3.1.

Characterization
…was used to approved the synthesized Fe3O4@HNTs-Doxorubicin PVA/Ca(OH)2/Au
nanocomposite Surveillance by Fourier-transform infrared (FTIR)As can be seen in Figure, two peaks
corresponding to AlO–H bonds of the alumina network in the inner surface of HNTs appear at 3626
and 3698 cm−1 [75]. The sharp peaks at 1050, 908, and 468 cm−1 can be assigned to bending
vibrations of Si–O–Si, AlO–H, and Al–O–H bands. The peaks at 536 cm−1 can be assigned to
bending vibrations of Si-O-Al band. In the spectra b, The two peaks of Al-O-H is are significantly
reduced in intensity after acid treatment and calcination. A broad peak shownshowed, successful
activation of Halloysite nanotubes, particular particularly the internal layers or alumina. The band Fe–
O stretching vibration and bending vibrations of Si-O-Al were Overlap and appeared at 570 cm−1 .
In the spectra c In figure C Tthe band of carbonyl functional group is confirmed by the appearance of
the peak at 1670cm−1 .the peak in 1629cm−1 can be assigned to C=C for an aromatic ring of
doxorubicin , In primary amines (RNH2), there are two bands in this region, the asymmetrical N–H
stretch and the symmetrical N–H stretch two bands from 3550 and 3250 cm-1. The characteristic band
broad peak around 3300 cm−1 is related to the stretching vibration of the O−H bands bonds in the
PVA structure. 1 according to the surfaces and pores of the silica network are covered with polymer
and drug, the peak intensity of the Si-O-Si bond decreases .
The Energy dispersive X-ray spectroscopy
The Energy dispersive X-ray spectroscopy in Figure identifies the presence of the elemental
composition of Fe3O4@HNTs-Doxorubicin PVA/Ca(OH)2/Au nanocomposite the C, N , Si , Al , Fe,
and O elements of PVA, Cu(OH)2, Doxorubicin , and Au are present in the nanocomposite film . The
presence oxygen , Aluminum and silicon atoms was were confirmed in all samples through the
appearance of the signals at 0.5 ,1.5 and 1.8 keV, respectively. The first and second released electrons
from the activated hallosyte structures caused peaks at 2.0 and 2.1 keV, respectively (spectrum b).
The appearance of AuNPs has been verified by a signal appeared at 2.0 keV (spectrum c). Also, two
weak peaks in the range of 2.0 keV confirm the successful combination of the AuNPs .Based on EDX
data, 43.60% of the total weight of the of Fe3O4@HNTs-Doxorubicin PVA/Ca(OH)2/Au corresponds
to oxygen , 5.62% to Nitrogen . The appearance of the Al signal (1.3% of the total weight)
originating from hallosyte halloysite also corroborates PVA attachment to HNTs. THe The
incorporation of AuNPs and calcium has been 0.45% ,0.25% of the total weight in the EDX data of
Fe3O4@HNTs-Doxorubicin PVA/Ca(OH)2/Au. that is related to PVA, In the same spectrum, as a
confirmation for the successful formation of the covalent bonds between the hallosyte and outer layer
of the PVA network. (spectrum d). Moreover, the distribution of the elements is visible by EDX
mapping images (Figure ).Finally, the abundance of the silicon, Ooxygen, Alminum,Ssi, calcium, and
gold elements in the sample have has been qualitatively confirmed .
vibrating-sample magnetometer (VSM) analysis.
The magnetic properties of the products were studied using vibrating-sample magnetometer (VSM)
analysis, and the corresponding M–H curves are shown in Figure 1a. Based on curve II in Figure ,
exhibits characteristic paramagnetic behavior with maximum saturation magnetization (Ms) of 60 emu
g−1 ) Based on these values, the magnetic shipping of the product to the target tissue may be
conveniently performed with the aid of using making use of an external magnetic field. Doxorubicin
drug loading had no effect on reducing the magnetization of halloysite nanotubes magnetized with
Fe3O4 particles, which is why (blue) and (red) graphs with saturation magnetism of approximately
(emu/g) 35 are superimposed. In addition, the final product (green diagram) shows the characteristic
behavior of paramagnetismPara magnetism, with a maximum saturation magnetization (emu/g) of 38.
As a result of this magnetic behavior, the magnetic delivery of the nanocarrier to the target tissue can
be easily achieved by applying an external magnetic field. It is expected that the saturation magnetism
of the final product with polymer coating will decrease with each layer, but with the presence of gold
nanoparticles, it increases by 3 °, which is probably due to the synergistic effect between the metal
nanoparticles and metal oxide. Therefore, gold nanoparticles coated with (vinyl alcohol) increased the
magnetic saturation .

