Single source precursor synthesized CuS nanoparticles for NIR phototherapy of cancer and photodegradation of organic carcinogen

Article abstract of DOI:10.1016/j.jphotobiol.2020.112084

Herein, we report cost effective and body compatible CuS nanoparticles (NPs) derived from a single source precursor as photothermal agent for healing deep cancer and photocatalytic remediation of organic carcinogens. These NPs efficiently kill MCF7 cells

Full text of DOI:10.1016/j.jphotobiol.2020.112084

Journal of Photochemistry & Photobiology, B: Biology xxx (xxxx) xxx
Contents lists available at ScienceDirect
Journal of Photochemistry & Photobiology, B: Biology
journal homepage: www.elsevier.com/locate/jphotobiol
Single source precursor synthesized CuS nanoparticles for NIR
phototherapy of cancer and photodegradation of organic carcinogen
a
b
a
c
c
Mehwish Arshad , Zhaojie Wang , Jamal Abdul Nasir , Eric Amador , Mingwu Jin ,
c
b
a,
*
c,*
Haibin Li , Zhigang Chen , Zia ur Rehman , Wei Chen
a
Department of Chemistry, Quaid-i-Azam University, 45320 Islamabad, Pakistan
b
College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
c
Department of Physics, University of Texas at Arlington, Arlington, TX 76019, USA
A R T I C L E I N F O
A B S T R A C T
Keywords:
Herein, we report cost effective and body compatible CuS nanoparticles (NPs) derived from a single source
precursor as photothermal agent for healing deep cancer and photocatalytic remediation of organic carcinogens.
These NPs efficiently kill MCF7 cells (both in vivo and in vitro) under NIR irradiation by raising the temperature of
tumor cells. Such materials can be used for the treatment of deep cancer as they can produce a heating effect
using high wavelength and deeply penetrating NIR radiation. Furthermore, CuS NPs under solar light irradiation
efficiently convert p-nitrophenol (PNP), an environmental carcinogen, to p-aminophenol (PAP) of pharmaceu-
tical implication. In a nutshell, CuS can be used for the treatment of deep cancer and for the remediation of
carcinogenic pollutants. There seems an intrinsic connection between the two functions of CuS NPs that need to
be explored in length.
CuS nanoparticles
Carcinogen
Photocatalysis
Phototherapy
Anticancer
1
. Introduction
In the modern world, better diagnosis and treatment modalities are
penetration power, imparting sufficient intensity to the tissues, and
higher spatial precision [10–12]. Nevertheless, efficient strategies are
desirable to transduce radiation into heat and discriminate tumor from
normal tissues [13,14]. In this context, the use of photothermal agents in
the NIR region to produce localized heat can be a commendable
approach. Nanomaterial-based photothermal therapy (PTT), in which
conversion of photon energy to heat induces cell destruction, has been
well explored and considered as a marginally invasive oncological
treatment. With the remarkable progress in nanotechnology, gold
nanostructures [12,17,19] carbon nanotubes [2,15], and copper sulfide
NPs [16–19]have been extensively studied for PTT in the NIR region.
In this quest, CuS-based NPs, with a broad absorption capability from
700 to 1100 nm, have emerged as efficient localized heat producing
materials upon NIR light irradiation [20]. To prepare CuS NPs, the
single-source precursor (SSP) technique is considered as one of the most
efficient and standard approache especially for the preparation of metal
chalcogen (MC) NPs [21,22]. In this method, the size and shape of NPs
can be easily tuned by changing the reaction time and temperature of the
thermolysis process [23]. The binding strength of the ligand to the metal
in the precursor complex determines the thermal stability and decom-
position kinetics, therefore, can control the growth mechanism of the
direly needed to fight against cancer. Among these strategies, hyper-
thermia is receiving the utmost attention owing to its effective and
relatively non-invasive behavior [1,2]. Hyperthermia is the heat treat-
◦
◦
ment of tissue in the temperature range 41 C - 45 C for tens of minutes
3,4]. During this heating process, tumors are destroyed preferentially
[
owing to the low blood supply and low heat tolerance than normal tis-
sues [1,5]. Hyperthermia of cancer cells could induce irreparable dam-
age to cell membranes and denature proteins [6,7]. Furthermore,
hyperthermia when combined with chemo- and radio-therapies, under
mild temperature increases, can enhance both perfusion and oxygena-
tion in tumor tissues, thus making the chemotherapy and radiotherapy
more effective [8].
