Applied Physics A (2023) 129:169

https://doi.org/10.1007/s00339-023-06463-x

Antibacterial studies of ZnO and silica capped manganese doped zinc

sulphide nanostructures
Sunil Kumar1 · Anita Jain2 · Sanjay Panwar3 · Indu Sharma4 · Suhaas Gupta5 · Milan Dopita5 · Ravi Kant Choubey6

Received: 14 October 2022 / Accepted: 28 January 2023

© The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature 2023

Abstract
To investigate a potential new antibacterial agent to combat increasing antimicrobial resistance, undoped and 1% manganese
doped Zinc Sulphide quantum dots (ZnS and Z ­ n0.99Mn0.01S QDs, respectively) were synthesised by co-precipitation method
and capped with increasing amounts of Zinc Oxide and Silica in aqueous media to prepare ZnS@ZnO, Z ­ n0.99Mn0.01S@
ZnO, and Z ­ n0.99Mn0.01S@SiO2 nanostructures. P-XRD analysis confirmed the cubic zinc-blende phase of the seed ZnS
QDs, ­Zn0.99Mn0.01S QDs, and ­Zn0.99Mn0.01S@SiO2 nanostructures, and the wurtzite phase of the ZnO in the ZnS@ZnO
and ­Zn0.99Mn0.01S@ZnO nanostructures, further confirmed using TEM studies, which also revealed the size of the largest
nanostructures to be in the range of a hundred nanometres. FTIR spectroscopy illustrated the quenching of characteristic ZnS
peaks with increasing capping material. UV–Visible absorption spectroscopy and subsequent Tauc analysis illustrated the
strong size confinement of the synthesised ZnS and Z ­ n0.99Mn0.01S QDs; Brus equation calculations revealed that the particle
size of the samples increases with increasing capping material. Photoluminescent emission spectroscopy illustrated the tune-
able emission properties of the prepared nanostructures; manganese doping induced the characteristic orange emission in
the ­Zn0.99Mn0.01S QDs, which was enhanced by ZnO, but quenched by S ­ iO2. The antimicrobial activity of all the prepared
samples was qualitatively evaluated using well known Agar well diffusion method against six human pathogenic bacteria:
Gram positive Bacillus subtilis and Staphylococcus aureus; Gram negative Salmonella Typhi, Escherichia coli, Klebsiella
pneumoniae and Pseudomonas aeruginosa. Qualitative antibacterial assay confirmed the high antibacterial potential of
the synthesised ZnS and ­Zn0.99Mn0.01S QDs, especially against E. coli. Increasing ZnO amount improves the antibacterial
activity of the nanostructures against different Gram-positive bacterial strains, while increasing ­SiO2 amount improves the
antibacterial activity of the nanostructures against both Gram positive strains and three of the four Gram negative bacte-
rial strains. Thus, the positive results suggest that the prepared ZnS@ZnO, ­Zn0.99Mn0.01S@ZnO, and Z ­ n0.99Mn0.01S@SiO2
nanostructures should be further studied as antimicrobial agents.

Keywords ZnS · ZnO · SiO2 · Optical properties · Antibacterial assay

4
* Suhaas Gupta Department of Biotechnology, Maharishi Markandeshwar
suhaas96@gmail.com Univeristy, Mullana, Ambala, Haryana 133207, India
5
* Ravi Kant Choubey Department of Condensed Matter Physics, Faculty
ravikantchoubey14@gmail.com of Mathematics and Physics, Charles University, Ke Karlovu
5, 12116 Prague, Czech Republic
1
Indira Gandhi University, Meerpur, Rewari, 6
Department of Applied Physics, Amity Institute of Applied
Haryana 122502, India
Sciences (AIAS), Amity University, Noida Campus,
2
Department of Physics, Maharishi Markandeshwar Sector‑125, Noida, Uttar Pradesh 201313, India
University, Mullana, Ambala, Haryana 133207, India
3
School of Basic and Applied Sciences, Maharaja Agrasen
University, Atal Shiksha Kunj, Kalujhanda, Barotiwala,
Solan, Himachal Pradesh 174103, India

