest of emission intensity from
Sm-FAp/Glycine, which samples
possessoflower Sm-FAp/Glycine, which to
particle size relative possess lower
other amino
acid assisted Sm-FAp samples. The luminescence activity was found to be profoundly sensitivewas
particle size relative to other amino acid assisted Sm-FAp samples. The luminescence activity to
found to
particle be and
size profoundly sensitive to
can be intensified by particle size and
the reduction can be intensified
of particle size by tailoringby thethe reduction
interfacesofwith particle
the
sizeof
use byorganic
tailoring the interfaces
modifiers [59,60].with
Thethe use ofsize
particle organic modifiers
of Sm-FAp was[59,60].
found to The particleinsize
decrease theof Sm-FAp
following
order of amino acid used: Sm-FAp/Histidine > Sm-FAp/Aspartic acid > Sm-FAp/Glutamic acid >>
was found to decrease in the following order of amino acid used: Sm-FAp/Histidine
Sm-FAp/Aspartic while
Sm-FAp/Glycine, acid >the Sm-FAp/Glutamic
order of emissionacid > Sm-FAp/Glycine,
intensity was Sm-FAp/Histidine while the< Sm-FAp/Aspartic
order of emission
intensity
acid was Sm-FAp/Histidine
< Sm-FAp/Glutamic < Sm-FAp/Aspartic acid < Sm-FAp/Glutamic acid <
acid < Sm-FAp/Glycine.
Sm-FAp/Glycine.
 Molecules 2016, 21, 1281 7 of 15
Molecules
Molecules2016,
2016,21,
21,1281
1281 77of
of15
15

Figure
Figure 5.5. Fluorescence
Figure Fluorescence
5. spectra
spectra
Fluorescence of (a)
of of
spectra Sm-FAp/Glutamic
(a)(a) Sm-FAp/Glutamicacid;
Sm-FAp/Glutamic acid; (b)
acid; (b) Sm-FAp/Aspartic
(b) Sm-FAp/Aspartic acid;
Sm-FAp/Aspartic acid; (c)
acid; (c)
Sm-FAp/Glycine;
Sm-FAp/Glycine; (d)
(d)Sm-FAp/Histidine.
(c) Sm-FAp/Glycine; Sm-FAp/Histidine.
(d) Sm-FAp/Histidine.

Figure 6. A perspective view of effect of amino acids on BET surface area, pore volume, pore size
Figure
Figure6.6.A
Aperspective
perspectiveviewviewof
ofeffect
effectof
ofamino
aminoacids
acidson onBET
BETsurface
surfacearea,
area,pore
porevolume,
volume,pore
poresize
sizeand
and
and emission intensity ((a) Sm-FAp/Glutamic acid; (b) Sm-FAp/Aspartic acid; (c) Sm-FAp/Glycine;
emission
emission intensity
intensity ((a)
((a) Sm-FAp/Glutamic
Sm-FAp/Glutamic acid;
acid; (b)
(b) Sm-FAp/Aspartic
Sm-FAp/Aspartic acid;
acid; (c)
(c) Sm-FAp/Glycine;
Sm-FAp/Glycine; (d)
(d)
(d) Sm-FAp/Histidine).
Sm-FAp/Histidine).
Sm-FAp/Histidine).

2.6.
2.6.Catalytic
CatalyticActivity
Activity
The
The effect
effect of
of the
the four
four catalysts
catalysts on
on the
the reaction
reaction of
of 2-nitro
2-nitro benzaldehyde
benzaldehyde with
with thiosemicarbazide
thiosemicarbazide
to
to yield 1,2,4-triazole moiety was investigated. In a typical reaction, equivalent molarproportions
yield 1,2,4-triazole moiety was investigated. In a typical reaction, equivalent molar proportionsof of
2-nitro
2-nitro benzaldehyde
benzaldehyde (1.0 (1.0 mmol)
mmol) andand thiosemicarbazide
thiosemicarbazide (1.0 (1.0 mmol)
mmol) were
were dissolved
dissolved in
in 5.0
5.0 mL
mL
ethanol
ethanol at
at room
room temperature,
temperature, withwith continuous
continuous stirring.
stirring. An
An appropriately
appropriately weighed
weighed (20
(20 mg)
mg) of
of the
the
Molecules 2016, 21, 1281 8 of 15

2.6. Catalytic Activity

The effect of the four catalysts on the reaction of 2-nitro benzaldehyde with thiosemicarbazide
to yield 1,2,4-triazole moiety was investigated. In a typical reaction, equivalent molar proportions of
2-nitro benzaldehyde (1.0 mmol) and thiosemicarbazide (1.0 mmol) were dissolved in 5.0 mL ethanol at
room temperature, with continuous stirring. An appropriately weighed (20 mg) of the selected amino
acid modified Sm-FAp was added as catalyst to the reaction mixture. The reaction was monitored
with TLC at regular time intervals. After confirming the completion of the reaction, the solid catalyst
was separated cautiously from the organic liquid product by filtration. The same procedure was
repeated for all the other catalysts. Among the catalysts, Sm-FAp/Glycine proved superior. While the
uncatalyzed reaction under similar reaction conditions took 2 h with 60% yield, the Sm-FAp/Glycine
reaction took 10 min with 98% yield. All the four reactions gave same product, but other three catalysts
gave relatively lower yields and had longer reaction times. In order to confirm the need for Sm
doping in the catalyst preparation, the reaction was carried out with un-doped FAp in the absence
of amino acid. When un-doped FAp was used as catalyst, the reaction took 35 min with 80% yield
(Table 2). Sm-FAp/Glycine with a high specific surface area and low particle size proved a better
catalyst compared to the other three amino acid assisted Sm-FAp catalysts. The final products were
characterized by IR, 1 H-NMR, 15 N-NMR and 13 C-NMR for confirmation of their structures. In the
FT-IR spectrum (Figure S2) of final product shows absorption frequencies at 3443, 3321, 3175 cm− 1
which indicate the stretching vibrations of three –NH groups present in the 1,2,4-triazole moiety.
In addition to this, a stretching vibrational frequency at 1276 cm− 1 confirms the presence of bonding
between carbon and sulphur (–C=S). Further, the observed signals of 1 H-NMR at δ 8.10, 8.37, 11.72 ppm
indicate the presence of three –NH secondary amine protons (Figure S3), which was confirmed by 15 N
spectrum (Figure S4). In 13 C-NMR, the signal at δ 178 ppm indicates the thiocarbonyl entity in the
structure (Figure S5).

Table 2. Catalytic performance of catalysts in the typical reaction a .

Catalyst Time (min) Yield (%)

Without catalyst 120 60
Un-doped FAp (without amino acid) 35 80
Sm-FAp/Glutamic acid 15 94
Sm-FAp/Aspartic acid 10 95
Sm-FAp/Glycine 10 98
Sm-FAp/Histidine 20 93
a Reaction conditions: 2-nitro benzaldehyde (1.0 mmol), thiosemicarbazide (1.0 mmol), catalyst (20 mg) and
ethanol (5.0 mL) were stirred at room temperature.