Numerous approaches including radiofrequency pulses, microwave
irradiation and ultrasound have been explored to deliver thermal energy
in a non-optical fashion to penetrate deeply into tissues. However, high
care may be required because of the possibility of producing unwanted
hyperthermic effects in nearby normal tissues [9]. Irradiation of near-
infrared (NIR) Laser can induce localized hyperthermia due to its deep
*
Corresponding authors.
E-mail addresses: zrehman@qau.edu.pk, hafizqau@yahoo.com (Z. Rehman), weichen@uta.edu (W. Chen).
https://doi.org/10.1016/j.jphotobiol.2020.112084
Received 1 June 2020; Received in revised form 1 November 2020; Accepted 9 November 2020
Available online 11 November 2020
1
011-1344/© 2020 Published by Elsevier B.V.
Please cite this article as: Mehwish Arshad, Journal of Photochemistry & Photobiology, B: Biology, https://doi.org/10.1016/j.jphotobiol.2020.112084

M. Arshad et al.
Journal of Photochemistry & Photobiology, B: Biology xxx (xxxx) xxx
Scheme 1. Synthesis of copper(II) precursor and CuS NPs.
JEM-2100). The FTIR absorption spectrum was recorded on a Bio-Rad
MC NPs [24].
ꢀ 1
As a photothermal agent, CuS NPs have some advantages including
easy and simple preparation, low cost and nano-size for targeting
Excalibur FTS model 3000MX in the frequency range of 4000–400 cm
.2. Synthesis of Single Source Precursor
Sodium 4-chlorobenzyl(butyl)carbamodithioate ligand and its cop-
.
[
25,26]. Similar to PTT, photodynamic therapy (PDT) is another effec-
2
tive photon mediated cancer treatment strategy, in which photoexcita-
tion of the photosensitizers (PSs) generate highly reactive oxygen
1
species (ROS) namely singlet oxygen ( O
2
), hydroxyl radicals (•OH) and
per complex were synthesized according to previous literature [22,40]
with slight modifications. 4-Chlorobenzaldehyde (35.6 mmol, 5 g) and
butylamine (35.6 mmol, 2.6 g) dissolved in methanol were mixed at
room temperature with constant stirring for 24 h. Yellow thick product
was obtained after evaporating solvent under low pressure. Afterward,
the product (E)-N-(4-chlorobenzylidene)butan-1-amine (25.2 mmol, 5
g) was solubilized in 20 mL methanol followed by the addition of sodium
borohydride (in excess, 48.2 mmol, 1.93 g) at room temperature. After 4
h of stirring, the solution was filtered and the filtrate was evaporated
under reduced pressure to get a viscous product, N-(4-chlorobenzyl)
butan-1-amine. The product (4 g, 20 mmol) was then solubilized in
methanol (20 mL) and mixed with sodium hydroxide (NaOH, in excess,
peroxides (R-O-O•) for the annihilation of cancer cells [27]. From a
clinical perspective, an ideal PS is the one that can be excited in a
wavelength range of 700 nm - 1000 nm, a region well between the
human tissue optical window. Due to its unique physicochemical char-
acteristics, CuS-based NPs have been explored, most recently, as PTT
and PDT agents [25,28,29].