13
Vol.:(0123456789)
169 Page 2 of 17
1 Introduction
Antibacterial agents act to either kill bacterial cells (bac-
tericidal) or suppress bacterial growth (bacteriostatic);
antibacterial and antimicrobial materials are relevant to
multiple industries, like food, packaging, textile, decora-
tion, construction, etc., along with the obvious applica-
tions in the healthcare and biomedical fields. Their overuse
has, however, led to multiple bacterial strains expressing
increased resistance to conventional drug regimes, a phe-
nomenon that is both increasingly common and problem-
atic; as the drug-resistance of bacterial strains increases,
necessary dose of drugs (and corresponding toxicity),
length and complexity of treatments, and mortality rates
also increase. Increased antibacterial resistance can mani-
fest due to various different mechanisms, including but not
limited to, gene mutation, decreased uptake of relevant
drugs into the cell, formation of biofilm to avoid contact
with the antibacterial agent, or deactivation of antibiotic
molecule; while these problems have been addressed to
some extent through the development of new drugs or the
modification of existing ones, the efforts have been out-
paced by the persistent evolution of pathogens. A compro-
mised ability to treat serious infections gravely threatens
human health, and hence, research on more long-term,
robust and reliable methods to combat increased antibac-
terial resistance is in vogue [1–4].
Nanoparticles having particle sizes in the strong-con-
finement regime are extremely popular materials for appli-
cation based research in a number of different fields (elec-
tro-optics like in photovoltaic cells and display devices,
magnetics like in spintronic devices, energy storage and
conversion, catalysis, building, filling and coating of nano-
composite assemblies, to name a few) due to their easily-
tailored novel electrical, optical, magnetic and chemical
properties that arise as a consequence of quantum confine-
ment of charge carriers and enhanced effective surface area
[5–7]. These novel material- and size-dependent properties
have found extensive potential and realised applications
in various biomedical fields like labelling, sensing and
detection of biomolecules, optical and magnetic imaging
of cells, targeted delivery of drugs and proteins, repair of
implants and prosthetics and destruction of tumours [8, 9].
Several nanoparticles are also well known to exhibit anti-
microbial properties against a number of pathogenic bac-
teria, particularly silver nanoparticles which are already
in use in biomedical fields in combination with organic
antibiotics [10]. Nanoparticles, while having high reac-
tivity due to enhanced surface properties, are relatively
stable and biocompatible in aqueous media even in harsh
conditions, and do not produce harmful byproducts if
appropriately incorporated for disinfection, making them
13
S. Kumar et al.
very promising candidates for the replacement or enhance-
ment of conventional antibiotic agents. Nanoparticle based
antimicrobial agents make use of multiple simultaneous
mechanisms to cause cell death in a broad spectrum of
bacterial strains, overcoming the problem of development
of antimicrobial resistance in bacteria [11, 12].
The present work highlights the antibacterial activity
of pristine and 1% manganese doped ZnS nanoparticles,
employed as seed material in nanostructures with increas-
ing amounts of ZnO or ­SiO2, against six different human
pathogenic bacteria. ZnS, ZnO, ­SiO2 nanoparticles and a
myriad of their nanocomposites have been shown to exhibit
antibacterial potential before. Recently, Panthi et al. showed
the light activated antibacterial activity of polyvinyl acetate
nanofibers doped with rice grain-shaped ZnS nanoparticles
[13]; Ananth et al. showed the shape-dependent antibacte-
rial activity of ZnS nanomaterials (rods, layers and spherical
aggregates) prepared with an atmospheric pressure soft jet
plasma device [14]; Kokilavani et al. showed the improved
antibacterial activity of ZnS/Ag2WO4 nanocomposites as
compared to ZnS and ­Ag2WO4 individually [15]; Bhar-
athi et al. compared the antibacterial activity of S­ iO2–ZnO
nanocomposites prepared with chemical synthesis and
green synthesis techniques [16]. Despite the vast amount
of research done on the antibacterial activity of ZnS, ZnO
and/or ­SiO2 nanocomposites [17], the authors are unaware of
any investigation carried out on the antibacterial efficacy of
the nanostructure scheme specified in the present work, i.e.,
ZnS@ZnO, ­Zn0.99Mn0.01S@ZnO and ­Zn0.99Mn0.01S@SiO2
nanostructures with increasing amounts of capping material;
previously, the authors of this work have investigated the
antibacterial efficacy of ZnS@SiO2 nanostructures, which
exhibited increased antibacterial activity against Bacillus
subtilis with increasing ­SiO2 shell thickness, and demon-
strated very good photo-stability [18]. The authors have also
previously investigated the usefulness of Manganese doping
on the optical properties of ZnS for potential biocompat-
ible applications [19, 20]. Structural and morphological
properties of the prepared samples were investigated with
the help of X-ray diffraction, transmission electron micros-
copy and Fourier transform infra-red spectroscopy; optical
properties were investigated with the help of UV–visible
absorption and photoluminescent emission spectroscopy.
The antimicrobial activity of all the prepared samples was
qualitatively evaluated using well known Agar well diffu-
sion method against six human pathogenic bacteria: Gram
positive Bacillus subtilis and Staphylococcus aureus; Gram
negative Salmonella Typhi, Escherichia coli, Klebsiella
pneumoniae and Pseudomonas aeruginosa.
Antibacterial studies of ZnO and silica capped manganese doped zinc sulphide nanostructures Page 3 of 17
2 Experimental methods
2.1 Synthesis of ZnS and ­Zn0.99Mn0.01S quantum
dots (QDs)
ZnS and ­Zn0.99Mn0.01S QDs were synthesised using the
co-precipitation method reported in our earlier published
articles, with slight modifications [19, 21]; Zinc Acetate
[Zn(CH3COO)2.H2O] was used as the ­Zn2+ source, Man-
ganese Acetate [Mn(CH 3COO) 2] was used as the ­M n 2+
source, and Sodium Sulphide ­[ Na 2S] was used as the
­S2− source.
To synthesise ZnS QDs, carefully measured amounts (to
make 0.5 M solutions) of zinc source and sulphur source
were dissolved separately in deionised water with vigorous
magnetic stirring for 30 min at room temperature. Then,
sulphur solution was added drop wise to the zinc solution;
precipitation of ZnS QDs soon starts, and was allowed
to continue for 1 h at room temperature with vigorous
magnetic stirring. The ZnS QD dispersion was then centri-
fuged at 4000 rpm for 5 min, followed by filtration of the
precipitate using Whatman 40 filter paper, and repeated
washing with deionised water to remove unreacted mate-
rial and adhered impurities. The washed precipitate was
allowed to dry in a vacuum oven at 60 °C for 24 h, and
then lightly grinded with a mortar-pestle to obtain a fine
powder of ZnS QDs which were used for characterisations
and further synthesis. Z
­ n0.99Mn0.01S QDs were synthesised
in the same scheme by simply replacing carefully meas-
ured amount of zinc source with the manganese source to
obtain 1% dopant concentration.
2.2 Synthesis of ZnS@ZnO and ­Zn0.99Mn0.01S@ZnO
samples
ZnS QDs and Z ­ n0.99Mn0.01S QDs, synthesised as described
above, were used as the seed material for the growth of
ZnO shell, synthesised using the same scheme as reported
in our earlier published articles [22, 23]. First, 0.2 g of
the required seed material was dispersed in 200 mL of
deionised water using ultrasonication for 1 h. Then, dif-
ferent amounts (10, 30, 50 and 100 mL) of 0.05 M Zinc
Nitrate [Zn(NO3)2] solution were added to the dispersion
under vigorous magnetic stirring at room temperature, fol-
lowed by slow titration with 0.1 M Sodium Hydroxide
[NaOH] solution, until the dispersion achieved 10pH, at
which point the ZnO has nucleated and starts to grow. The
dispersion was then centrifuged at 4000 rpm for 5 min,
followed by filtration of the precipitate using Whatman
40 filter paper, and repeated washing with deionised water
to remove unreacted material and adhered impurities.
169
The washed precipitate was allowed to dry in a vacuum
oven at 60 °C for 24 h, and then lightly grinded with a
mortar-pestle to obtain a fine powder of ZnS@ZnO and
­Z n 0.99Mn 0.01S@ZnO, where the thickness of ZnO shell
was controlled by the amount of Zn(NO3)2 used during
synthesis; obtained powder samples were used for all
characterisations.
2.3 Synthesis of ­Zn0.99Mn0.01S@SiO2 samples
Zn0.99Mn0.01S QDs, synthesised as described above, were
used as the seed material for the growth of S ­ iO2 shell by
Stober process, with small modifications to the scheme
reported in our earlier published articles [18, 20]. First,
0.8 g of the seed ­Zn0.99Mn0.01S QDs was dispersed in a
mixture of 5 mL deionised water and 20 mL ethanol using
ultrasonication for 1 h. Then, different amounts (0.25,
0.5, 0.75 and 1 mL) of Tetraethyl Orthosilicate [TEOS,
Si(OC 2H 5) 4] were added to the dispersion under vigor-
ous magnetic stirring at room temperature. 0.5 mL of
25% Ammonium Hydroxide ­[NH4OH] was then injected
into the dispersion to act as a catalyst for the continuous
hydrolysis of the silica precursor and creation of ­S iO 2.
After vigorous magnetic stirring for 1 h at room tempera-
ture, the dispersion was centrifuged at 4000 rpm for 5 min,
followed by filtration of the precipitate using Whatman 40
filter paper, and repeated washing with deionised water to
remove unreacted material and adhered impurities. The
washed precipitate was allowed to dry in a vacuum oven
at 90 °C for 24 h, and then lightly grinded with a mortar-
pestle to obtain a fine powder of ­Z n 0.99Mn 0.01S@SiO 2,
where the thickness of the S ­ iO2 shell was controlled by
the amount of TEOS used during the synthesis; obtained
powder samples were used for all characterisations.
2.4 Characterisations
Powder X-ray diffraction (P-XRD) was carried out on
Rigaku D/MAX IIIC diffractometer in the Bragg–Brentano
geometry with Cu–Kα radiation (1.54056Å) in the range of
20°–70°. Transmission electron microscopy (TEM) images
were recorded using Hitachi H-7500 TEM operating at
120 kV and equipped with a CCD camera. Fourier trans-
form infrared (FTIR) spectroscopy was carried out on Perki-
nElmer Spectrum RX-I (40) in the range of 2000–400 ­cm−1.
UV–visible absorption spectroscopy was carried out on
double beam PerkinElmer Hitachi 330 UV–Vis-NIR spec-
trophotometer in the range 200–600 nm. Photoluminescent
emission (PLE) spectroscopy was carried out on Horiba
Jobin Yvon FluoroMax-3 spectrofluorometer using a Xenon
lamp as the excitation source.
13
169 Page 4 of 17 S. Kumar et al.

2.5 Antimicrobial assay

The antimicrobial activity of all the prepared samples

was evaluated using well known Agar well diffusion
method, which is a relatively quick and easily executable
semi-quantitative test to assess the antibacterial activity
of diffusible antibacterial agents [24]. Inhibitory action
of the prepared ZnS@ZnO, ­Z n 0.99Mn 0.01S@ZnO, and
­Z n 0.99Mn 0.01S@SiO 2 nanostructures was quantitatively
evaluated against six human pathogenic bacteria: Gram
positive Bacillus subtilis and Staphylococcus aureus;
Gram negative Salmonella Typhi, Escherichia coli, Kleb-
siella pneumoniae and Pseudomonas aeruginosa; anti-
microbial susceptibility discs (6 mm in diameter) of Tet-
racycline (30 µg/disc) and Gentamicin (10 µg/disc) were
used as the positive control, while pure ethanol was used
Fig. 2  Powder X-ray diffraction plots of the prepared Z
­ n0.99Mn0.01S@
as the negative control. Isolated colonies of the bacteria ZnO samples
were picked up from revived cultures with an inoculat-
ing loop and inoculated in saline water; inoculum den-
sity was adjusted against McFarland 0.5 standard solu- 3 Results and discussion
tion of ­BaSO4 (0.05 mL 1% ­BaCl2 + 9.95 mL 1% ­H2SO4)
which leads to an approximate bacteria cell density of 3.1 Powder X‑ray diffraction
1.5 × ­1 0 8 CFU/mL. 1 mL of the inoculum was spread
onto a Mueller Hinton Agar plate and four wells of 6 mm Figures 1, 2 and 3 show the P-XRD plots of the prepared
diameters were made, one in each of the quadrants, using ZnS@ZnO, ­Z n 0.99Mn 0.01S@ZnO and ­Z n 0.99Mn 0.01S@
a sterile cork borer. 5 mg/mL dispersions of all the syn- SiO2 samples, respectively; the P-XRD patterns of all the
thesised samples were made in ethanol, and 100 µL of the prepared samples were analysed using the software pack-
dispersions were poured into the wells. The plates were age MStruct [25–27], which is an extension of the FOX/
incubated overnight at 37 °C, and antimicrobial activity ObjCryst program [28, 29], with implementation of the
of the synthesised samples was evaluated by measuring whole powder pattern modelling (WPPM) method [30] for
the diameter of the inhibition zone. All the tests were per- real structure determination. Peak positions were determined
formed in triplicate and reported values (in mm) are the by refining unit-cell parameters and accounting for the peak
average of three results. position shift due to refraction at the sample interface; peak