Scanning Electron Microscopic Imaging.

The morphology, size, and composition state of the Fe3O4@HNTs-Doxorubicin PVA/Ca (OH)2/Au
nanocomposite was investigated with SEM (Figure). Fe3O4@HNTs-Doxorubicin PVA/Ca (OH)2/Au
, respectively Ffrom images a) and f) of Fig, it can be clearly seen that HNT morphology features have
openings that can be utilized for drug loading. The natural halloysite nanotubes are aggregated before
the ball milling process .(a). A Ddispersion of particles with a narrower size distribution was obtained
after milling ((b,c)). In addition, in figure (d), the points distributed on the halloysite nanotube show
the magnetic nanoparticles well. The outer surface of halloysite nanotubes has many pores, so it can be
expected that iron oxide nanoparticles are present in these pores. in figure (e)AuNPs with a mean
diameter of 100 nm were used for the incorporation into the exterior walls of the HNTs. The AuNPs
appear to have a near-spherical shape. Facets of the polyhedral AuNPs originating from the FCC fcc
structure of gold were apparent. AuNPs were prepared using a synthetic procedure similar to that used
for small seeds via reduction with borohydride, with no inherent shape selection. All possible seed
geometries were present (cubooctahedralcuboctahedra, icosahedral, and some decahedral) based on
our studies on similar AuNPs. shows that the roughness of the outer surfaces of the HNTs increased
significantly after the incorporation of AuNPs. According to the literature, the exterior surface of
HNTs is described as mesoporous []; therefore, AuNPs can be incorporated into these pores.
(f)Imaging was performed on a dispersed sample of the final product, in which the bright tiny dots
confirmed the presence of gold nanoparticles. The presence of a layer of natural polyvinyl alcohol
polymer prevented the accumulation of nanotubes, as can be seen in the figure .
Transmission electron microscopy TEM
Transmission electron microscopy TEM imaging confirms that the Fe3O4@HNTs-Doxorubicin -Ca
(OH)2 and AuNPs were uniformly integrated through the PVA polymer network to form the desired
hybrid nanocomposite. (Figure 2f). Of course, it should be noted that the data obtained from the
dynamic light scattering analysis shows that the particle size is about 20 nm, which is also predictable
because the measurement is based on the water-covered state of the sample. The presence of a thin
layer around the nanotubes is the proof of the existence of the polymer, which has worked well as a
cap for the open space of the nanotubes.
Dynamic-Light Scattering (DLS)
It is important to study whether Thethe prepared nanocomposite was stable in the solution . To
establish this, dynamic light uneven (DLS) calculations were performed (Figure). Bbecause the basis
of the performance of this analysis The performance of this analysis is based on the Brownian motion
of particulate matter in the fluid phase. To establish this, dynamic light uneven (DLS) calculations
were performed (Figure). It shows a broad peak with an average size of approximately 2 µm. While
after the grinding process (red curve), the average size of the particles has reached below 1 μm (as
confirmed by scanning electron microscope imaging), and its with a second peak at about 2.5 μm
shows the accumulation of particles. The EM observations depicted in Figure are in good agreement
with this increase in the size of 1 μm brought about by the PVA coating. Particle aggregation occurs
because of hydrogen bonding between the composite NPs and PVA molecules. This expansion in size
is also confirmed by DLS measurements (Figure). Figure The figure depicts FESEM images at a
higher magnification of the aggregated and individual PVA-encapsulated Fe3O4@HNTs-Doxorubicin
PVA/Ca (OH)2/Au NPs (product). Furthermore, uniform peripheral attachment of AuNPs to the PVA
shell (Figure ) was observed. In addition, a diagram of dynamic light scattering analysis for the
prepared gold nanoparticles is given in Figure (4-5). As can be seen from the shape and size of the
scanning electron microscope images and dynamic light scattering analysis of gold nanoparticles
According to the SEM and DLS analysis, these particles have shown a uniform particle size
distribution with a size of 30 nm.