The treatment of carcinogenic environmental pollutants through safe
and environment friendly approaches is a hot research topic at present
time [30–33]. Nitrophenols, a group of carcinogenic pollutants, are
listed among the top organic pollutants by the US Environmental Pro-
tection Agency (EPA) [34]. Various disorders caused by these nitro-
aromatic compounds include methemoglobinemia, low ATP production,
damaging lungs, nervous system and skin disorders, dermatitis, hor-
monal disorders, renal failure, and eye irritations [35]. The reduction of
p-nitrophenol (PNP) to p-aminophenol (PAP) is an essential organic
transformation, as it converts the carcinogenic PNP pollutant into a
pharmaceutically valuable PAP, which can be used in antipyretic and
analgesic drugs such as paracetamol, corrosion inhibitor, lubricant and
dyeing agent [36]. However, this PNP-to-PAP conversion requires a
suitable catalyst. Various metal-based nanocatalysts have been used, but
in most cases, their application is hindered by factors like toxicity, low
activity, high cost and non-recyclable nature [37–39].
1
.42 g, 35.6 mmol) in a dropwise manner with constant stirring. After
dissolution of NaOH, methanolic carbon disulfide (in excess, 2.14 mL,
◦
3
5.6 mmol) was introduced dropwise into the reaction media at 0 C.
After 6 h of mixing, the solvent was evaporated to obtain sodium 4-
chlorobenzyl(butyl)carbamodithioate ligand (Fig. S1). The ligand (5 g,
1
6.9 mmol) was reacted with CuCl
2
•2H
2
O (1.5 g, 8.7 mmol) in
methanol-water mixture. After 3 h of stirring at room temperature, the
solution was filtered to obtain brown colored precipitates of copper(II)
2 2 4
dithiocarbamate (C24H30Cl CuN S ) that were washed with chloroform
and dried (Scheme 1).
Herein, we report cost-effective, stable, and easily recyclable CuS
NPs for the PPT and the conversion of a carcinogen of PNP to a phar-
maceutically valued product of PAP. As per our knowledge, this is the
primary article on CuS NPs covering both PPT (post-cancer treatment)
and carcinogen remediation (pre-cancer treatment).
2
.3. Synthesis of CuS Nanoparticles (NPs)
CuS NPs have been synthesized by thermolysis of SSP as described in
previous reports [36,42]. Copper(II) dithiocarbamate (1 g, 2 mmol) was
added into a three necked flask containing 12–14 mL of octylamine. The
◦
temperature was allowed to rise up to 180 C with continuous stirring.
2
. Experimental
The greenish black colored sulfide NPs were formed immediately. The
gas liberated was permitted to escape through a bent tube connected to a
test tube containing concentrated lead nitrate solution. The formation of
2
.1. Materials and Characterization
black color PbS NPs in the test tube indicated the release of H
2
S during
Chemicals were purchased from Sigma-Aldrich (4-chlor-
◦
the reaction. After an hour of stirring at 180 C, the suspension was
filtered and washed with methanol to obtain CuS NPs.
obenzaldehyde, butylamine, 4-nitrophenol, NaBH
4
octylamine) and
Riedel-de-Haen (CS and NaOH), and solvents (ethanol, chloroform,
2
methanol, diethyl ether, toluene, DMF, DCM) from Dae Jung and Fluka
companies. The melting point was measured by Sanyo electro thermal
melting point mechanical apparatus, and UV–Vis spectra of CuS and PNP
reduction by Shimadzu spectrophotometer 1800. The phase structures
2
.4. PNP Reduction on CuS NPs
1
0 mL solution of sodium borohydride (1 mM) was mixed with 10 mL
and other crystallographic parameters were identified by X-ray diffrac-
ꢀ 6
PNP solution (1 × 10 M) firstly, and then 40
μ
L aqueous suspension of
3
tion (XRD, PANalytical XʹPert , Cu-K
α: λ = 0.154 nm). Size, morphol-
CuS NPs (0.1 mg/30 mL) was added to it to initiate reduction. Then 3 mL
of the gently mixed solution was used to record the UV–Vis spectrum for
PNP conversion to PAP.
ogies and microstructures were determined by the scanning electron
microscope (SEM; S-4800) and transmission electron microscope (TEM,
2

M. Arshad et al.
Journal of Photochemistry & Photobiology, B: Biology xxx (xxxx) xxx
Fig. 1. (a) UV–Vis spectrum (b) XRD pattern (c) TEM and (d) HR-TEM images of CuS NPs.