Fig. 1  Powder X-ray diffraction plots of the prepared ZnS@ZnO Fig. 3  Powder X-ray diffraction plots of the prepared Z
­ n0.99Mn0.01S@
samples SiO2 samples

13
Antibacterial studies of ZnO and silica capped manganese doped zinc sulphide nanostructures Page 5 of 17
intensities were calculated from a known crystal structure
(as in FOX/ObjCryst) with absorption correction. Broaden-
ing of the peaks was modelled using numerical convolution
of a known pseudo-Voigt instrumental broadening function
and several other refinable parameters; for the sake of com-
putational simplicity, it was assumed that the distribution of
crystallite sizes takes the form of a log-normal distribution,
and that the nano-crystallites were spherical in shape. All the
figures depict the observed intensity values, the calculated
intensity values, and their difference.
Figure 1 shows the P-XRD plots of the prepared ZnS@
ZnO samples. Characteristic peaks observed for the syn-
thesised ZnS QDs are (111), (220) and (311), which match
with the bulk zinc-blende ZnS PDF No. 05-0566, confirm-
ing the required phase of the synthesised seed cubic ZnS
material; obtained lattice parameter a = 5.3815 Å is slightly
smaller than the lattice parameter reported in the ZnS PDF
No. 05-0566 (= 5.4053 Å). In the samples containing ZnO,
characteristic peaks observed are (100), (002), (101), (102),
(110), (103), (200), (112) and (201), which match with the
bulk wurtzite ZnO PDF No. 36–1451; as the amount of
Zn(NO3)2 used during the synthesis is increased, character-
istic diffraction peaks of wurtzite ZnO become more well
defined, and the intensity of the characteristic (111) peak
of the seed cubic ZnS QDs is quenched. For all the pre-
pared ZnS@ZnO samples, obtained lattice parameters of the
wurtzite ZnO were slightly larger than the lattice parameters
reported in the ZnO PDF No. 36-1451; lattice parameter of
the cubic seed ZnS QDs further decreased in the presence
of ZnO, but did not vary much with increasing ZnO amount.
Figure 2 shows the P-XRD plots of the prepared
­Zn0.99Mn0.01S@ZnO samples. Characteristic peaks observed
for the synthesised ­Zn0.99Mn0.01S QDs are (111), (220) and
(311), which match with the bulk zinc-blende ZnS PDF No.
05-0566, confirming the required phase of the synthesised
seed cubic Z ­ n0.99Mn0.01S material, and indicating that the
­Mn2+ ions used as dopant occupy (empty) sites in the ZnS
lattice without drastically changing the unit cell structure
of the of the host cubic material; obtained lattice parameter
a = 5.3495 Å is smaller still than the lattice parameter of
the synthesised undoped ZnS QDs obtained above. In the
samples containing ZnO, characteristic peaks observed are
(100), (002), (101), (102), (110), (103), (200), (112) and
(201), which match with the bulk wurtzite ZnO PDF No.
36–1451; as the amount of Zn(NO3)2 used during synthesis
is increased, characteristic peaks of wurtzite ZnO become
more well defined, and the intensity of the characteristic
(111) peak of the seed cubic ­Zn0.99Mn0.01S QDs is quenched.
For all the prepared ­Zn0.99Mn0.01S@ZnO samples, obtained
lattice parameters of the wurtzite ZnO were slightly larger
than the lattice parameters reported in the ZnO PDF No.
36-1451; lattice parameter of the cubic seed ­Zn0.99Mn0.01S
QDs initially increased in the presence of ZnO, but gradually
169
decreased with increasing ZnO amount, until it was smaller
than that of the synthesised ­Zn0.99Mn0.01S QDs.
Figure 3 shows the P-XRD plots of the prepared
­Zn0.99Mn0.01S@SiO2 samples. Characteristic peaks observed
for all the samples are (111), (220) and (311), which match
with the bulk zinc-blende ZnS PDF No. 05-0566, indicat-
ing that the Z­ n0.99Mn0.01S@SiO2 nanostructure adapts the
structure of the seed cubic Z ­ n0.99Mn0.01S material. For all
the prepared Z ­ n0.99Mn0.01S@SiO2 samples, obtained lat-
tice parameters of the cubic seed Z ­ n0.99Mn0.01S QDs were
smaller than the lattice parameter reported in the ZnS PDF
No. 05–0566; the lattice parameter initially decreased drasti-
cally in the presence of ­SiO2, but gradually increased with
increasing ­SiO2 shell thickness.
3.2 Transmission electron microscopy
Figure 4a, b show the TE micrograph of the synthesised
ZnS and ­Zn0.99Mn0.01S QDs, respectively. Generally, ZnS
exhibits poor contrast in electron microscopy, however the
micrographs confirm the presence of spherical ZnS nano-
particles with some agglomeration up to few tens of nano-
metres, while the ­Zn0.99Mn0.01S QDs exhibit slightly better
monodispersity and smaller size due to incorporation of
manganese in the lattice [19, 20].
Figure 4c, d show the TE micrograph of the prepared
ZnS@ZnO(30 mL) and ZnS@ZnO(100 mL) samples,
respectively, confirming the formation of the ZnS@ZnO
nanocomposite from the seed ZnS QDs. Increasing the
amount of Zn(NO3)2 used during synthesis increases the par-
ticle size of the samples, and the micrograph of the ZnS@
ZnO(100 mL) sample exhibits the pure wurtzite structure
of the ZnO shell, with a size of upto few hundreds of nano-
metres. Figure 4e, f show the TE micrograph of the pre-
pared ­Zn0.99Mn0.01S@ZnO(10 mL) and Z ­ n0.99Mn0.01S@
ZnO(30 mL) samples, respectively, confirming the forma-
tion of the ­Zn0.99Mn0.01S@ZnO nanocomposite from the
seed ­Zn0.99Mn0.01S QDs. Increasing the amount of Zn(NO3)2
used during synthesis increases the particle size and agglom-
eration tendency of the samples. Figure 4g, h show the TE
micrograph of the prepared ­Zn0.99Mn0.01S@SiO2(0.5 mL)
and ­Zn0.99Mn0.01S@SiO2(1 mL) samples, respectively. Sto-
ber process used during synthesis produces spherical ­SiO2
particles and increasing the amount of the TEOS used dur-
ing synthesis increases the particle size and dispersity of
the samples.
3.3 Fourier transform infrared spectroscopy
Figure 5 shows the FTIR spectra of the prepared ZnS@ZnO
samples. Broad peaks common to all the samples around
1560 ­cm−1 and 1398 ­cm−1 are attributed to the antisym-
metric and symmetric stretching of the ­COO − in the
13
169 Page 6 of 17 S. Kumar et al.

Fig. 4  Transmission electron

micrograph of the prepared:
a ZnS QD; b ­Zn0.99Mn0.01S
QD; c ZnS@ZnO(10 mL);
d ZnS@ZnO(100 mL); e
­Zn0.99Mn0.01S@ZnO(10 mL); f
­Zn0.99Mn0.01S@ZnO(30 mL); g
­Zn0.99Mn0.01S@SiO2(0.5 mL);
and h ­Zn0.99Mn0.01S@
SiO2(1 mL) samples

Zn-carboxylate group, respectively; broad band around 900-
1500 ­cm−1 is commonly attributed to frequencies of oxygen
bending and stretching [19, 31–33]. Synthesised ZnS QDs
exhibit a C–C stretching doublet peak at 1339 ­cm−1, absence
of which in the prepared ZnS@ZnO samples can be an indi-
cator of surface modification of the ZnS QDs by ZnO [34].
Synthesised ZnS QDs also exhibit the following peaks: O–H
bending peak at 670 ­cm−1; characteristic Zn–S stretching
peak at 615 ­cm−1, which is absent in the FTIR spectra of the
prepared ZnS@ZnO samples; and characteristic metal-oxide
stretching mode at 485 ­cm−1 [35, 36]. The FTIR spectra
of the prepared ZnS@ZnO samples also exhibit the Zn–O
bond stretching frequencies at increasing wavenumbers, in
the range 495–515 ­cm−1, with increasing ZnO concentration
or bulk character; minor peak exhibited around 421 ­cm−1
corresponds to the Raman-active E2 (high) mode of hex-
agonal ZnO. The weak bands around 1100–1200 ­cm−1 are
characteristic of inorganic ions, and the weak bands around
600–900 ­cm−1 are attributed to vibrational frequencies aris-
ing due to changes in the lattice at the microstructural level
[37, 38].
Figure 6 shows the FTIR spectra of the prepared
­Zn0.99Mn0.01S@ZnO samples. Broad peak common to all
the samples around 1623 ­cm−1 is attributed to the vibra-
tion of the C=O bond in the Zn-carboxylate group; broad
peaks around 1560 ­cm−1 and 1423 ­cm−1 are attributed to the