The reaction probably occurs on the surface of Sm-FAp rather than inside cages of the catalyst.
The surface provides Lewis acidic and basic sites to catalyze the reaction. The C-N bond can be
formed by the nucleophilic addition of thiosemicarbazide to a carbonyl group of 2-nitrobenaldehyde.
The Lewis or Brønsted basic sites on the surface of Sm-FAp facilitate the formation of nucleophilic
center in the thiosemicarbazide. The reaction is followed by the attack of the nucleophilic center by
the electrophile in the carbonyl group in order to form a bond (Figure 7). The doping of samarium
on FAp enriches the Lewis acidic centers on surfaces of Sm-FAp, which generate more active sites for
the formation of electrophilic center in the carbonyl group. The high specific surface area containing
Sm-FAp/Glycine enhances the number of catalytic active sites which make it a better catalyst. The TPD
results indicate the existence of acidic sites on the surfaces of the catalysts, Sm-FAp/Glycine being
the most acidic (Table 1), in accordance with the catalytic performance exhibited by Sm-FAp/Glycine
relative to the other catalysts. The catalytic performances were statistically tested with ANOVA and
results are statistically significant (Table S2).
 Molecules 2016, 21, 1281 9 of 15
Molecules 2016, 21,
Molecules 2016, 21, 1281
1281 99 of
of 15
15

Figure 7. Perspective view of Sm-FAp surfaces facilitating the reaction.

Figure 7. Perspective view of Sm-FAp surfaces facilitating the reaction.
Figure 7. Perspective view of Sm-FAp surfaces facilitating the reaction.
Rathinam et al. have reported the preparation of 5-aryl-1,2,4-triazolidine-3-thione and its
derivatives
Rathinam using al.polyethylene
et al. havehavereported glycol
reported aspreparation
solvent of
thethepreparation [61].
of Jayavant et al. have prepared
5-aryl-1,2,4-triazolidine-3-thione
5-aryl-1,2,4-triazolidine-3-thione andand the
its
1,2,4-triazolidine-3-thiones
its derivatives
derivatives using
using polyethyleneusing glycol
polyethylene substituted thiosemicarbazide
glycolasas solvent
solvent [61].[61]. Jayavant and aldehydes
Jayavant etet al. have with
have ionic liquid,
prepared
prepared the
[C16MPy]AlCl3Br [62] as medium.
1,2,4-triazolidine-3-thiones
1,2,4-triazolidine-3-thiones Mane et al. have
using substituted prepared 5-aryl-1,2,4-triazolidine-3-thiones
thiosemicarbazide
thiosemicarbazide and aldehydes
and aldehydes with ionic liquid, in the
presence
[C16 of
MPy]AlCl33Br
16MPy]AlCl sulfamic
Br[62] acid
[62]asasmedium.as
medium.catalyst
ManeMane from
ethave
et al. the
al. have mixture
prepared of
prepared aldehyde, hydrazine hydrate,
5-aryl-1,2,4-triazolidine-3-thiones
5-aryl-1,2,4-triazolidine-3-thiones in and
the
trimethylsilyl
in the presence isothiocyanate
of sulfamic acid [63].
as Survey
catalyst from of the the
mixture
presence of sulfamic acid as catalyst from the mixture of aldehyde, hydrazine hydrate, and literature
of suggests
aldehyde, hydrazine that
5-(2-nitrophenyl)-1,2,4-triazolidine-3-thione
hydrate,
trimethylsilyland trimethylsilyl
isothiocyanateisothiocyanate
[63]. synthesized
[63].
Survey in the
Survey
of this
of study
the is a new
literature
literature compound.
suggests
suggests that
that
Furthermore, there were no reports of 1,2,4-triazoles
5-(2-nitrophenyl)-1,2,4-triazolidine-3-thione
5-(2-nitrophenyl)-1,2,4-triazolidine-3-thione or in any
synthesized
synthesized in other
in this organic
this study is
study syntheses
is a newusing Sm-FAp
compound.
compound.
as catalysts (Scheme
Furthermore,
Furthermore, there
therewere 1). no
were To evaluate
reportsofofthe
noreports optimum quantity
1,2,4-triazoles
1,2,4-triazoles ororininany of
any Sm-FAp/Glycine
other
otherorganic
organic synthesesrequired,
syntheses using
usingthe reaction
Sm-FAp
Sm-FAp as
was carried
catalysts (Scheme
as catalysts out
(Scheme with
1). Tovaried
1). evaluateamounts
To evaluatethe the of
optimum catalyst
optimum from
quantity 10 mg to 50
of Sm-FAp/Glycine
quantity mg.
of Sm-FAp/Glycine Results
required, show that 20
the reaction
required, mg
was
the reaction of
catalyst
carried
was is optimal
out
carried with to varied
out varied
with achieve
amounts maximum
amounts of benefit
of catalyst from 10
catalyst under
mg 10
from the50
to given
mg mg. conditions
Results
to 50 show
mg. Results (Table
that S3).mg
20
show Toofassess
that mg the
20catalystof
efficacy
is optimal of
to the process
achieve a
maximum series of reactions
benefit under were
the conducted
given conditions with different
(Table
catalyst is optimal to achieve maximum benefit under the given conditions (Table S3). To assess the S3). Tosubstituted
assess the aromatic
efficacy
aldehydes
of the process
efficacy of theas aprecursors
process under ofthe
series ofa reactions
series were optimized
conducted
reactions were conditions. Sm-FAp/Glycine
with different
conducted withsubstituted proved an
aromatic
different substituted excellent
aldehydes
aromatic
catalyst
as in as
precursors
aldehydes all under
reactions
the and
precursors produced
optimized
under respective
theconditions.
optimized thio-1,2,4-triazoles
Sm-FAp/Glycine
conditions. with an
proved
Sm-FAp/Glycine impressive
provedyields
excellent catalyst(Table
in all3,
an excellent
entries
reactions 1–4).
catalyst inand all produced
reactions and respective thio-1,2,4-triazoles
produced with impressive
respective thio-1,2,4-triazoles yields
with (Table 3,yields
impressive entries(Table
1–4). 3,
entries 1–4).

Scheme1.1.Typical
Scheme Typicalreaction.
reaction.
Scheme 1. Typical reaction.
Afterthe
After thefirst
first cycle,
cycle, the the catalyst
catalyst material
material was recovered
was recovered thorough thorough
vacuumvacuumfiltrationfiltration
and washed and
washed
with After with
water,the water, followed
first cycle,
followed by drying
the catalyst
by drying in vacuum in vacuum
material for
for 2 hwas
at 602 h
◦ at 60
recovered °C. The activity
thorough
C. The activity of recovered
vacuum filtration
of recovered catalyst
catalyst wasand
was tested
washed
tested with
for for
furtherfurther
water,cycles. cycles.
followed Thedrying
by catalyst
The catalyst in displayed
vacuum
displayed forexcellent
at 60efficiency
2 h efficiency
excellent °C. The for five
foractivity
five ofcycles
cycles withwith
<2%<2%
recovered lossloss
catalyst
of
of activity.
was tested
activity. OtherOther
for amino amino
furtheracid acid
cycles. assisted
The catalyst
assisted Sm-FAp
Sm-FApdisplayed showed about
excellent
showed about 6%–9% 6%–9%
efficiency decrease
decreaseforinfive in activity
cycles
activity bywith by the 5th
<2%cycle.
the 5th loss
cycle.
of
The The Other
activity.
recovery recovery
and amino andacid
reusability reusability
assisted
of of thewith
Sm-FAp
the catalyst catalyst
goodwith
showed aboutgood
catalytic catalytic
6%–9% performance
decrease
performance is in addedisadvantage
anactivity anthe
by added
5th
advantage
cycle.
in in synthesis.
The recovery
synthesis. and reusability of the catalyst with good catalytic performance is an added
advantage in synthesis.
Molecules 2016, 21, 1281 10 of 15