2
.5. Optical and Photothermal Test
microscope.
Prior to the experiment, the CuS NPs and polyvinyl pyrrolidone
2
.7. In vivo PTT of Murine Tumors
(
PVP) were mixed with overnight stirring to evenly disperse in an
aqueous solution. The UV–Vis spectra were recorded via the UV–Vis-NIR
spectrophotometer (Youke Shanghai; UV1900). To quantify, the pho-
tothermal efficiencies of CuS-PVP NPs, a 1064 nm semiconductor laser
Experimental procedures and upkeep of mice were permitted by the
Animal Welfare and Research Ethics Committee of Donghua University.
Severe combined immunodeciency (SCID) mice were inoculated sub-
cutaneously with MCF7 cells for 14 days. Once the tumors nurtured in
size up to ~8 mm in diameter, 16 SCID mice were allocated randomly
into 4 groups (Control- group I; Laser-group II; CuS-PVP-group III; CuS-
PVP + Laser-group IV). For the treatment of the control and laser group,
(
Xi’an Tours Radium Hirsh Laser Technology Co., Ltd. China) was
irradiated on dispersions in a plastic tube and the temperature change
was noted by means of an infrared thermal imaging camera (FLIR A300).
2
.6. Cytotoxicity and in vitro PTT of Cancer Cells
100
and IV, 100
an hour, the groups II and IV mice were irradiated by the 1064 nm laser
μ
L saline solution was injected into the tumor, while for group III
ꢀ
1
μ
L of CuS-PVP (0.2 g L ) dispersed in PBS was used. After
The in vitro cytotoxicity of MCF7 breast adenocarcinoma cells was
ꢀ 2
studied via the Cell Counting Kit-8 (CCK-8) assay. The MCF7 cells were
(power density: 1.0 W cm ). After 10 min laser treatment, the tumors
were isolated, stained with hematoxylin/eosin (H&E), and then studied
using an inverted fluorescence microscope.
4
seeded into a 96-well cell culture plate (5 × 10 cells per well) in DMEM
(
Dulbecco’s modied Eagle’s medium). These plates were then placed in
◦
cell incubator containing 5% CO
2
at 37 C for 24 h. Afterward, cells were
ꢀ 1
incubated with CuS-PVP (0, 0.015, 0.03, 0.06, 0.12, 0.25, 0.50 g L in
DMEM) under aforesaid conditions. Subsequently, CCK-8 (10 L) was
3. Results and Discussion
μ
added into an individual well and incubated for an hour. The absorbance
of individual well, subtracting background at 450 nm, was recorded
through Multiskan MK3 monochromator-based multifunction micro-
plate reader.
3.1. Morphology, Crystal Phase and Optical Performance
In order to investigate the structural details and formation mecha-
nism of NPs, the FTIR analysis of the synthesized CuS NPs was under-
ꢀ
ꢀ 1
1
ꢀ 1
ꢀ 1
For the in vitro NIR-PTT of cancer cells, MCF7 cells in a 96-well
culture plate (104 cell/well) were incubated in the presence and
taken (Fig. S2). The absorption peaks at 2920 cm and 2927 cm
correspond to symmetric stretches while 2852 cm and 2843 cm
ꢀ
1
◦
absence CuS-PVP (0.2 g L ) for half an hour at 37 C. MCF7 cells were
peaks appear due to asymmetric stretches of the methylene group. The
presence of –NH group is indicated by stretching bands around 3432
ꢀ 2
then irradiated for 10 min by 1064 nm laser (1.0 W cm ). The standard
CCK-8 assay was used to determine relative cell viabilities. Furthermore,
the propidium iodide (PI) and calcein-AM were used for 15 min to stain
cells. After washing with PBS, the treated cells were imaged by a digital
2
ꢀ
1
ꢀ 1
ꢀ 1
H bending vibrations around 1592 cm
cm and 3440 cm and N
–
ꢀ
ꢀ 1
1
ꢀ 1
ꢀ 1
and 1577 cm . The peaks observed at 1362 cm , 1373 cm , 1007
ꢀ 1
ꢀ 1
ꢀ 1
cm , 997 cm , 715 cm and 731 cm are related to mixed stretching
3