13
Antibacterial studies of ZnO and silica capped manganese doped zinc sulphide nanostructures Page 7 of 17
Fig. 5  Fourier transform infrared spectra of the prepared: a ZnS QD;
b ZnS@ZnO(10 mL); c ZnS@ZnO(30 mL); d ZnS@ZnO(50 mL);
and e ZnS@ZnO(100 mL) samples
Fig. 6  Fourier transform infrared spectra of the prepared: a
­ n0.99Mn0.01S QD; b ­Zn0.99Mn0.01S@ZnO(10 mL); c ­Zn0.99Mn0.01S@
Z
ZnO(30 mL); d ­Zn0.99Mn0.01S@ZnO(50 mL); and e ­Zn0.99Mn0.01S@
ZnO(100 mL) samples
antisymmetric and symmetric stretching of the C ­ OO− in the
Zn-carboxylate group, respectively; broad band around 900-
1500 ­cm−1 is commonly attributed to frequencies of oxygen
bending and stretching [19, 39]. Synthesised Z ­ n0.99Mn0.01S
QDs exhibit a C–C stretching doublet peak at 1340 ­cm−1,
absence of which in the prepared Z ­ n 0.99Mn 0.01S@ZnO
samples can be an indicator of surface modification of the
­Zn0.99Mn0.01S QDs by ZnO [34]. Synthesised Z ­ n0.99Mn0.01S
QDs also exhibit the following peaks: intense peak at
1106 ­cm−1, whose absence in the FTIR spectra of the
undoped ZnS QDs indicates the effect the doped M ­ n2+ ions
have on the host ZnS; O–H bending peak at 671 ­cm−1; char-
acteristic Zn–S stretching peak at 617 ­cm−1, which is absent
in the FTIR spectra of the prepared Z ­ n0.99Mn0.01S@ZnO
169
samples; and characteristic metal-oxide stretching mode at
486 ­cm−1 [35, 36, 40, 41]. The FTIR spectra of the prepared
­Zn0.99Mn0.01S@ZnO samples also exhibit the Zn–O bond
vibration modes in the range 491–548 ­cm−1 [36]. The weak
bands around 1100-1200 ­cm−1 are characteristic of inorganic
ions, and the weak bands around 600-900 ­cm−1 are attrib-
uted to vibrational frequencies arising due to changes in the
lattice at the microstructural level [22, 37, 38].
Figure 7 shows the FTIR spectra of the prepared
­Zn0.99Mn0.01S@SiO2 samples. Preliminary analysis reveals
that the FTIR spectra of all the samples are similar and share
a lot of common peaks: broad peaks around 1556 ­cm−1 and
1406 ­cm−1 are attributed to the antisymmetric and sym-
metric stretching of the C ­ OO− in the Zn-carboxylate group,
respectively; weak peak around 1340 ­cm−1 is attributed
to the doublet of C–C stretching; broad band around 900-
1500 ­cm−1 is commonly attributed to frequencies of oxygen
bending and stretching; peak around 672 ­cm−1 is attributed
to O–H bending; and broad peak around 495 ­cm−1 is attrib-
uted to the metal-oxide stretching mode [18, 19, 31–36].
However, FTIR spectrum of the synthesised Z ­ n0.99Mn0.01S
QDs exhibits some key differences: broad peak at 1616 ­cm−1
is attributed to the vibration of the C=O bond in the Zn-car-
boxylate group; intense peak at 1106 ­cm−1, whose absence
in the FTIR spectra of the undoped ZnS QDs indicates
the effect the doped M ­ n2+ ions have on the host ZnS; and
characteristic Zn–S stretching peak at 617 c­ m−1; decreased
intensity of these peaks in the FTIR spectra of the prepared
­Zn0.99Mn0.01S@SiO2 samples can be an indicator of surface
modification of the Z ­ n0.99Mn0.01S QDs by S ­ iO2 [35, 36,
39–41].The weak bands around 1100-1200 ­cm−1 are char-
acteristic of inorganic ions, and the weak bands around 600-
900 ­cm−1 are attributed to vibrational frequencies arising
Fig. 7  Fourier transform infrared spectra of the prepared:
a ­Zn0.99Mn0.01S QD; b ­Zn0.99Mn0.01S@SiO2(0.25 mL); c
­Zn0.99Mn0.01S@SiO2(0.5 mL); d ­Zn0.99Mn0.01S@SiO2(0.75 mL); and
e ­Zn0.99Mn0.01S@SiO2(1 mL) samples
13
169 Page 8 of 17
Fig. 8  UV–Visible absorption spectra of the prepared: a ZnS@ZnO; b ­Zn0.99Mn0.01S@ZnO; and c ­Zn0.99Mn0.01S@SiO2 samples
due to changes in the lattice at the microstructural level [32,
37, 38].
3.4 UV–visible absorption spectroscopy
Figures 8a–c show the UV–visible absorption spectra
of the prepared ZnS@ZnO, Z ­ n 0.99Mn 0.01S@ZnO and
­Zn0.99Mn0.01S@SiO2 samples, respectively. Energy band
gap (Eg) values of the core ZnS material for all the prepared
samples were determined from the UV–visible absorption
data using the Tauc relation [42–45], given as
(𝛼h𝜈)n = 𝛽 h𝜐 − Eg ,
( )
where α is the absorption coefficient, h is the Planck con-
stant, ν is the frequency of the photon, n = 2 for direct band
gap semiconductors like ZnS, and β is an arbitrary constant.
To obtain the values of energy band gap for all the prepared
samples, linear portion of the Tauc plot between (αhν)2 on
the y-axis and Eg on the x-axis is extrapolated to the x-inter-
cept. Figures 9, 10 and 11 show the Tauc plots of the pre-
pared ZnS@ZnO, ­Zn0.99Mn0.01S@ZnO and ­Zn0.99Mn0.01S@
SiO2 samples, respectively. Absorption edge (λa) values of
13
S. Kumar et al.
the core ZnS material for all the prepared samples were cal-
culated from the Eg values using the relation
hc
𝜆a = .
Eg
Particle sizes (R) of the core ZnS material for all the pre-
pared samples were calculated from the Eg values using the
effective mass approximation model of the Brus equation
[46, 47], given as
ℏ2 𝜋 2 1.8e2
Eg = Egbulk + 2
− ,
2𝜇R 4𝜋𝜀0 𝜀r R
where Egbulk is the bulk energy band gap (= 3.6 eV for
cubic zinc-blende ZnS), ℏ is the reduced Planck constant,
µ is the reduced mass of the exciton, e is the elementary
charge of an electron, ε0 is the permittivity of free space,
and εr is the relative permittivity of ZnS (= 8.9). Obtained
values of Eg, λa and R are summarised in Table 1, includ-
ing values of the absorption peak and energy band gap of
the ZnO shell material that can be easily obtained from the
UV–visible absorption spectra of the prepared ZnS@ZnO
and ­Zn0.99Mn0.01S@ZnO samples.
Antibacterial studies of ZnO and silica capped manganese doped zinc sulphide nanostructures Page 9 of 17
Fig. 9  Tauc plots of the pre-
pared ZnS@ZnO samples
Fig. 10  Tauc plots of the
prepared ­Zn0.99Mn0.01S@ZnO
samples
Pristine ZnS QDs exhibit the largest band gap energy
(3.93 eV) as a result of being the most strongly confined
nanoparticles out of all the samples; pristine ZnS QDs
also exhibit the smallest size (2.1 nm), and ­Zn0.99Mn0.01S
QDs exhibit the next smallest particle size (2.3 nm) with a
corresponding band gap energy of 3.84 eV. Capping with
­SiO2 does not drastically affect the energy band gap (or the
169
­ n0.99Mn0.01S material, which is to
particle size) of the seed Z
be expected due to the optically transparent nature of ­SiO2
and the small amounts of TEOS used during synthesis; for
the maximum amount of TEOS used during the synthesis,
the ­Zn0.99Mn0.01S@SiO2(1 mL) sample exhibits a band gap
energy of 3.82 eV and corresponding particle size of 2.5 nm.
In the case of the prepared ZnS@ZnO sample, capping with
13
169 Page 10 of 17
Fig. 11  Tauc plots of the
prepared ­Zn0.99Mn0.01S@SiO2
samples
ZnO induces a more noticeable trend of decreasing band
gap energy of the core ZnS material, and a corresponding
increase in the particle size of the same; for the maximum
amount of Zn(NO 3)2 used during the synthesis, ZnS@
ZnO(100 mL) sample exhibits a particularly decreased band
gap energy of 3.62 eV (and corresponding particle size of
5.3 nm), which is close to the bulk energy band gap value
of ZnS. In comparison, increasing the amount of Zn(NO3)2
used during the synthesis of the Z ­ n0.99Mn0.01S@ZnO sam-
ples also induces the same decreasing trend in the band
gap energy of the core ZnS material, but not as drastically
as for the prepared ZnS@ZnO samples; however, all the
­Zn0.99Mn0.01S@ZnO samples exhibit a strong absorption
peak around 363 nm, corresponding to the direct band gap
energy (~ 3.4 eV) of nano-sized ZnO.
3.5 Photoluminescent emission spectra
Figure 12a shows the PLE spectra of the prepared ZnS@
ZnO samples in the range of 325–575 nm with an excita-
tion wavelength of 320 nm. Synthesised ZnS QDs exhibit
a continuous emission from 380 to 440 nm, attributed to
the defect related emission band [19, 21]. The prepared
ZnS@ZnO samples exhibit a limited discretisation of this
broad band, possibly due to the increase in crystallinity as
a result of ZnO capping; the band exhibits a peak at about
400 nm, attributed to the near band-edge emission. Peaks at
about 450 nm can be attributed to the transitions between
doubly ionised Z­ n2+ vacancy level and the valence band,
peaks at about 467 nm can be attributed to the transitions
13
S. Kumar et al.
between acceptor and donor trap energy levels, and peaks
at about 481 nm and 491 nm can be attributed to transi-
tions facilitated by oxygen antisite defects. Green emission
peak at about 557 nm can be attributed to transition between
donor–acceptor complexes or singly ionised oxygen vacan-
cies [48–51].
Figure 12b shows the PLE spectra of the prepared
­Zn0.99Mn0.01S@ZnO samples in the range of 350–600 nm
with an excitation wavelength of 325 nm; prepared samples
exhibit near band edge emission at about 404 nm. Prepared
samples also exhibit minor peak at about 422 nm, which
can be attributed to the transitions between ­Zn2+ intersti-
tial level to the valence band, and a sharp peak at about
450 nm, which can be attributed to the transitions between
doubly ionised Z ­ n2+ vacancy level and the valence band [50,
52]; these peaks exhibit very slight red-shift with increasing
ZnO amount. The prepared samples also exhibit an orange
emission peak at about 590 nm, well known to be charac-
teristic of the 4T1 → 6A1 transition of the doped M­ n2+ [44];
in the case of the prepared ­Zn0.99Mn0.01S@ZnO(100 mL)
sample at 575 nm the emission peak of the ­Mn2+ transition
fuses with the yellow-green emission of the ZnO, exhibited
at about 560 nm in the rest of the samples. The prepared
­Zn0.99Mn0.01S@ZnO(100 mL) samples also exhibit a well-
defined peak at 472 nm and a minor hump at 529 nm, which
could be emissions arising from transitions facilitated by
­Zn2+ and ­O2− interstitials, respectively [48].
Figure 12c shows the PLE spectra of the prepared
­Zn0.99Mn0.01S@SiO2 samples in the range of 350–600 nm
with an excitation wavelength of 325 nm; prepared samples
Antibacterial studies of ZnO and silica capped manganese doped zinc sulphide nanostructures Page 11 of 17 169