Molecules
Molecules
Molecules
Molecules
Molecules 2016,2016,
2016, 21,
2016,
2016, 21,
21, 1281
21, 1281
1281
21,1281
1281 1281 10ofof 15 10 of10
10 of 15of
1015of 15
15
Molecules
Molecules 2016,
2016,
Molecules 21,
2016, 21,
21, 1281
1281 of 1,2,4-triazolidine-3-thione moiety with different substituted aromatic 10 10
1015of
of 15
15
Table 3. List of synthesis
aldehydes with
Table 3. Sm-FAp/Glycine
Table
Table 3.
Table 3.
3. List
List
List of
List of of as
of synthesis
of synthesis of
synthesis
synthesis of heterogeneous
of catalyst
1,2,4-triazolidine-3-thione
1,2,4-triazolidine-3-thione
1,2,4-triazolidine-3-thione
1,2,4-triazolidine-3-thione *. with
moiety
moiety
moiety
moiety with
with
with different
different
different
different substituted
substituted
substituted
substituted aromatic
aromatic
aromatic
aromatic
Table
Table 3.3. List
Table
Table List
3. of synthesis
3. List
of
List synthesis
of
of of 1,2,4-triazolidine-3-thione
synthesis
of
synthesis 1,2,4-triazolidine-3-thione
of
of moiety
1,2,4-triazolidine-3-thione moiety
moiety
1,2,4-triazolidine-3-thione moietywith
with different
with
with substituted
different
different
different substituted
substituted
substitutedaromatic
aromatic
aromatic
aromatic
aldehydes
aldehydes
aldehydes
aldehydes
aldehydes
aldehydes with
with
withwith
with
with Sm-FAp/Glycine
Sm-FAp/Glycine
Sm-FAp/Glycine
Sm-FAp/Glycine
Sm-FAp/Glycine
Sm-FAp/Glycine as
as as
as heterogeneous
heterogeneous
heterogeneous
heterogeneous
asheterogeneous
heterogeneous
as heterogeneous catalyst
catalyst *.*. *.
*.
catalyst
catalyst
catalyst
catalyst *.
*.
aldehydes
aldehydeswith Sm-FAp/Glycine
with Sm-FAp/Glycine as as catalyst
heterogeneous *.
catalyst *.
Entry
Entry
Entry
Aldehyde
Aldehyde
Aldehyde
Product
Product
Product
Yield % % %Time
Yield
Yield
(min)
Time
Time (min)
(min)
Entry
Entry
Entry
Entry
Entry Aldehyde
Aldehyde
Aldehyde Product
Product
Product
Product
Product Yield
Yield
Yield
Yield %
%%
Yield
% %Time
Time
Time
Time
Time (min)
(min)
(min)
(min)
(min)
OCH
OCH OCH
OCH 33 HN
3 HN NH
OCH
OCH
OCH
OCH
OCH 3 33
3
OCH
33 33
OCH
OCH
OCH
OCH 3
OCH
OCH HN
HN
33HN33 HN
HN NHNH
HN NH
NH NH
NH
NH
CHO
CHO CHO
CHO
CHO
CHO
CHO CHO
1111 11 N
NN N SS S
N S 92
N
H
HH
N
N
H S S
H
S
S 92 92
92 92 92 15 15
15
15 15
H H
H
H H
H33CO
CO
HH333CO
CO
CO
H CO
CO OCH
OCHOCH
OCH
OCH
OCH
3 33
3 H H
H33CO
CO
HH333CO
CO CO OCH
OCHOCH
OCH
3 33
H 3 H3 3CO OCHOCH
33 3
3 H CO
3 H3
H CO
3CO
OCH
OCHOCH
3
OCH
33 33
CHO
CHOCHO
CHO HN
HN
HN HN
HN
HN NH
NH
NH NH
NH
NH
CHO
CHOCHO
CHO HN HN NH NH

2222 22 NN N
N SS S
S 93
N
HH H
H
N S
N
N
H
S
S
S 93 93
93 93 93 20 20
20
20
20 20
H H
H
Br Br
Br Br
Br
Br Br
Br
Br Br Br
Br
Br Br
Br
Br
CHO
CHO HNHN
HN
HN HN NHNH
NH
HN NH
NH NH
NH
CHO
CHO
CHO HN HN NH

N
NN N
N S
N SS S
S
N N S
H
HH H S S
H
3333 33 H H
H 96 96
96
96 96 96 15 15
15
15
15 15
H CO H33CO
HH3333CO
CO
H33
CO H H
H33CO
CO
HH333CO
CO
CO
H CO
CO
OCH
OCH H 3 H3 3CO
OCH
OCH
OCH 3 33
3 OCH
OCH
OCH
OCH
OCH 3
OCH 33
33 33 OCH 3
OCH
33 3 3
HN
HN
HNHN NHNH
NH
HN NH
NH NH
CHO
CHO
CHO
CHO HN HNHN NH
NH
CHO
4 4 N
NN N SS S
S
N S
N S 94 94 10
444 4 N
H
HH N
H
H
H
S
S 94 94
94 94
94 94 10 10
10
10 10
H H
Et Et
Et Et
Et Et Et
Et
Et
Et Et
Et
Et
** Reaction
*** Reaction
Reaction
Reaction
Reaction
** Reaction conditions:
conditions:
conditions:
conditions:
conditions: substituted
substituted
substituted
substituted
substituted
conditions: substituted benzaldehyde
benzaldehyde
benzaldehyde
benzaldehyde
benzaldehyde
benzaldehyde (1.0(1.0
(1.0
(1.0 (1.0 mmol),
mmol),
mmol),
mmol),
mmol),
(1.0 thiosemicarbazide
thiosemicarbazide (1.0(1.0
(1.0
thiosemicarbazide
thiosemicarbazide
thiosemicarbazide
mmol), (1.0
thiosemicarbazide (1.0 mmol)
mmol)
mmol)
mmol)
mmol)
(1.0 catalyst
catalyst
catalyst
catalyst
catalyst
mmol) catalyst
* Reaction conditions:
Reaction substituted
conditions: substituted benzaldehyde
benzaldehyde(1.0 mmol), thiosemicarbazide (1.0 mmol) catalyst
* Reaction
and
and conditions:
and
and ethanol
ethanol (5.0
ethanol
ethanol (5.0substituted
(5.0
mL)
(5.0
mL) mL)
were
mL)
were benzaldehyde
were
were stirred
stirred at
stirred
stirred at at
room
at
room room mmol),(1.0
(1.0temperature.
temperature.
room temperature.
temperature.
mmol), thiosemicarbazide
thiosemicarbazide (1.0 mmol)(1.0 mmol)
catalyst catalyst
and ethanol
andand ethanol
ethanol(5.0(5.0
mL) were
mL) stirred
were atatroom
stirred room
at
at room temperature.
temperature.
(5.0 mL)andwereethanol
and stirred(5.0
ethanol mL)
at(5.0
room were
mL) stirred
were stirred
temperature. temperature.
room temperature.