M. Arshad et al.
Journal of Photochemistry & Photobiology, B: Biology xxx (xxxx) xxx
2
Fig. 2. Optical absorption and PTT performance of CuS-PVP dispersions under 1064 nm laser (1 W/cm ). (a) UV–Vis absorbance spectra of CuS-PVP dispersions with
different concentrations. The inset shows a photograph of a CuS dispersion (b) Plot of linear fitting of absorbance value at 1064 nm (A1064) vs concentration (c)
Temperature changes of CuS-PVP dispersions vs irradiation time and (d) Temperature changes in 300 s vs CuS concentration.
of N–C=S moiety [43–45]. The FTIR results show the presence of
organic moiety on the surface of synthesized NPs. Based on the molec-
ular structure of octylamine (the thermolysing solvents), it can be
assumed that the CuS NPs are capped by 1,1-diethyl-3-octylthiourea (in
situ generated species) [46].
of ꢀ 0.61 eV (ECB = EVB ꢀ E
g
). The XRD pattern was used to examine the
structure, size, phase purity and crystalline nature of CuS NPs. Fig. 1b
o
o
o
o
o
shows 2θ ( ) values at 27.33 (101), 29.37 (102), 31.87 (103), 32.92
o
o
o
o
(006), 48.06 (110), 52.77 (114), 59.47 (116) and 73.99 (208), which
match well with JCPDS card no. 00–001-1281 with the space group
P63/mmc, the space group number 194 and lattice parameters a =
3.8020 (Å), b = 3.8020 (Å) and c = 16.4300 (Å). The sharp and prom-
inent nature of peaks confirms the crystallinity of the hexagonal covel-
lite CuS NPs [51]. The calculated size of NPs is about 62 nm from Debye
Scherer’s formula (D = 0.89λ/βcosθ).
For CuS NPs, the characteristic absorption edge of covellite around
6
30 nm was observed [47,48]. (Fig. 1a). A band gap potential (E
g
) of
.E) vs energy (eV) plot (Fig. S3) using
g
) equation [49]. Valence band edge potentials (EVB) of
2
2
.63 eV was calculated from (
α
n
(
α
hν
) = A(h
ν
ꢀ E
NPs were calculated using the equation: EVB
=
χ
semiconductor ꢀ E
e
+ 0.5E
g
[
50], where
χ
semiconductor is equal to the electronegativity (for CuS,
The SEM image (Fig. S4) shows hexagonal nanoplates like
morphology for CuS NPs. The TEM and HRTEM (high-resolution) images
of CuS NPs are depicted in Figs. 1c & 1d. It can be seen in both the SEM
and TEM image that the distribution of particle size is not uniform and
χsemiconductor = 5.27), E
4
g
is equal to the band gap energy (eV) and E
e
(=
.5 eV) to the free electron’s energy on hydrogen scale for semi-
conductor. Thus, 2.02 eV was obtained for EVB, which leads to ECB value
Fig. 3. (a) Temperature curve of CuS-PVP with laser on/off. (b) Time constant ( s) of CuS-PVP.