exhibit near band edge emission at about 405 nm. Prepared

3.82

2.5
324.6

–
–
samples also exhibit minor peak at about 423 nm, which can

1.0
be attributed to the transitions between ­S2− vacancy level to
the valence band, a sharp peak at about 450 nm, which can

Zn0.99Mn0.01S@SiO2 (x mL)

3.83

2.4
323.7

–
–
0.75
be attributed to the transitions between acceptor vacancies
and donor vacancies, and peak at about 557 nm (which nar-
rows and blue-shifts with increasing ­SiO2 amount) which

3.83

2.4
323.7

–
–
0.5 can be attributed to elemental sulphur species [19, 21]. Peak
at about 590 nm is well known to be characteristic orange
3.84
emission of the 4T1 → 6A1 ­Mn2+ transition [44, 52], whose
2.4
322.9

–
–
0.25

emission intensity decreases with increasing ­SiO2 amount.

From the PLE spectra of the prepared samples it is clear that
the emission intensity of the synthesised ZnS QDs is not
3.4
3.7

364.3
3.3
335.1
100

only highly tuneable by varying the material or amount of

capping or doping, but is also highly photo-stable for long-
­ n0.99Mn0.01S@ZnO, and ­Zn0.99Mn0.01S@SiO2 samples
Zn0.99Mn0.01S@ZnO (x mL)

3.73

3.4
363.8
3.0
332.4

term antibacterial application.

50

3.6 Antibacterial assay
326.3

3.41
363
3.8

2.6
30

Figures 13, 14 and 15 represent qualitative analysis of

the synthesised ZnS@ZnO, ­Z n 0.99Mn 0.01S@ZnO and
322.9

­Zn0.99Mn0.01S@SiO2 nanostructures by agar well-diffusion

3.43
3.84

361
2.4
10

method against the six human pathogenic bacteria. The Agar

well-diffusion method is a relatively quick method with eas-
Zn0.99Mn0.01S

ily executable semi-quantitative tests to assess the antibacte-

rial activity of diffusible antibacterial agents. The antibacte-
rial activity of the synthesised ZnS@ZnO, Z ­ n0.99Mn0.01S@
3.85
322
2.3

–
–

ZnO and ­Zn0.99Mn0.01S@SiO2 nanostructures; shows maxi-

mum inhibitory action against B. subtilis and E. coli with a
3.06
3.62

404.7
5.3
342.5

zone of inhibition 17 and 22 mm, respectively. The visible

100
Table 1  UV–visible absorption spectroscopy parameters of the prepared ZnS@ZnO, Z

presence of inhibition zones larger in diameter than the wells

bored in the Agar plate clearly indicate the antibacterial
3.24
3.71

381.7
3.2
334.2

activity of the synthesised nanostructures.

50

Table 2 summarises the antibacterial activity of the

ZnS@ZnO (x mL)

synthesised samples, along with the inhibition zone diam-

3.78
328
2.7
30

eters produced in the positive and negative controls, and

–
–

Fig. 16 graphically illustrates the same; synthesised ZnS and

3.86

2.3
321.2

­Zn0.99Mn0.01S QDs exhibit the maximum inhibitory action

–
–
10

against E. coli, with zones of inhibition measuring 24 mm

and 22 mm, respectively.
3.93

2.1
315.5

–
–

In the case of pristine ZnS QDs and ­Zn0.99Mn0.01S QDs,

ZnS

the antibacterial activity against Gram negative bacteria is

greater than against Gram positive bacteria, possibly as a
Particle size (nm) from Brus equation

result of the slender membrane of Gram negative bacteria

UV–visible absorption parameters

as compared to the multi-layered cell walls of Gram posi-

Absorption edge (nm) λa of ZnS
Band gap (eV) from Tauc Plot

Absorption peak (nm) of ZnO

tive bacteria; antibacterial activity against E. coli is better

than even that of the positive control. With the inclusion
Band gap (eV) of ZnO

of ZnO capping of varying thickness on the pristine ZnS

QDs, the antibacterial activity of the samples against Gram
negative bacteria decreases, while the antibacterial activ-
ity against Gram positive bacteria slightly improves. In
the case of the Z ­ n0.99Mn0.01S@ZnO samples, the antibac-
terial activity against Gram positive B. subtilis and Gram