3.
3. Materials
3. Materials andand Methods
Methods
3.3.Materials
Materials and
Materials
and Methods
and Methods
Methods
3. Materials and Methods
3.1.3.1.
3.1. Materials
3.1. Materials
Materials
Materials
3.1. Materials
3.1. MaterialsAllAll analytical
analytical grade grade chemicals
chemicals werewere purchased
purchased and andused used without
without any any further
further purification.
purification.
AllAll
All analytical
analytical
analytical grade
grade grade chemicals
chemicals
chemicals were
werewere purchased
purchased
purchased and
and and used
used used without
withoutwithoutany
any anyfurther
further
further purification.
purification.
purification.
Calcium
Calcium
Calcium
Calcium nitrate,
nitrate,
nitrate,
nitrate, Ca(NO
Ca(NO Ca(NO
Ca(NO 33)33·4H
) 33)33·4H
·4H) ·4H O O
22O 22was
Owaswas
was purchased
purchased
purchased
purchased fromfrom
from
from Merck
Merck Merck
Merck (Darmstadt,
(Darmstadt,
(Darmstadt,
(Darmstadt, Germany),
Germany),
Germany),
Germany), Samarium
Samarium
Samarium
Samarium
All Calcium
analytical grade
nitrate, Ca(NO chemicals
3)3·4H
3 3 33 3 2O 2was
3 2 2 werepurchased
purchased fromand Merck used without Germany),
(Darmstadt, any further purification.
Samarium
nitrate,
nitrate,
nitrate, Sm(NOSm(NO
Sm(NO
nitrate, Sm(NO 33)33·6H
) 33)33·6H
·6H) ·6H O O
22O 22was
Owas was
was procured
procured
procured
procured fromfrom
from
from Sigma-Aldrich
Sigma-Aldrich
Sigma-Aldrich
Sigma-Aldrich (St.
(St.(St.
Louis,Louis,
Louis,
(St. MO,
MO,
Louis, MO,
MO,USA),USA),
USA), Amino
Amino
Amino
USA), Amino acids
acids
acids
acids
Calciumnitrate,
nitrate, Sm(NO
Ca(NO
(glutamic
(glutamic acid,
3)3·6H
acid,
3 3
)3 3
3 3·24H
3 aspartic
aspartic 3
O 2was
2 2
O
2 acid,
acid, wasprocured
purchased
glycine,
glycine,
from Sigma-Aldrich
from
histidine)
histidine) wereMerck
were
(St. Louis, MO,
(Darmstadt,
purchased
purchased from from
BDHBDH
USA), Amino
Germany), Samarium
chemicals
chemicals LtdLtd
acids nitrate,
(Poole,
(Poole,
(glutamic
(glutamic acid,
acid, asparticaspartic acid, acid, glycine,
glycine, histidine)
histidine)were
were purchased
(glutamic acid, aspartic acid, glycine, histidine) were purchased from BDH chemicals Ltd (Poole, purchased from BDH
from BDH chemicals
chemicals Ltd
Ltd(Poole,
(Poole,
Sm(NO3UK).)3 ·UK).
6H 2O was
Other
Other procured
reactants
reactants such such as from
as Sigma-Aldrich
tri-sodium
tri-sodium phosphate
phosphate Na(St. 33Louis, MO, USA), Amino acids (glutamic
UK).
UK). Other
UK). Other
Other reactants
reactants
reactants such
such such asastri-sodium
tri-sodium
as tri-sodium phosphate
phosphate
phosphate Na333Na
Na
(PO
3(PO
Na
(PO
(PO
33(PO
44)·12H
44)·12H
4)·12H
22O
44)·12H
4)·12H 2O
22O and
and
2Oand
22and
O and sodium
sodium
sodium
sodium
sodium
fluoride,
fluoride,
fluoride, NaF
NaF
fluoride,
fluoride, NaF
NaF
were
NaF were
were
werewere
acid, aspartic
purchasedacid,
purchased
purchased
purchased
purchased
fromglycine,
from
from
from
from Merck.
Merck.
Merck.
Merck.
Merck. histidine)
Water
Water
Water
Water
Water used
used
used
were
used
in
used in
all
inall
in
purchased
all experiments
experiments
allexperiments
in experiments
all experimentsis from
is
highly
isishighly
highly BDH
highly
is highly purifiedchemicals
purified
purified
purified
purified
deionized
deionized
deionizedLtd
deionized
deionized
(Poole,
water.
water.
water.
water.
water.
UK). Other
reactants such as tri-sodium phosphate Na3 (PO4 )·12H2 O and sodium fluoride, NaF were purchased
3.2.3.2.
3.2. Preparation
Preparation
Preparation of
of Sm-FAp Sm-FAp by by
Using Using Amino
Amino Acids
Acids
from Merck.
3.2. 3.2. Preparation
Water
Preparation ofofSm-FAp
used Sm-FAp
ofin Sm-FApall by byUsingUsing
by
experiments UsingAmino
Amino
Amino isAcids
Acids purified deionized water.
highly
Acids
A A typical
typical solution
solution of of
of 25.0
25.0 mLmL
mL deionized
deionized water
water containing
containing thethe
the mixture
mixture of of
of 1.51.5
1.5 mmol
mmol
AA Atypical
typical
typical solution
solution
solution of 25.0
of 25.0
25.0 mLmLdeionized
deionized water
deionized water
water containing
containing
containing the mixture
the mixture
mixture of of
1.5 mmol
1.5 mmol
mmol
3.2. Preparation
Na333Na
Na
Na
PO333PO
3PO
Na
PO 34PO
of4444·12H
44·12H
4·12H
·12H Sm-FAp
·12H
2O
O
2O
(0.570
22O 22(0.570
2O 2(0.570
byg),
(0.570 Using
g),
g),
(0.570 g),
2.02.0
2.0
g),
2.0 Amino
mmolmmol
mmol
2.0
mmol
of Acids
of glutamic
glutamic
of glutamic
mmol
of glutamic
of acid
glutamic acid
acid
acid
(0.330
(0.330
(0.330
acid g) g)
and
g) and
(0.330
(0.330 g)
and
and
g) and0.50.5
0.5
0.5
mmolmmol
mmol
0.5
mmol
of of
NaF
of NaF
mmol
of NaF
of NaF (0.020
(0.020
(0.020
NaF g) g) were
were
g) were
(0.020
(0.020 g) were
g) were
stirred
stirred
stirred continuously
continuously
continuously
stirred until
until
until
continuously until aa clear
aaclear
clear solution
solution
solution
clear waswas
was
solution obtained.
obtained.
obtained.
was After
After
After
obtained. adjusting
adjusting
adjusting
After thethe
the
adjusting pHpH
pH
the of
pH of
thethe
ofthe
of solution
solution
solution
the to
solution to
11–11–
to11–
to 11–
stirred
A typical continuously
stirred continuously
solution of until
25.0 a clear
until
mL solution
adeionized
clear solution was
water obtained.
was obtained.
containing After adjusting
After
the the the
adjusting
mixture pH of the
pH
ofvigorous
1.5 of solution
the
mmol Na3to
solution PO 11–
to ·11–
11.5 11.5
with with1M 11 NaOH,
M NaOH, 2.5 4 12H2 O
11.5
11.5 with
11.5
with with11MM MNaOH,
NaOH,NaOH, 2.52.5
2.5
mmol
mmol
2.5
mmol
mmol
mmol of
of
of
Ca(NO
ofCa(NO
of Ca(NO
Ca(NO
Ca(NO 3)3)
3·4H
33)33·4H
33)33·4H
3·4H
33)33·4H
2O
22O (0.5903
22O (0.5903
2O(0.5903
22(0.5903
O (0.5903 g)
g)
g)
was
g)was
was
g) was
was added
added
added
added
added
withwith
with
withwith vigorous
vigorous
vigorous
vigorous
stirring.
stirring.
stirring.
stirring.
stirring.
After
After
After
AfterAfter
(0.570 g),few
2.0
fewfew
few mmol
minutes,
minutes,
minutes,
minutes, of glutamic
5.0%5.0%
5.0%
5.0% molar
molar
molar
molar acid (0.330
concentration
concentration
concentration
concentration g)
of and
of
Sm(NO
ofSm(NO
Sm(NO
of Sm(NO
Sm(NO 0.5 3)
mmol
33)33·6H
33)33·6H
3·6H
33)33·6H
22Oof
22O (0.074
2O(0.074
NaF
(0.074
22(0.074
O (0.074g) (0.020
g)
was
g)was
was
g) was added
added
added
was g)
added were stirred
slowly
slowly
slowly
slowlyto to
the
tothe the
thethe
to continuously
solution
solution
solution
solution
few minutes, 5.0% molar concentration of 3) 3·6H 2O g) added slowly to solution
until a clear followed
followedsolution
followed withwith
with was continuous
continuous
obtained.
continuous stirring
stirring
stirringAfter forfor
for aboutabout
adjusting
about 5 h. 55 The
h.
theThe beaker
pH beaker was
of was
the was
thenthen
solution allowed
allowed to
to 11–11.5 to stand
stand forfor
for
with 10 10
Mmin
min
101min NaOH,
followed
followed with with continuous
continuous stirring
stirring for for
aboutabout 55h. h. The
h.
The The beaker
beakerbeaker was wasthen
thenthenallowed
allowed
allowed tostand
to stand
to standfor for
10 min
10 min
and andthen then centrifuged
centrifuged at at
2000 2000rpm rpm followed
followed by by
severalseveral washings
washings withwith deionized
deionized water.
water. After
After
2.5 mmol and of
andand Ca(NO
then
then then 3 )3 ·4H2 O
centrifuged
centrifuged
centrifuged at(0.5903
at 2000
at
2000 2000 rpm
rpm g)
rpmwas
followed added
followed
followed bybyby with
several
several vigorous
several washings stirring.
washings
washings with
withwith After few
deionized
deionized
deionized minutes,
water.
water.
water. After5.0%
After
After
decanting
decanting
decanting thethe
the supernatant
supernatant
supernatant solution,
solution, the the
samplessamples were were collected
collected and and dried.
dried. The Thedrieddried samples
samples werewere
decanting
molar concentration
decanting the theofsupernatant 3solution,
Sm(NOsolution,
supernatant )3solution,
·6H2 O the(0.074
the samples
the
samplessamples g)were were
waswere collected
collected
added
collected andand
slowly
and dried.
dried.
dried. The
to The
the The dried
dried
solution
dried samples
samples
samplesfollowedwere
werewerewith
calcinated
calcinated
calcinated
calcinated to
to to
350
350
to 350
°C
°C
350 °C
for
for
°C for
33hh33in
for h
in
h ain
a
in aa flow
flow
flow of
flowof of
air.
air.
of air.
The
The
air. The
Thesame
same same
same procedure
procedure
procedure
procedure was
waswas
was repeated
repeated
repeated
repeated for
for for
the
the
for the preparation
preparation
preparation
the preparation of of
of of
calcinated
continuous stirring to for
350 about
°C for 35 hh.inThe a flow of air.was
beaker Thethen sameallowed procedure to was repeated
stand for 10 for
min theandpreparation
then of
centrifuged
otherother
other
otherthreethree
three
three samples
samples
samples
samples using
using
using
using eithereither
either
either2.0
2.02.0
mmol
mmol
2.0 mmol
mmol ofof of aspartic
aspartic
aspartic
of aspartic acid
acidacid (0.266
(0.266
(0.266
acid g),
g),
(0.266 g), glycine
glycine
glycine
g), glycine (0.150(0.150
(0.150 g)
(0.150g) g)
or
or
g) or histidine
histidine
histidine
or histidine
other three samples using either 2.0 mmol of aspartic acid (0.266 g), glycine (0.150 g) or histidine
at 2000 rpm followed
(0.310
(0.310 g). by several washings with deionized water. After 44 decanting the supernatant
(0.310
(0.310
(0.310 g).g).
g). AllAll
All
g).
All thethe
the
All
the the four
four
four
four
four
synthesized
synthesized
synthesized
synthesized
synthesized
materials
materials
materials
materials
materials
were
were
were
were
were characterized.
characterized.
characterized.
characterized.
characterized.
Table
Table
Table
Table
summarizes
4 summarizes
44summarizes
Table summarizes
summarizes thethe
the
the
details
details
details
the details
details of of
of
of of
solution,the
thethe
the samples
sample
sample were collected
proportions.
proportions. and dried. The dried samples were calcinated to 350 ◦ C for 3 h in
thethe
sample
sample
sample proportions.
proportions.
proportions.
a flow of air. The same procedure was repeated for the preparation of other three samples using either
2.0 mmol of aspartic acid (0.266 g), glycine (0.150 g) or histidine (0.310 g). All the four synthesized
materials were characterized. Table 4 summarizes the details of the sample proportions.
Molecules 2016, 21, 1281 11 of 15