τ
4

M. Arshad et al.
Journal of Photochemistry & Photobiology, B: Biology xxx (xxxx) xxx
Fig. 4. (a) Cell viability of MCF7 incubated with varying concentrations of CuS-PVP for 24 h (b) In vitro photothermal ability of CuS-PVP and (c) Confocal images of
calcein AM (green, live cells) and propidium iodide (red, dead cells) co-stained cells treated with PBS (a), laser (b), CuS-PVP (c), CuS-PVP + Laser (d). (scale bar 100
μ
m). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
seems spread with an average size of 59 nm as shown in the size dis-
tribution curve (Fig. S4 and S5, Fig. 1c). These results align with XRD,
thus all together confirming the formation of well-crystallized CuS NPs.
calculated according to Roper’s report [52], which was determined to be
42.2% (the calculation process is shown in the Supporting information).
The calculated
conducting nanozyme (HSN, 98.9%) [12], but higher than that of some
conventional photothermal nanoagents, such as Bi Se (34.6%) [53],
η
T
is lower than that of the reported hybrid semi-
2
3
3
.2. Photothermal Performance of CuS-PVP
Cu2-xSe nanocrystals (22%) and Au nanorods (21%) [54]. The above
results illustrate the excellent photothermal effect of the CuS.
Before commencing the experiment, the CuS NPs and polyvinyl
pyrrolidone (PVP) were mixed into an aqueous solution with overnight
stirring to make the materials evenly dispersed in the aqueous solution.
The optical properties of CuS-PVP aqueous dispersions containing
3.3. In vitro Cytotoxicity and PTT
ꢀ 1
varying concentrations (0.05–0.25 g L ) were studied via UV–vis-NIR
spectroscopy (Fig. 2a). With an increase of CuS-PVP concentration, the
absorbance increases in the NIR region. In particular, the NIR band
absorption goes up linearly with the concentration of CuS-PVP (Fig. 2b).
The excellent NIR photoabsorption can obtain good photothermal per-
formance. The 1064 nm laser was irradiated to visualize the photo-
thermal performance of CuS-PVP. Upon irradiating with of 1064 nm
The cytotoxicity of CuS-PVP was evaluated in vitro on MCF7 cells via
the standard CCK-8 assay. Incubation in the presence of different con-
ꢀ 1
centrations of CuS-PVP (0.015 to 0.5gL ) for 24 h, the mean cell
viability remained above 80% (at high level) for concentrations less than
ꢀ 1
0.25 g L (Fig. 4a). The low cytotoxicity of CuS-PVP makes it a potential
candidate for PTT. Then, we studied the photothermal therapeutic ef-
ꢀ 2
ficacy in vitro. With the irradiation of laser (1.0 W cm ), cell viability
decreased to about 10% for the CuS-PVP Laser group, but few cells were
dead in the other three groups (PBS, NIR, CuS-PVP) (Fig. 4b). To show
the therapeutic effect more vividly, MCF7 cells were incubated with
ꢀ
2
◦
laser (intensity = 1.0 W cm ), a negligible increase (less than 4 C) in
◦
temperature of pure water from 30 C in 5 min was observed. However,
in the presence of aqueous dispersion CuS-PVP (0.05, 0.1, 0.17 and 0.25
ꢀ
1
◦
ꢀ 1
g L ), the temperature can increase 15–45 C in 5 min, demonstrating
CuS-PVP (0.2 g L ) and then illuminated by a 1064-nm laser (intensity
ꢀ 2
the efficiency of CuS-PVP to convert 1064 nm laser into thermal energy
1.0 W cm ). After 10 min of irradiation, MCF7 cells were co-stained
with PI and calcein-AM to observe the effect using a fluorescence
confocal microscope.
(
Fig. 2c). The temperature increase (ΔT) in 300 s is almost linear with
ꢀ
1
the change of concentration of CuS-PVP from 0 to 0.25 g L (Fig.2d).