13
 169 Page 12 of 17
Fig. 12  Photoluminescent emission spectra of the prepared: a ZnS@ZnO; b ­Zn0.99Mn0.01S@ZnO; and c ­Zn0.99Mn0.01S@SiO2 samples
Fig. 13  Representative Agar plates for the well-diffusion investiga-
tion of antibacterial activity of the prepared: a ZnS and Z
­ n0.99Mn0.01S
QDs; b ZnS@ZnO; c ­Zn0.99Mn0.01S@ZnO; and d ­Zn0.99Mn0.01S@
SiO2 samples against Gram positive Bacillus subtilis; e ZnS and
negative Salmonella Typhi increases with an increase in
the thickness of ZnO shell; the maximum inhibition zone
exhibited is 14 mm and 16 mm, respectively. For the synthe-
sised ­Zn0.99Mn0.01S@SiO2 samples, increasing thickness of
13
S. Kumar et al.
­Zn0.99Mn0.01S QDs; f ZnS@ZnO; g ­Zn0.99Mn0.01S@ZnO; and h
­Zn0.99Mn0.01S@SiO2 samples against Gram positive Staphylococcus
aureus
­SiO2 shell generally induces a trend of increasing antibac-
terial activity against both Gram positive and Gram nega-
tive strains (maximum inhibition zone exhibited against
B. subtilis was 17 mm); this is in agreement with reports
Antibacterial studies of ZnO and silica capped manganese doped zinc sulphide nanostructures Page 13 of 17
Fig. 14  Representative Agar plates for the well-diffusion investiga-
tion of antibacterial activity of the prepared: a ZnS and Z
­ n0.99Mn0.01S
QDs; b ZnS@ZnO; c ­Zn0.99Mn0.01S@ZnO; and d ­Zn0.99Mn0.01S@
Fig. 15  Representative Agar plates for the well-diffusion investiga-
tion of antibacterial activity of the prepared: a ZnS and Z
­ n0.99Mn0.01S
QDs; b ZnS@ZnO; c ­Zn0.99Mn0.01S@ZnO; and d ­Zn0.99Mn0.01S@
SiO2 samples against Gram negative Klebsiella pneumoniae; e ZnS
of ­SiO2 nanocomposites exhibiting enhanced antibacte-
rial activity [14, 53, 54] ­Zn0.99Mn0.01S@SiO2 samples also
exhibit markedly better antibacterial activity than previously
investigated ZnS@SiO2 nanostructures, which exhibited a
maximum inhibition zone of 12 mm and 10 mm against B.
subtilis and Escherichia coli [18]. In conclusion, an appreci-
able enhancement in antibacterial activity was observed in
­Zn0.99Mn0.01S@ZnO samples as compared to ZnS@SiO2.
There is no common consensus, as of yet, on a single
mechanism to explain the antibacterial activity of nanoparti-
cles, and the different possible mechanisms that can explain
the antibacterial activity of ZnS and ZnO nanoparticles can
169
SiO2 samples against Gram negative Salmonella Typhi; e ZnS and
­Zn0.99Mn0.01S QDs; f ZnS@ZnO; g ­Zn0.99Mn0.01S@ZnO; and h
­Zn0.99Mn0.01S@SiO2 samples against Gram negative Escherichia coli
and ­Zn0.99Mn0.01S QDs; f ZnS@ZnO; g ­Zn0.99Mn0.01S@ZnO; and h
­Zn0.99Mn0.01S@SiO2 samples against Gram negative Pseudomonas
aeruginosa
be broadly classified into physical, biological or chemical
mechanisms depending on the process behind it. Physical
processes involve the penetration of the outer cell membrane
of the bacteria, causing a disturbance in the cell permeability
due to cell wall decomposition, which can lead to leakage
of proteins, minerals and genetic material, and eventual cell
death. These physical processes and the antibacterial activ-
ity caused by them depend on the nanoparticle size, surface
morphology and surface area, and increase with surface-to-
volume ratio [14, 55]. Biological processes suppress protein
metabolism, inhibit active transport, and disturb the enzy-
matic system of the bacteria to cause cell death. These may
13
169 Page 14 of 17 S. Kumar et al.

be facilitated by the binding or adsorption between the nano-

­ n0.99Mn0.01S@SiO2 samples, and the positive and negative controls against six human pathogenic bac-

(10 µg/disc)
+ve control
Gentamicin
particle surface and the bacteria outer membrane caused by
electrostatic or Van der Waals forces, or by the release of
­Zn2+ and direct cellular internalisation [14, 55, 56].

22
22

24
21
21
22
Tetracycline
The incorporation of ZnO in our prepared nanostructures
(30 µg/disc) suggests the possibility of chemical processes, that involve
+ve control the generation of reactive oxygen species (ROS) [57, 58]
like hydrogen peroxide and hydroxyl radicals that oxidize

15
16

16
17
17
16
cellular proteins and lipids and cause damage to the cel-
lular genetic material, leading to cell death. Nanoparticles
−ve control

exhibit defect energy levels in the forbidden band gap that

Zn0.99Mn0.01S@SiO2 (x mL) Ethanol

increase the capacity of transporting charge carriers to the

nanoparticle surface and transferring that energy to a nearby
0
0

0
0
0
0
oxygen molecule leading to the generation of ROS [14, 59].
1.0

17
12

11
14
11
10
4 Conclusion
0.75

14
10

11
12
10
10

In the present work, ZnS and Z ­ n0.99Mn0.01S QDs were syn-

0.5

10
11

10
10
10
11

thesised using the co-precipitation method, and used as

seed material for the subsequent synthesis of ZnS@ZnO,
0.25

­Zn0.99Mn0.01S@ZnO and ­Zn0.99Mn0.01S@SiO2 nanostruc-

10
10

10
10
10
10

tures, synthesised in separate wet chemical processes with

Zn0.99Mn0.01S@ZnO (x mL)

100

increasing amounts of Zn(NO3)2 and TEOS, employed as

14
11

16
10
11
11

the precursors for ZnO and S ­ iO2 shell, respectively. Soft-

ware package MStruct was used to analyse the P-XRD pat-
50

13
12

14
12
11
11

terns of all the samples; zinc-blende phase was confirmed

for the synthesised ZnS and Z ­ n 0.99 Mn 0.01 S QDs. The
30

11
11

13
10
12
12

ZnS@ZnO and ­Z n 0.99Mn 0.01S@ZnO samples exhibited

Table 2  Inhibition zone diameters of the prepared ZnS@ZnO, ­Zn0.99Mn0.01S@ZnO, and Z

increasing intensity of wurtzite ZnO phase with increas-

10

10
10

12
12
11
14

ing Zn(NO3)2 used during synthesis; Z ­ n0.99Mn0.01S@SiO2

samples exhibited the same phase as the seed zinc-blende
Zn0.99Mn0.01S

­Z n0.99Mn0.01S. TE micrographs confirmed the spherical

shape of the synthesised ZnS and ­Zn0.99Mn0.01S QDs, and
the wurtzite phase of the ZnS@ZnO(100 mL) sample.
12

12
22
17
14

FTIR spectra of the prepared samples exhibited a number

8

of characteristic peaks; peak at around 1340 ­cm−1 in the

100

11
12

11
11
11
12

FTIR spectra of the synthesised ZnS and Z ­ n0.99Mn0.01S

QDs is attributed to the C–C doublet peak, whose absence
in the FTIR spectra of the prepared ZnS@ZnO and
ZnS@ZnO (x mL)

50

12
12

11
10
12
10

­Zn0.99Mn0.01S@ZnO nanostructures could be an indica-

tion of surface modification of the seed material by ZnO.
30

12
11

12
11
11
12

The synthesised Z ­ n0.99Mn 0.01S QDs also exhibit a peak

at around 1106 ­cm−1 due to the doping of ­Mn2+ ions in
10

13
10

12
10
10
10

the host ZnS lattice, which is quenched along with the

characteristic Zn–S stretching peak 617 ­cm−1 in the FTIR
ZnS

10

14
24
12
14

spectra of the prepared Z ­ n0.99Mn0.01S@SiO2 nanostruc-

8

ture. UV–visible absorption spectra of the synthesised

Salmonella Typhi

ZnS and Z ­ n 0.99Mn 0.01S QDs exhibited strong blue-shift

K. pneumoniae
Inhibition Zone
Diameter (mm)

P. aeruginosa
Gram negative
Bacteria strain

with respect to the absorption edge of bulk ZnS; energy

Gram positive
terial strains

B. subtilis
S. aureus

band gap value (~ 3.9 eV) obtained from the Tauc rela-
E. coli

tion and particle size (~ 2.2 nm) obtained from the Brus
equation confirmed the strong size confinement of the