Table 4. Chemical composition of amino assisted Sm-FAp.

Ca(NO3 )3 ·4H2 O Na3 PO4 ·12 H2 O Amino Acid

Sample Sm(NO3 )3 ·6H2 O NaF (mmol)
(mmol) (mmol) (2.0 mmol)
a 2.5 0.074 g 1.5 0.5 Glutamic acid (0.330 g)
b 2.5 0.074 g 1.5 0.5 Aspartic acid (0.266 g)
c 2.5 0.074 g 1.5 0.5 Glycine (0.150 g)
d 2.5 0.074 g 1.5 0.5 Histidine (0.310 g)

3.3. Characterization
The synthesized products were investigated by powder X-ray diffractometry (Bruker D8 Advance
diffractometer with Ni filtered Cu Kα radiation, V = 45 kV, I = 40 mA) for identifying the phase and
crystallinity. The spectra were recorded on a preferential scan rate of 2◦ /min and a step size of 0.02◦ in
a 2θ range of 10◦ to 70◦ at room temperature. FT-IR was conducted on Perkin Elmer, Spectrum 100
spectrometer (Waltham, MA, USA) over a range of 4000 to 400 cm−1 at resolution of 4 cm−1 to
detect the phosphate bands for confirmation of the formation of fluorapatites. Morphology, size and
nanostructure of the products were investigated using a field emission scanning electron microscope
(FESEM, Zeiss Ultra Plus, Göttingen, Germany) operating at 5–20 kV and a high resolution transmission
electron microscope (HRTEM, JEOL 2100, Hitachi, Japan) with an accelerating voltage of 200 kV.
All samples were coated with an Au film to get a good resolution for FESEM. The identification and
confirmation of fluorine and samarium in the products was carried out by the elemental analysis
through Electron dispersive X-ray (EDX, AZtec software, Oxford instruments, Oxon, UK) spectrometer
unit, attached to FESEM. The Sm loading was further determined by using Perkin Elmer Inductively
coupled plasma Optical Emission Spectrometer (ICP-OES, Shelton, CT, USA) Optima 5300 DV.
Prior to ICP analysis, samples were solubilized in aqua regia and homogenized by a microwave
digestion process. Textural properties, surface area and pore properties of products were determined
by N2 sorption isotherm using Micromeritics TriStar II 3020, Norcross, GA, USA at 77 K. Before
sorption measurement, all samples were promptly degassed whole night at 180 ◦ C to eliminate
the space occupied by unwanted gases. The TPD experiments were conducted on Micromeritics
Autochem 2020, Norcross, GA, USA to determine the acidic sites on the surface of the catalysts. Before
the conduct of TPD analysis, the samples were pretreated at 200 ◦ C under the helium flow to evacuate
the pores. Fluorescence measurements were performed using Perkin Elmer, LS-55 fluorescence
spectrophotometer (Waltham, MA, USA). Spectral data such as 1 H-NMR and 13 C-NMR for synthesized
organic products were recorded using a Bruker Advance 400 spectrometer (Salt Lake city, UT, USA) at
ambient temperature.