To further evaluate the photothermal conversion performance
The images from the control, laser and CuS-PVP groups show green
color (live cells), which indicates no therapeutic efficacy in these three
(
η
T
Fig.3), the photothermal conversion efficiency ( ) of CuS was
5

M. Arshad et al.
Journal of Photochemistry & Photobiology, B: Biology xxx (xxxx) xxx
Fig. 5. (a) Infrared thermal images of the mice injected with saline or CuS-PVP solution under the laser irradiation; (b) The plot of change in temperature in the
ꢀ 2
ꢀ 1
tumor area vs irradiation time. (1064 nm, 1 W cm ; CuS-PVP, 0.2 g L ).
Fig. 6. Representative H&E-stained histological images (scale bar 100 m) of the tumor sections after 24-h injection.
μ
groups. On the contrary, the image of the CuS-PVP laser group is almost
all red, showing effective cell killing (Fig. 4c). Herein, the photo- ther-
mal agent (CuS-PVP) combined with 1064-nm laser can achieve the high
photothermal therapeutic efficacy in vitro.
damage) are observed in group (IV) (Fig.6). Thus, CuS-PVP combinates
with 1064 nm laser can ablate cancer cells with high efficiency.
3
.5. PNP (Carcinogen) Conversion to PAP (Pharmaceutical Value)
3
.4. CuS-PVP for PTT in vivo
The catalytic potential of CuS NPs has been evaluated for a prototype
reaction, the reduction of PNP (carcinogen) to PAP (of pharmaceutical
value) using NaBH as a hydrogen source [49]. As both PNP and PAP
absorb radiation of different wavelengths, reaction progress can be
tracked by UV–Vis spectrophotometer. Upon introduction of NaBH , the
deepening of the yellow color was observed with bathochromic shift
from 317 nm (PNP) to 400 nm (p-nitrophenolate anions) (Fig. S6). After
24 h, no peak pertinent to PAP was observed indicating a catalyst driven
reaction (Fig. S7). However, upon addition of CuS NPs, PNP peak
gradually diminished and a new peak pertinent to PAP at 290 nm
emerged with time [55]. The reaction has a marked induction time (i.e.
time required for reactants and catalyst to get in touch) and follows
pseudo first order kinetics.
To investigate the PTT in vivo, mice with well-developed tumor were
4
picked randomly into 4- groups as follow: group (I)-Control; group (II)-
Laser; group (III)-CuS-PVP; and group (IV)-CuS-PVP + Laser. After laser
irradiation at 30 min, post-injection of tumors of mice in group (II) and
4
(
IV) and recording full-body thermal images by a thermal imaging
◦
camera revealed less than 4 C increase in temperature at the tumor site
during the whole illumination time of group (II), whereas the temper-
◦
◦
ature in IV-group goes up promptly from ~35 C to ~55 C (Fig. 5a&b).
After PTT, the tumors were removed from the mice, covered with
paraffin, and then crysectioned into slices. The slides were analyzed by
the microscopic image after staining with hematoxylin/eosin (H&E).
H&E-stained histological analysis shows that there are no obvious can-
cer cell destruction (maintained size, shape or nuclear structure) in 3
groups (I, II and III). In comparison, severe cancer cells damage
The effect of temperature on the catalytic conversion of PNP to PAP
◦
was studied varying temperatures from 25 to 50 C (Fig. S8). Notably,
the induction time seems to decrease as the temperature rises, i.e. from 6
◦
◦
(
destroyed cell membranes, lack of granular structures and nuclear
min (25 C) to 1 min (50 C). Furthermore, a threefold increase in the
6

M. Arshad et al.
Journal of Photochemistry & Photobiology, B: Biology xxx (xxxx) xxx
#
Fig. 7. Enthalpy and entropy calculation for reduction of PNP to PAP from (a) kapp vs T (b) lnkapp vs 1/T to calculate E
a
(c) lnkapp/T vs 1/T for calculation of ∆S and
#
∆
H (d) Recyclable nature of CuS NPs.
#
#
entropy (∆S ) and enthalpy (∆H ) were calculated from the plot of
Table 1
#
lnkapp/T vs 1/T, which gives a straight plot with a slope of -ΔH /R and an
Comparison of selected metal-sulfide photocatalysts for the photocatalytic
conversion of 4-PNP to 4-PAP.