13
Antibacterial studies of ZnO and silica capped manganese doped zinc sulphide nanostructures Page 15 of 17
Fig. 16  Histogram illustrating the antibacterial activity of the prepared: a ZnS@ZnO; b ­Zn0.99Mn0.01S@ZnO; c ­Zn0.99Mn0.01S@SiO2 samples;
and d positive control(s) against six human pathogenic bacterial strains
synthesised ZnS and Z ­ n0.99Mn0.01S QDs. Band gap val-
ues generally decreased (and corresponding particle sizes
increased) with an increase in the amount of Zn(NO3) 2
and TEOS used during the synthesis of the ZnS@ZnO,
­Zn0.99Mn0.01S@ZnO, and Z ­ n0.99Mn0.01S@SiO2 samples.
PLE spectra of the synthesised ZnS and ­Zn0.99Mn0.01S QDs
exhibited surface defect mediated emission bands, which
was increasingly quenched with an increase in the ZnO or
­SiO 2 shell thickness. Characteristic orange emission of
the dopant ­Mn2+ 4T1 → 6A1 transition in the synthesised
­Zn0.99Mn0.01S QDs is enhanced with ZnO capping, but is
increasingly quenched with increasing S ­ iO2 capping. The
PLE spectra not only illustrated the highly tuneable emis-
sion properties, but also highlighted the enhanced surface
properties of the synthesised ZnS@ZnO, Z ­ n0.99Mn0.01S@
ZnO, and ­Z n 0.99Mn 0.01S@SiO 2 nanostructures, both of
which are incredibly useful for biomedical applications.
Antibacterial assay showed the incredible antibacterial
potential of the synthesised ZnS and ­Zn0.99Mn0.01S against
E. coli. Increasing thickness of the ZnO shell increases
the antibacterial activity of the prepared ZnS@ZnO sam-
ples against S. aureus and the prepared ­Zn0.99Mn0.01S@
ZnO samples against B. subtilis. Increasing thickness of
the ­SiO2 shell increases the antibacterial activity of the
prepared ­Zn0.99Mn0.01S@SiO2 samples against both Gram
positive bacterial strains and against E. coli.
169
Acknowledgements S.K., A.J. and S.P. are thankful to the Department
of Science (DST), New Delhi, India for supporting part of this research
work (vide Project No. SR/FTP/PS-69/2008), dated 15/1/2010. Ravi
Kant Choubey is thankful to the Council of Science & Technology,
Lucknow, Uttar Pradesh, India for the financial support (Vide No.
CST/4051).
Author contributions All the authors contributed to the present work,
conception and design, Material preparation, data collection and analy-
sis were performed by the authors. The author’s contribution is shown
below. The first draft of the manuscript was written by SK, RKC and
SG and all the authors commented on the previous version of the manu-
script. All the authors read and approved the final manuscript.
Availability of data and materials The data used in the manuscript can
be available from the corresponding author upon reasonable request.
Declarations
Conflict of interest I hereby confirm that, the work described has not
been published before; it is not under consideration for publication
anywhere else; and publication has been approved by all co-authors
of this manuscript.
Research data policy and data availability statements All data gener-
ated or analysed during this study have been deposited in this manu-
script. All the compared data were properly cited and included in the
reference section following the journal style. Also, the data will be
available from the corresponding author on reasonable request.
13
 169 Page 16 of 17 S. Kumar et al.