4. Conclusions
In summary, nanostructured Sm doped fluorapatites were prepared by a co-precipitation method
employing four different amino acids as growth modifiers. Amino acid assisted synthesis showed
varied characteristics in term of morphology, size, surface area and pore properties of the Sm-FAp.
The glycine-assisted sample exhibited the highest surface area relative to the other amino acids-assisted
samples. All samples exhibited desirable fluorescence, but their maximum emission wavelength
intensity varied with amino acid being used. Of all samples, the glycine-assisted sample displayed
the highest emission intensity at longer wavelengths, while histidine assisted sample showed a blue
shift, but with lower intensity. Amino acids used for growth modifications in the synthesis of materials
promptly alter the physical characteristics and which finally affect the properties as well as the possible
application of the materials. Glycine-assisted Sm-FAp showed the best catalytic activity towards value
added organic transformations of aromatic aldehyde to 1,2,4-triazole moiety with 98% yield. Structural
features of the catalysts play a prominent role and the choice of application of those materials greatly
depends upon their physical characteristics.
Molecules 2016, 21, 1281 12 of 15

Supplementary Materials: The following are available online at www.mdpi.com/1420-3049/21/10/1281/s1,

Table S1: Elemental analysis by EDX and ICP-OES, Table S2: Statistical report using ANOVA, Table S3:
Optimization of the amount of Sm-FAp/Glycine as catalyst in the model reactiona , Figure S1: X-ray
diffraction pattern of (a) FAp/without amino acid; (b) Sm-FAp/without amino acid; (c) Sm-FAp/Glutamic
acid; (d) Sm-FAp/Aspartic acid;+.2 (e) Sm-FAp/Glycine; (f) Sm-FAp/Histidine before annealing at 350 ◦ C,
Figures S2–S5: FT-IR, 1 H-, 15 N-, 13 C-NMR spectra of 5-(2-nitrophenyl)-1,2,4-triazolidine-3-thione, Figures S6–S17:
1 H-, 13 C-, 15 N-NMR spectra of entries 1–4.

Acknowledgments: The authors sincerely acknowledge the receipt of financial assistance and research facilities
from the National Research Foundation, Pretoria, South Africa and University of KwaZulu-Natal, Durban,
South Africa respectively.
Author Contributions: K.K.G. and S.M. conceived and designed the experiments; S.N.M. and K.K.G. performed
the experiments; K.K.G., S.M. and S.B.J. analyzed the data; K.K.G, S.M. and S.B.J. wrote the paper. All authors
read and approved the final manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Gomez, J.M.; Iafisco, M.; Delagado, J.M.; Sarda, S.; Drouet, C. Progress on the preparation of nanocrystalline
apatites and surface characterization: Overview of fundamental and applied aspects. Prog. Cryst. Growth
Charact. Mater. 2013, 59, 1–46. [CrossRef]
2. Sharifnabi, A.; Fathi, M.H.; Yekta, B.E.; Hossainalipour, M. The structural and bio-corrosion barrier
performance of Mg-substituted fluorapatite coating on 316Lstainlesssteel human body implant.
Appl. Surf. Sci. 2014, 288, 331–340. [CrossRef]
3. Kheradmandfard, M.; Fathi, M.H. Preparation and characterization of Mg-doped fluorapatite nanopowders
by sol–gel method. J. Alloy. Compd. 2010, 504, 141–145. [CrossRef]
4. Stanic, V.; Radosavljevic, A.S.; Radovanovic, V.Z.; Nastasijevic, B.; Cincovic, M.M.; Markovi, J.P.;
Budimir, M.D. Synthesis, structural characterisation and antibacterial activity of Ag+-doped fluorapatite
nanomaterials prepared by neutralization method. Appl. Surf. Sci. 2015, 337, 72–80. [CrossRef]
5. Nathanael, A.J.; Hong, S.I.; Mangalaraj, D.; Ponpandian, N.; Chen, P.C. Template free growth of
novel hydroxyapatite nanorings: Formation mechanism and their enhanced functional properties.
Cryst. Growth Des. 2012, 12, 3565–3574. [CrossRef]
6. Hu, X.; Zhu, J.; Li, X.; Zhang, X.; Meng, Q.; Yuan, L.; Zhang, J.; Fu, X.; Duan, X.; Chen, H.; et al. Dextran-coated
fluorapatite crystals doped with Yb3+ /Ho3+ for labeling and tracking chondrogenic differentiation of bone
marrow mesenchymal stem cells in vitro and in vivo. Biomaterials 2015, 52, 441–451. [CrossRef] [PubMed]
7. Bayliss, P.; Erd, D.C.; Mrose, M.E.; Sabina, A.P.; Smith, D.K. Mineral Powder Diffraction File Data Book; JCPDS
International Centre for Diffraction Data: Swarthmore, PA, USA, 1986; Powder Diffraction File Number:
15–876; p. 383.
8. Comodi, P.; Liu, Y.; Zanazzi, P.F.; Montagnoli, M. Structural and vibrational behaviour of fluorapatite with
pressure. Part 1: In situ single-crystal X-ray diffraction investigation. Phys. Chem. Miner. 2001, 28, 219–224.
[CrossRef]
9. Viipsi, K.; Sjorberg, S.; Tonsuaadu, K.; Shchukarev, A. Hydroxy- and fluorapatite as sorbents in Cd(II)–Zn(II)
multi-component solutions in the absence/presence of EDTA. J. Hazard. Mater. 2013, 252–253, 91–98.
10. Peld, M.; Tonsuaadu, K.; Bender, V. Sorption and Desorption of Cd2+ and Zn2+ Ions in Apatite-Aqueous
Systems. Environ. Sci. Technol. 2004, 38, 5626–5631. [CrossRef] [PubMed]
11. Maeda, Y.; Washitake, Y.; Nishimura, T.; Takahiro, I.; Keisuke, Y.; Takayoshi, U.; Uemura, S.
Calcium-phosphate vanadate apatite (CPVAP)-catalyzed aerobic oxidation of propargylic alcohols with
molecular oxygen. Tetrahedron 2004, 60, 9031–9036. [CrossRef]
12. Saber, A.; Smahi, A.; Solhy, A.; Nazih, R.; Elaabar, B.; Maizi, M.; Sebti, S. Heterogeneous catalysis of
Friedel-Crafts alkylation by the fluorapatite alone and doped with metal halides. J. Mol. Catal. A Chem. 2003,
202, 229–237. [CrossRef]
13. Venugopal, A.; Scurrell, M.S. Hydroxyapatite as a novel support for gold and ruthenium catalysts: Behaviour
in the water gas shift reaction. Appl. Catal. A 2003, 245, 137–147. [CrossRef]
14. Mondelli, C.; Ferri, D.; Baiker, A. Ruthenium at work in Ru-hydroxyapatite during the aerobic oxidation of
benzyl alcohol: An in situ ATR-IR spectroscopy study. J. Catal. 2008, 258, 170–176. [CrossRef]
Molecules 2016, 21, 1281 13 of 15