XRD
X-ray powder diffraction (XRD) spectroscopy was used to obtain more confirmation on the presence
of the used ingredients in the structure of the Fe3O4@HNT composite in the solid state. The XRD
patterns of the HNT and Fe3O4@HNT are shown in Fig the XRD patterns of Fe3O4@HNT was were
successfully provided. The crystalline reflections at the diffraction angles (2θ) of 30.08, 35.54, 43.27,
57.11, and 62.80 degrees as marked in Fig. These peak positions and relative peak intensities
corresponded to the characteristic peaks of Fe3O4 ref The XRD pattern of the Halloysite showed
distinct diffraction peaks due to the crystalline property of the HNTs. This XRD pattern was indexed
to ICDD (International Centre for Diffraction Data) 00-029-1487. The crystal structures of natural and
acid treated acid-treated halloysites were studied by X-ray diffraction. During acid treatment, the
characteristic peaks of quartz and alunite were preserved. The characteristic (0 0 1) , and the peak of
halloysite (0.01) disappeared. As acid treatment durations increased, the characteristic peaks of
halloysite-(7A )˚ at (2θ) of 12.36◦, 18.18◦ and 25.28◦ started to decrease. Ref*..in this work for
activation HNT with Calcination and acid treatment, Tthe intensity of the broad peak increases with
acid treatment durations, indicating enhanced destruction by hydrochloric acid .

Ultraviolet-Visible Diffuse Reflectance Spectroscopy (UV-DRS)

To verify successful loading of doxorubicin into the hallosyte, solid-state UV−visible diffuse
reflectance spectroscopy (UV-DRS) spectra were compared with the individual magnetized halloysite
nanotubes and Fe3O4@HNTs-Doxorubicin PVA/Ca (OH)2/Au spectrum. As shown in Figure The
optical properties of the samples have been shown, the activity of magnetized halloysite nanotubes
showed strong absorption in the ultraviolet region with a wavelength less than 300 nm, which can be
attributed to the intrinsic absorption of its molecular chains.. Halloysite has strong absorption in this
range, which is probably due to the inherent absorption of Si-O-Si and Al-O-Si. (purple curve)
Compared to the spectrum of magnetic halloysite without polymer coating (red curve) , the spectrum
of halloysite nanotubes with natural polymer coating and gold nanoparticles (green curve) showed
significant visible-light absorption, indicating the success of the final product. Based on these
observations, it can be concluded that the incorporation of AuNPs significantly increases the optical
activity of the prepared nanocarrier and makes it suitable for photothermal treatment. It suits This
increase in light absorption activity can be attributed to active functional groups in the chemical
structure of doxorubicin.
BET Surface Area Analysis
The adsorption/desorption of N2 gas Brunauer−Emmett−Teller (BET) surface area analysis was used
to evaluate the porosity type of the samples. As presented in Figure, the BET surface area, pore
volume, and average pore width for the neat halloysite Nanotube (HNTs) (red curves) are 368.39
m2/g, 0.50 cm3/g, and 54.97 nm, indicating type IV isotherm of the mesoporous materials with very
narrow capillary pores. The results of halloysite nanotube analysis showed that the surface area and
the average size of the holes are 187.90 m2/g and 98.89 nm, respectively After placing iron oxide
nanoparticles on the surface of halloysite nanotubes (yellow curve), the specific surface area has
decreased and the size of the holes has increased. With drug loading, the pore volume of halloysite
nanotubes has decreased significantly, which indicates the placement of drug molecules in the
nanotube cavities. As expected, these values decreased to 153.13 m2/g, 0.41 cm3/g, and 107.88 nm
after the incorporation of doxorubicin into the pores (green curve). Tthe BET surface area was By
placing the polymer coating on the surface, it has increased the average size of the holes and the
specific surface compared to the previous stage. (purple curve). The most likely explanation is that the
PVA matrix causes particle aggregation and integration, forming heterogeneous and diverse voids
within the network. These results will demonstrate the successful loading of doxorubicin into the pores
and surface coating of the particles during the stepwise manufacturing process.