References 22. A. Jain, S. Panwar, T.W. Kang, S. Kumar, J. Mater. Sci. Mater.
Electron. 24(12), 5147–5154 (2013). https://​doi.​org/​10.​1007/​
s10854-​013-​1537-z
1. L. Zhang, J. Ma, B. Lyu, Y. Zhang, V.K. Thakur, C. Liu, Green
23. A. Jain, S. Panwar, T.W. Kang, H.C. Jeon, S. Kumar, R.K.
Chem. 23(19), 7576–7588 (2021). https://​d oi.​o rg/​1 0.​1 039/​
Choubey, J. Mater. Sci. Mater. Electron. 25(4), 1716–1723 (2014).
D1GC0​1766G
https://​doi.​org/​10.​1007/​s10854-​014-​1788-3
2. B.Y. Lu, G.Y. Zhu, C.H. Yu, G.Y. Chen, C.L. Zhang, X. Zeng,
24. M. Balouiri, M. Sadiki, S.K. Ibnsouda, J. Pharm. Anal. 6(2),
Q.M. Chen, Q. Peng, Nano Res. 14(1), 185–190 (2021). https://​
71–79 (2016). https://​doi.​org/​10.​1016/j.​jpha.​2015.​11.​005
doi.​org/​10.​1007/​s12274-​020-​3064-6
25. Z. Matej, R. Kuzel, L. Nichtova, Powder Diffr. 25(2), 125–131
3. Y. Gao, Y. Dong, S. Yang, A. Mo, X. Zeng, Q. Chen, Q. Peng,
(2010). https://​doi.​org/​10.​1154/1.​33923​71
J. Colloid Interface Sci. 617, 533–541 (2022). https://​doi.​org/​
26. Z. Matej, A. Kadlecova, M. Janecek, L. Matejova, M. Dopita, R.
10.​1016/j.​jcis.​2022.​03.​032
Kuzel, Powder Diffr. 29(S2), S35–S41 (2014). https://​doi.​org/​10.​
4. C. Yu, S. Sui, X. Yu, W. Huang, Y. Wu, X. Zeng, Q. Chen, J.
1017/​S0885​71561​40008​52
Wang, Q. Peng, Colloids Surf. B Biointerfaces 217, 112663
27. MStruct-software for Micro Structure analysis by powder diffrac-
(2022). https://​doi.​org/​10.​1016/j.​colsu​r fb.​2022.​112663
tion (xray.cz/mstruct)
5. M.M. Modena, B. Rühle, T.P. Burg, S. Wuttke, Adv. Mater.
28. V. Favre-Nicolin, R. Cerny, J. Appl. Cryst. 35(6), 734–743 (2002).
31(32), 1901556 (2019). https://​doi.​org/​10.​1002/​adma.​20190​
https://​doi.​org/​10.​1107/​S0021​88980​20152​36
1556
29. FoxWiki-FOX, Free Objects for Crystallography Wiki (fox.
6. A. Mohajerani, L. Burnett, J.V. Smith, H. Kurmus, J. Milas, A.
vincefn.net)
Arulrajah, A. Horpibulsuk, A. Abdul Kadir, Materials 12(19),
30. P. Scardi, M. Leoni, Acta Cryst. A58(2), 190–200 (2002). https://​
3052 (2019). https://​doi.​org/​10.​3390/​ma121​93052
doi.​org/​10.​1107/​S0108​76730​10212​98
7. S. Shrestha, B. Wang, P. Dutta, Adv. Colloid Interface Sci. 279,
31. G. Ghosh, M.K. Naskar, A. Patra, M. Chatterjee, Opt. Mater.
102162 (2020). https://​doi.​org/​10.​1016/j.​cis.​2020.​102162
28(8–9), 1047–1053 (2006). https://​doi.​org/​10.​1016/j.​optmat.​
8. P.L. Suarez, M. Garcia-Cortes, M.T. Fernandez-Arguelles, J.R.
2005.​06.​003
Encinar, M. Valledor, F.J. Ferrero, J.C. Campo, J.M. Costa-
32. B.S. Rema Devi, R. Raveendran, A.V. Vaidyan, Pramana 68(4),
Fernández, Anal. Chim. Acta 1046, 16–31 (2019). https://​doi.​
679–687 (2007). https://​doi.​org/​10.​1007/​s12043-​007-​0068-7
org/​10.​1016/j.​aca.​2018.​08.​018
33. N.V. Hullavarad, S.S. Hullavarad, J. Vac. Sci. Technol. A 26(4),
9. Y. Hui, X. Yi, F. Hou, D. Wibowo, F. Zhang, D. Zhao, H. Gao,
1050–1057 (2008). https://​doi.​org/​10.​1116/1.​29403​46
C.X. Zhao, ACS Nano 13(7), 7410–7424 (2019). https://​doi.​org/​
34. M. Sharma, S. Kumar, O.P. Pandey, J. Nanopart. Res. 12(7),
10.​1021/​acsna​no.​9b039​24
2655–2666 (2010). https://​doi.​org/​10.​1007/​s11051-​009-​9844-2
10. C. Bankier, R.K. Matharu, Y.K. Cheong, G.G. Ren, E. Clout-
35. A.K. Thottoli, A.K.A. Unni, J. Nanostruct. Chem. 3(1), 1–12
man-Green, L. Ciric, Sci. Rep. 9(1), 1–8 (2019). https://​doi.​org/​
(2013). https://​doi.​org/​10.​1186/​2193-​8865-3-​56
10.​1038/​s41598-​019-​52473-2
36. I. Ahemen, O. Meludu, E. Odoh, Br. J. Appl. Sci. Technol. 3(4),
11. Y. Jing, B. Mu, M. Zhang, L. Wang, H. Zhong, X. Liu, A. Wang,
1228 (2013)
Colloids Surf. A Physicochem. Eng. Asp. 600, 124965 (2020).
37. S. Muthukumaran, R. Gopalakrishnan, Opt. Mater. 34(11), 1946–
https://​doi.​org/​10.​1016/j.​colsu​r fa.​2020.​124965
1953 (2012). https://​doi.​org/​10.​1016/j.​optmat.​2012.​06.​004
12. Y. Gao, Y. Chen, Y. Cao, A. Mo, Q. Peng, Eur. J. Med. Chem.
38. K. Raja, P.S. Ramesh, D. Geetha, Spectrochim. Acta A Mol. Bio-
213, 113056 (2021). https://​d oi.​o rg/​1 0.​1 016/j.​e jmech.​2 020.​
mol Spectrosc. 131, 183–188 (2014). https://​doi.​org/​10.​1016/j.​
113056
saa.​2014.​03.​047
13. G. Panthi, R. Ranjit, S. Khadka, K.R. Gyawali, H.Y. Kim, M.
39. Y. Wang, B. Wu, C. Yang, M. Liu, T.C. Sum, K.T. Yong, Small
Park, Adv. Compos. Hybrid Mater. 3(1), 8–15 (2020). https://​
12(4), 534–546 (2016). https://​doi.​org/​10.​1002/​smll.​20150​3352
doi.​org/​10.​1007/​s42114-​020-​00141-9
40. Y. Hu, Z. Wei, B. Wu, B. Shen, Q. Dai, P. Feng, AIP Adv. 8(1),
14. A. Ananth, I. Han, M. Akter, J.H. Boo, E.H. Choi, J. Ind. Eng.
15014 (2018). https://​doi.​org/​10.​1063/1.​50108​33
Chem. 90, 389–398 (2020). https://​doi.​org/​10.​1016/j.​jiec.​2020.​
41. Y. Hu, B. Hu, B. Wu, Z. Wei, J. Li, J. Mater. Sci. Mater. Elec-
07.​042
tron. 29(19), 16715–16720 (2018). https://​d oi.​o rg/​1 0.​1 007/​
15. S. Kokilavani, S.A. Al-Farraj, A.M. Thomas, H.A. El-Serehy,
s10854-​018-​9764-y
L.L. Raju, S.S. Khan, Ceram. Int. 47(9), 12997–13006 (2021).
42. J. Tauc, A. Menth, D.L. Wood, Phys. Rev. Lett. 25(11), 749
https://​doi.​org/​10.​1016/j.​ceram​int.​2021.​01.​163
(1970). https://​doi.​org/​10.​1103/​PhysR​evLett.​25.​749
16. D.S. Bharathi, A. Boopathyraja, S. Nachimuthu, K. Kannan,
43. J. Tauc, A. Menth, J. Non. Cryst. Solids 8, 569–585 (1972).
J. Clust. Sci. 33, 2499–2515 (2021). https://​doi.​org/​10.​1007/​
https://​doi.​org/​10.​1016/​0022-​3093(72)​90194-9
s10876-​021-​02170-w
44. A. Kumar, S. Mukherjee, H. Sharma, D.K. Rana, A. Kumar,
17. S. Kumar, K.H.S. Bhatti, K. Singh, S. Gupta, S. Sharma, V.
R. Kumar, R.K. Choubey, Mater. Sci. Semicond. Process. 155,
Kumar, R.K. Choubey, Phys. Scripta 96, 125807 (2021). https://​
107226 (2023). https://​doi.​org/​10.​1016/j.​mssp.​2022.​107226
doi.​org/​10.​1088/​1402-​4896/​ac1eb3
45. A. Kumar, M. Kumar, V. Bhatt, S. Mukherjee, S. Kumar, H.
18. S. Kumar, A. Jain, S. Panwar, I. Sharma, H.C. Jeon, T.W. Kang,
Sharma, M.K. Yadav, S. Tomar, J.H. Yun, R.K. Choubey, Sens.
R.K. Choubey, Int. J. Appl. Ceram. Technol. 16(2), 531–540
Actuators A. Phys. 331, 112988 (2021). https://​doi.​org/​10.​1016/j.​
(2019). https://​doi.​org/​10.​1111/​ijac.​13145
sna.​2021.​112988
19. S. Tomar, S. Gupta, S. Mukherjee, A. Singh, S. Kumar, R.K.
46. L.E. Brus, J. Chem. Phys. 79(11), 5566–5571 (1983). https://​doi.​
Choubey, Semiconductors 54(11), 1450–1458 (2020). https://​
org/​10.​1063/1.​445676
doi.​org/​10.​1134/​S1063​78262​01102​4X
47. L.E. Brus, J. Chem. Phys. 80(9), 4403–4409 (1984). https://​doi.​
20. S. Tomar, S. Gupta, S. Mukherjee, A. Singh, S. Kumar, V.
org/​10.​1063/1.​447218
Kumar, R.K. Choubey, Phys. Scr. 96(6), 65802 (2021). https://​
48. S.K. Mishra, R.K. Srivastava, S.G. Prakash, R.S. Yadav, A.C.
doi.​org/​10.​1088/​1402-​4896/​abed7e
Panday, Optp-Electron. Rev. 18(4), 467–473 (2010). https://​doi.​
21. S. Gupta, R.K. Choubey, L.K. Sharma, M.P. Ghosh, M. Kar, S.
org/​10.​2478/​s11772-​010-​0037-4
Mukherjee, Semicond. Sci. Technol. 34(10), 105006 (2019).
49. T.K. Kundu, N. Karak, P. Barik, S. Saha, Int. J. Soft Comput. Eng.
https://​doi.​org/​10.​1088/​1361-​6641/​ab3a00
1, 19–24 (2011)

13
Antibacterial studies of ZnO and silica capped manganese doped zinc sulphide nanostructures Page 17 of 17
50. D. Das, P. Mondal, RSC Adv. 4(67), 35735–35743 (2014). https://​
doi.​org/​10.​1039/​C4RA0​6063F
51. D. Mandal, L.K. Sharma, S. Mukherjee, Appl. Phys. A 122(12),
1–10 (2016). https://​doi.​org/​10.​1007/​s00339-​016-​0573-y
52. R.K. Chandrakar, R.N. Baghel, V.K. Chandra, B.P. Chandra,
Superlattices Microstruct. 86, 256–269 (2015). https://​doi.​org/​
10.​1016/j.​spmi.​2015.​07.​043
53. Z.A. Baka, M.M. El-Zahed, Bioresour. Bioprocess. 9(1), 1–19
(2022). https://​doi.​org/​10.​1186/​s40643-​022-​00591-7
54. M.M. El-Zahed, M.I. Abou-Dobara, A.K. El-Sayed, Z.A.M. Baka,
Nova Biotechnol. Et Chim. 21(1), 1023 (2022). https://d​ oi.o​ rg/1​ 0.​
36547/​nbc.​1023
55. R. Kumar, P. Sakthivel, P. Mani, Appl. Phys. A 125(8), 1–12
(2019). https://​doi.​org/​10.​1007/​s00339-​019-​2823-2
56. S. Vijayan, C.S. Dash, G. Umadevi, M. Sundararajan, R. Mari-
appan, J. Clust. Sci. 32(6), 1601–1608 (2021). https://​doi.​org/​10.​
1007/​s10876-​020-​01923-3
169
57. C. Hwang, M.H. Choi, H.E. Kim, S.H. Jeong, J.U. Park, NPG Asia
Mater. 14, 72 (2022). https://d​ oi.o​ rg/1​ 0.1​ 038/s​ 41427-0​ 22-0​ 0420-5
58. V.L. Prasanna, R. Vijayaraghavan, Langmuir 31, 9155 (2015).
https://​doi.​org/​10.​1021/​acs.​langm​uir.​5b022​66
59. H. Labiadh, K. Lahbib, S. Hidouri, S. Touil, T.B. Chaabane, Asian
Pac. J. Trop. Med. 9(8), 757–762 (2016). https://d​ oi.o​ rg/1​ 0.1​ 016/j.​
apjtm.​2016.​06.​008
Publisher's Note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.
Springer Nature or its licensor (e.g. a society or other partner) holds
exclusive rights to this article under a publishing agreement with the
author(s) or other rightsholder(s); author self-archiving of the accepted
manuscript version of this article is solely governed by the terms of
such publishing agreement and applicable law.
13