15. Kaneda, K.; Mizugaki, T. Development of concerto metal catalysts using apatite compounds for green organic
syntheses. Energy Environ. Sci. 2009, 2, 655–673. [CrossRef]
16. Wang, K.; Kennedy, G.J.; Cook, R.A. Hydroxyapatite-supported Rh(CO)2 (acac) (acac = acetylacetonate):
Structure characterization and catalysis for 1-hexene hydroformylation. J. Mol. Catal. A Chem. 2009, 298,
88–93. [CrossRef]
17. Gruselle, M. Apatites: A new family of catalysts in organic synthesis. J. Organomet. Chem. 2015, 793, 93–101.
[CrossRef]
18. Mohamed, Z.; Younes, A.; Ahmed, R.; Said, S.; Hamid, D.; Marc, D. Fluorapatite: Efficient catalyst for the
Michael addition. Tetrahedron Lett. 2003, 44, 2463–2465.
19. Hara, T.; Kanai, S.; Mori, K.; Mizugaki, T.; Ebitani, K.; Jitsukawa, K.; Kaneda, K. Highly Efficient C–C
Bond-Forming Reactions in Aqueous Media Catalyzed by Monomeric Vanadate Species in an Apatite
Framework. J. Org. Chem. 2006, 71, 7455–7462. [CrossRef] [PubMed]
20. Mason, H.E.; McCubbin, F.M.; Smirnov, A.; Phillips, B.L. Solid-state NMR and IR spectroscopic investigation
of the role of structural water and F in carbonate-rich fluorapatite. Am. Mineral. 2009, 94, 507–516. [CrossRef]
21. Gruselle, M.; Tonis, K.; Rene, T.; Alexandrine, F.; Kadri, K.; Valdek, M.; Rainer, T.; Birgit, M.; Kaia, T. Calcium
Hydroxyapatites as Efficient Catalysts for the Michael C–C Bond Formation. ACS Catal. 2011, 1, 1729–1733.
[CrossRef]
22. Yu, H.; Deng, D.G.; Li, Y.Q.; Xu, S.Q.; Li, Y.Y.; Yu, C.P.; Ding, Y.Y.; Lu, H.W.; Yin, H.Y.; Nie, Q.L. Electronic
structure and luminescent properties of Ca5 (PO4 )2 (SiO4 ):Eu2+ green-emitting phosphor for white light
emitting diodes. Opt. Commun. 2013, 289, 103–108. [CrossRef]
23. Shang, M.M.; Li, G.G.; Geng, D.L.; Yang, D.M.; Kang, X.J.; Zhang, Y.; Lian, H.Z.; Lin, J. Blue Emitting
Ca8 La2 (PO4 )6 O2 :Ce3+ /Eu2+ Phosphors with High Color Purity and Brightness for White LED: Soft-Chemical
Synthesis, Luminescence, and Energy Transfer Properties. J. Phys. Chem. C 2012, 116, 10222–10231. [CrossRef]
24. Wang, Q.; Ci, Z.P.; Wang, Y.H.; Zhu, G.; Wen, Y.; Shi, Y.R. Crystal structure, photoluminescence properties
and energy transfer of Ce3+ , Mn2+ co-activated Ca8 NaGd(PO4 )6F2 phosphor. Mater. Res. Bull. 2013, 48,
1065–1070. [CrossRef]
25. Michalis, K.; Sonia, A.C.C.; Pedro, B.T.; Josel, F. Redox properties and VOC oxidation activity of Cu catalysts
supportedon Ce1−x Smx Oδ mixed oxides. J. Hazard. Mater. 2013, 261, 512–521.
26. Dominguez, R.D.; Alarcon, F.G.; Aguilar, F.M.; Sanchez, A.R.I.; Falcony, C.; Dorantes, R.H.J.; González, V.J.L.;
Rivas, L.D.I. Effect on the stabilization of the anatase phase and luminescent properties of samarium-doped
TiO2 nanocrystals prepared by microwave irradiation. J. Alloy. Compd. 2016, 687, 121–129. [CrossRef]
27. Florence, H.; Marie, I.L.; Jean, L.N. A new preparation of samarium dibromide and its use in stoichiometric
and catalytic pinacol coupling reactions. Tetrahedron Lett. 2002, 44, 5507–5510.
28. Hua, Y.W.; Hai, B.W.; Xin, H.L.; Jian, H.L.; Mei, H.Y.; Chuan, J.H.; Wei, Z.W.; Hui, L.W. Samarium-modified
vanadium phosphate catalyst for the selective oxidation of n-butane to maleic anhydride. Appl. Surf. Sci.
2015, 351, 243–249.
29. Jiang, D.; Li, D.; Xie, J.; Zhu, J.; Chen, M.; Lu, X.; Dang, S. Shape-controlled synthesis of F-substituted
hydroxyapatite microcrystals in the presence of Na2 EDTA and citric acid. J. Colloid Interface Sci. 2010, 350,
30–38. [CrossRef] [PubMed]
30. Vasiliev, A.N.; Zlotnikov, E.; Khinast, J.G.; Riman, R.E. Chemisorption of silane compounds on
hydroxyapatites of various morphologies. Scr. Mater. 2008, 58, 1039–1042. [CrossRef]
31. Neira, I.S.; Kolenko, Y.V.; Lebedev, O.I.; Tendeloo, G.V.; Gupta, H.S.; Guitian, F.; Yoshimura, M. An Effective
Morphology Control of Hydroxyapatite Crystals via Hydrothermal Synthesis. Cryst. Growth Des. 2009, 9,
466–474. [CrossRef]
32. Zhiqiang, N.; Yadong, Li. Removal and Utilization of Capping Agents in Nanocatalysis. Chem. Mater. 2014,
26, 72–83.
33. Chen, H.; Sun, K.; Tang, Z.; Law, R.V.; Mansfield, J.F.; Jakubowska, A.C.; Clarkson, B.H. Synthesis of
Fluorapatite Nanorods and Nanowires by Direct Precipitation from Solution. Cryst. Growth Des. 2006, 6,
1504–1508. [CrossRef] [PubMed]
34. Jones, F.; Ogden, M.I. Controlling crystal growth with modifiers. CrystEngComm 2010, 12, 1016–1023.
[CrossRef]
Molecules 2016, 21, 1281 14 of 15