#
intercept of (ln(k
b
/h) + ΔS /R) (Erying equation i.e., lnk/T = ln(k
b
/h) +
#
#
ΔS /R - ΔH /R (1/T)) [56,57] (Fig. 7c). When the catalyst was tested for
five cycles at room temperature, only a slight decrease in activity was
observed (Fig. 7d), which indicates the recyclable behavior of the
catalyst. In addition, the selectivity of the reaction was examined by
scanning the absorption region (200 nm to 800 nm) under different
conditions. The absence of any extra peak within this region indicated
that the process has been selectively proceeded [58].
Photocatalysts
Amount [g
Light
Activity
[min]
k
app
Ref.
ꢀ
1
a
ꢀ 1
L
]
λ(nm)
[min
]
◦
2
5
C
CdS
0.25
2
≥450
nm
270
˃ 100
70
n/a
[59]
[60]
[60]
[40]
ZnS-nanorods
Solar
light
Solar
light
Solar
light
Na
0.006
0.03
ZnS-nanorods/
rGO
2
The data in Table 1 shows that CuS NPs are many folds efficient if
taking into account both amount and efficiency (Kapp) than the previ-
ously reported catalysts.
CdS-nanorod
0.1
14
0.202
NiS
0.016
0.005
5
0.536
n/a
[62]
[63]
CdS-Flower
˃ 420
nm
90
3.6. Photocatalytic mechanism
CuS-Nanoplates
0.0033
Solar
light
6
0.535
This
work
The proposed mechanism for the conversion of PNP to PAP on CuS
NPs is described as follows. Upon solar irradiation, the valance band
(VB) electrons of CuS are readily excited to the conduction band (CB),
a
To compare the amount of catalyst and 4-NP in an accurate manner, the data
ꢀ 1
was converted into gram/l (g L ), considering the solution of 4-NP in one liter
and the amount of photocatalyst in gram.
+
where preferential adsorption of H ions and the nitro group occurs first,
2
followed by subsequent activation of O N-C group (Fig. 8a). This follows
apparent rate constant was observed with the temperature change from
an abstraction of oxygen from the nitro group on the surface of CuS. The
nitro group is reduced by high energy electrons of CB owing to the
comparable band off-set of the CB of CuS to the reduction potential of
the nitro group [64] (Fig. 8b). The subsequent amination process,
◦
2
5 to 50 C (Fig. S9). The average kinetic energy of molecules increases
at an elevated temperature, which in turn increases the diffusion rate of
the reactant. Hence, an increase in collision frequency and fast diffusion
rate triggers the conversion of reactants into products. By plotting lnk vs
+
through adsorbed surface H ions, happens on the exterior of the cata-
+
1
/T (Arrhenius equation i.e., lnk = ln A – E
a
/RT) gives a slope E
a
/RT that
lyst. The adsorbed H ions on the surface of the catalyst are the outcome
ꢀ
1
‾
‾
+
corresponds to E
a
value of 7.64 kJmol
(Fig. 7a & b). Activation
of the oxidation of BH
trons during this oxidation process fill the holes in the VB. Based on the
4 4
into B(OH) ion and 4H . The generated elec-
7

M. Arshad et al.
Journal of Photochemistry & Photobiology, B: Biology xxx (xxxx) xxx
ꢀ
Fig. 8. (a) Proposed Langmuir- Hinshelwood mechanism and (b) the band edge positions of CuS and relative redox potentials of 4-PNP and BH
-PNP to 4-PAP.
4
for the reduction of
4
Langmuir-Hinshelwood mechanism, the photoreduction of PNP to PAP
Appendix A. Supplementary data
using NaBH
4
as hydrogen source could, therefore, involve first the
+
adsorption of the nitro group and H ions on the surface of the catalyst
and then the reduction and amination processes [65].
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jphotobiol.2020.112084.
4
. Conclusion
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