35. Hwang, E.T.; Tatavarty, R.; Chung, J.; Gu, M.B. New Functional Amorphous Calcium Phosphate
Nanocomposites by Enzyme-Assisted Biomineralization. ACS Appl. Mater. Interfaces 2013, 5, 532–537.
[CrossRef] [PubMed]
36. Maruyama, T.; Fujimoto, Y.; Maekawa, T. Synthesis of gold nanoparticles using various amino acids.
J. Colloid Interface Sci. 2015, 447, 254–257. [CrossRef] [PubMed]
37. Shankar, S.; Rhim, J.W. Amino acid mediated synthesis of silver nanoparticles andpreparation of
antimicrobial agar/silver nanoparticles composite films. Carbohydr. Polym. 2015, 130, 353–363. [CrossRef]
[PubMed]
38. Li, M.; Wu, X.; Zhou, J.; Kong, Q.; Li, C. Single-crystal Au microflakes modulated by amino acids and their
sensing and catalytic properties. J. Colloid Interface Sci. 2016, 467, 115–120. [CrossRef] [PubMed]
39. Srivastava, S.K.; Hasegawa, T.; Yamada, R.; Ogino, C.; Mizuhata, M.; Kondo, A. Green synthesis of Au, Pd
and Au@Pd core–shell nanoparticles via a tryptophan induced supramolecular interface. RSC Adv. 2013, 3,
18367–18372. [CrossRef]
40. Zhang, H.G.; Zhu, Q.S.; Wang, Y. Morphologically Controlled Synthesis of Hydroxyapatite with Partial
Substitution of Fluorine. Chem. Mater. 2005, 17, 5824–5830. [CrossRef]
41. Nasrollahzadeh, M.; Sajadi, S.M.; Mirzaei, Y. An efficient one-pot synthesis of 1,4-disubstituted 1,2,3-triazoles
at room temperature by green synthesized Cu NPs using Otostegia persica leaf extract. J. Colloid Interface Sci.
2016, 468, 156–162. [CrossRef] [PubMed]
42. Yu, W.; Jiang, L.; Shen, C.; Xu, W.; Zhang, P. A highly efficient synthesis of N-glycosyl-1,2,3-triazoles using a
recyclable cellulose-copper(0) catalyst in water. Catal. Commun. 2016, 79, 11–16. [CrossRef]
43. Iniyavan, P.; Balaji, G.L.; Sarveswari, S.; Vijayakumar, V. CuO nanoparticles: Synthesis and application as
an efficient reusable catalyst for the preparation of xanthene substituted 1,2,3-triazoles via click chemistry.
Tetrahedron Lett. 2015, 56, 5002–5009. [CrossRef]
44. Sahu, J.K.; Ganguly, S.; Kaushik, A. Triazoles: A valuable insight into recent developments and biological
activities. Chin. J. Nat. Med. 2013, 11, 456–465. [CrossRef]
45. Kumar, P.; Joshi, C.; Srivastava, A.K.; Gupta, P.; Boukherroub, R.; Jain, S.L. Visible Light Assisted
Photocatalytic [3 + 2] Azide–Alkyne “Click” Reaction for the Synthesis of 1,4-Substituted 1,2,3-Triazoles
Using a Novel Bimetallic Ru-Mn Complex. ACS Sustain. Chem. Eng. 2016, 4, 69–75. [CrossRef]
46. Turker, L. Azo-bridged triazoles: Green energetic materials. Def. Tech. 2016, 12, 1–15. [CrossRef]
47. Singh, S.; Jonnalagadda, S.B. Synthesis and characterization of thermally stable metal substituted
hydroxyapatites for the selective oxidation of light paraffins. Bull. Chem. Soc. Ethiop. 2013, 27, 57–68.
48. Pillai, M.K.; Singh, S.; Jonnalagadda, S.B. Solvent-free Knoevenagel condensation over Cobalt hydroxyapatite.
Synth. Commun. 2010, 41, 3710–3715. [CrossRef]
49. Singh, S.; Jonnalagadda, S.B. Selective oxidation of n-pentane over V2 O5 supported on hydroxyapatite.
Catal. Lett. 2008, 120, 200–206.
50. Pillai, M.K.; Singh, S.; Jonnalagadda, S.B. Solvent-free Knoevenagel condensation over iridium and platinum
hydroxyapatites. Kinet. Catal. 2011, 52, 536–539. [CrossRef]
51. Gangu, K.K.; Dadhich, A.S.; Mukkamala, S.B. Hydrothermal synthesis, crystal structure and luminescence
property of a three dimensional Sm(III) coordination polymer with 2,5-pyridinedicarboxylic acid. J. Chem. Sci.
2015, 127, 2225–2230. [CrossRef]
52. Palazzo, B.; Dominic, W.; Michele, L.; Elisabetta, F.; Luca, B.; Gianmario, M.; Claudia, L.B.; Giuseppe, C.;
Norberto, R. Amino acid synergetic effect on structure, morphology and surface properties of biomimetic
apatite nanocrystals. Acta Biomater. 2009, 5, 1241–1252. [CrossRef] [PubMed]
53. Antonakos, A.; Liarokapis, E.; Leventouri, T. Micro-Raman and FTIR studies of synthetic and natural apatites.
Biomaterials 2007, 28, 3043–3054. [CrossRef] [PubMed]
54. Frindell, K.L.; Bartl, M.H.; Popitsch, A.; Stucky, G.D. Sensitized Luminescence of Trivalent Europium by
Three-Dimensionally Arranged Anatase Nanocrystals in Mesostructured Titania Thin Films. Angew. Chem.
Int. Ed. 2002, 41, 959–962. [CrossRef]
55. Cuimiao, Z.; Shanshan, H.; Dongmei, Y.; Xiaojiao, K.; Mengmeng, S.; Chong, P.; Jun, L. Tunable luminescence
in Ce3+ , Mn2+ -codoped calcium fluorapatite through combining emissions and modulation of excitation:
A novel strategy to white light emission. J. Mater. Chem. 2010, 20, 6674–6680.
56. Zaitoun, M.A.; Momani, K.; Jaradat, Q.; Qurashi, I.M. Synthesis and luminescence properties of encapsulated
sol–gel glass samarium complexes. Spectrochim. Acta A 2013, 115, 810–814. [CrossRef] [PubMed]
 Molecules 2016, 21, 1281 15 of 15

57. Sreedhar, V.B.; Basavapoornima, C.H.; Jayasankar, C.K. Spectroscopic and fluorescence properties of
Sm3+ -doped zinc fluorophosphate glasses. J. Rare Earths 2014, 32, 918–926. [CrossRef]
58. Venkatramu, V.; Babu, P.; Jayasankar, C.K.; Troster, T.; Sievers, W.; Wortmann, G. Optical spectroscopy of
Sm3+ ions in phosphate and fluorophosphate glasses. Opt. Mater. 2007, 29, 1429–1439. [CrossRef]
59. Pramod, K.S.; Jilavi, M.H.; Nass, R.; Schmidt, H. Tailoring the particle size from µm→nm scale by using a
surface modifier and their size effect on the fluorescence properties of europium doped yttria. J. Lumin. 1999,
82, 187–193.
60. Kim, Y.; Kang, S. Effect of particle size on photoluminescence emission intensity in ZnO. Acta Mater. 2011, 59,
3024–3031. [CrossRef]
61. Rathinam, R.; Lalitha, A. PEG-assisted two-component approach for the facile synthesis of
5-aryl-1,2,4-triazolidine-3-thiones under catalyst-free conditions. RSC Adv. 2015, 5, 51188–51192.
62. Jayavant, D.P.; Pore, D.M. [C16 MPy]AlCl3 Br: An efficient novel ionic liquid for synthesis of novel
1,2,4-triazolidine-3-thiones in water. RSC Adv. 2014, 4, 14314–14319.
63. Mane, M.M.; Pore, D.M. A novel one pot multi-component strategy for facile synthesis of
5-aryl-[1,2,4]triazolidine-3-thiones. Tetrahedron Lett. 2014, 55, 6601–6604. [CrossRef]

Sample Availability: Samples of the compounds are available from the authors.

© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC-BY) license (http://creativecommons.org/licenses/by/4.0/).

View publication stats