Enhanced Stability and Highly Bright Electroluminescence of AgInZnS/CdS/ZnS Quantum Dots through Complete Isolation of Core and Shell via a CdS Interlayer.

An approach for synthesizing AgInZnS/CdS/ZnS core-shell-shell quantum dots (QDs) that demonstrate exceptional stability and electroluminescence (EL) performance is introduced. This approach involves incorporating a cadmium sulfide (CdS) interlayer between an AgInZnS (AIZS) core and a zinc sulfide (ZnS) shell to prevent the diffusion of Zn ions into the AIZS core and the cation exchange at the core-shell interface. Consequently, a uniform and thick ZnS shell, with a thickness of 2.9 nm, is formed, which significantly enhances the stability and increases the photoluminescence quantum yield (87.5%) of the QDs. The potential for AIZS/CdS/ZnS QDs in electroluminescent devices is evaluated, and an external quantum efficiency of 9.6% in the 645 nm is achieved. These findings highlight the importance of uniform and thick ZnS shells in improving the stability and EL performance of QDs.

Visible Light Motivated the Photocatalytic Degradation of P-Nitrophenol by Ca2+-Doped AgInS2.

4-Nitrophenol (4-NP) is considered a priority organic pollutant with high toxicity. Many authors have been committed to developing efficient, green, and environmentally friendly technological processes to treat wastewater containing 4-NP. Here, we investigated how the addition of Ca2+ affects the catalytic degradation of 4-NP with AgInS2 when exposed to light. We synthesized AgInS2 (AIS) and Ca2+-doped AgInS2 (Ca-AIS) with varying amounts of Ca2+ using a low-temperature liquid phase method. The SEM, XRD, XPS, HRTEM, BET, PL, and UV-Vis DRS characteristics were employed to analyze the structure, morphology, and optical properties of the materials. The effects of different amounts of Ca2+ on the photocatalytic degradation of 4-NP were investigated. Under visible light illumination for a duration of 120 min, a degradation rate of 63.2% for 4-Nitrophenol (4-NP) was achieved. The results showed that doping with an appropriate amount of Ca2+ could improve the visible light catalytic activity of AIS. This work provides an idea for finding suitable cheap alkaline earth metal doping agents to replace precious metals for the improvement of photocatalytic activities.

Improved Luminous Efficiency of AgInS2 Quantum Dots and Zeolitic Imidazolate Framework-70 Composite for White Light Emitting Diode Applications.

The application of multiple quantum dots (QDs) in the field of white light emitting diodes (WLEDs) is still an important challenge due to their low luminous efficiency and quenching phenomenon. In this paper, we prepared AgInS2 QDs/zeolitic imidazolate framework-70 (AIS/ZIF-70) composite by a microwave hydrothermal method. Owing to the high porosity and stability of ZIF-70, it could effectively prevent quenching issues due to the aggregation of QDs. Since the ZIF-70 and QDs were chemically bonded, the formation of the ZnS layer could effectively passivate the surface defect and thus the quantum yield reached 21.49 % in aqueous solution. The luminous efficiency (LE) of the assembled AIS/ZIF-based WLED was reinforced by 6.8 times with a molar ratio of AgIn/Zn=18, i. e. at 5.26 % molar fraction of ZIF-70. Moreover, the color rendering index (CRI) and correlated color temperature (CCT) of AIS/ZIF-based WLED were 84.3 and 3631 K, respectively, indicating its potential application in solid-state lighting.

Double-shelling AgInS2nanocrystals with GaSx/ZnS to make them emit bright and stable excitonic luminescence.

This paper presents the successful synthesis of AgInS2nanocrystals (NCs) double-shelled with GaSxand ZnS for emitting bright and narrow excitonic luminescence from AgInS2core NCs. Additionally, the AgInS2/GaSx/ZnS NCs with a core/double-shell structure have demonstrated high chemical and photochemical stability. The AgInS2/GaSx/ZnS NCs were prepared via three steps: (i) synthesis of AgInS2core NCs by solvothermal method at 200 °C for 30 min, (ii) shelling GaSxon AgInS2core NCs at 280 °C for 60 min to produce the AgInS2/GaSxcore/shell structure, and (iii) the outermost ZnS shelling at 140 °C for 10 min. The synthesized NCs were characterized in detail by using appropriate techniques such as x-ray diffraction, transmission electron microscopy, and optical spectroscopies. The luminescence evolution of the synthesized NCs is as follows: from the broad spectrum (peaking at 756 nm) of the AgInS2core NCs to become the narrow excitonic emission (at 575 nm) prominent beside the broad one after shelling with GaSx, then only the bright excitonic luminescence (at 575 nm) without broad emission after double-shelling with GaSx/ZnS. The double-shell has made the AgInS2/GaSx/ZnS NCs not only remarkably enhance their luminescence quantum yield (QY) up to ∼60% but also maintain the narrow excitonic emission stably for a long-term storage over 12 months. The outermost ZnS shell is believed to play a key role in enhancing QY and protecting AgInS2and AgInS2/GaSxfrom certain damage.

Systematic synthesis of different-sized AgInS2/GaSxnanocrystals for emitting the strong and narrow excitonic luminescence.

This paper presents for the first time the systematic synthesis of AgInS2(AIS) nanocrystals (NCs) with different sizes of 2.6-6.8 nm just by controlling only the reaction temperature. The synthesis of AIS core NCs was carried out in 2 steps: (i) synthesis of Ag2S NCs and then (ii) partial exchange of Ag+with In3+in the template Ag2S NCs. For step (i), Ag2S NCs of different sizes were synthesized by reaction of the Ag and S precursors at different temperatures of 30 °C to 130 °C, for the same reaction time of 30 min. For step (ii), AIS NCs were created by the exchange of Ag+with In3+at 120 °C for 60 min. Finally, GaSxwas shelled on AIS core NCs to produce the AgInS2/GaSxcore/shell structures. The synthesized AIS/GaSxNCs demonstrate the clear excitonic absorptions and strong, narrow excitonic luminescence peaking at 530-606 nm depending on the size of AIS core NCs.

Electrochemiluminescence ultrasensitive immunoassay for carbohydrate antigen 125 based on AgInS2/ZnS nanocrystals.

We developed a near-infrared (NIR) electrochemiluminescence (ECL) immunosensor for sensitively and selectively determining carbohydrate antigen 125 (CA125) with toxic-element-free and environmental-friendly AgInS2/ZnS nanocrystals (NCs) as tags. The core/shell-structured AgInS2/ZnS NCs not only can be conveniently prepared via an aqueous synthetic procedure, but also has high photoluminescence quantum yield (PLQY) of up to 61.7%, highly monodispersed, water-soluble, and desired biological compatibility. As AgInS2/ZnS NCs can be oxidized via electrochemically injecting holes into their valence band at + 0.84 V, both the monodispersed AgInS2/ZnS NCs in solution and the surface-confined AgInS2/ZnS NCs immobilized in sandwich-typed immuno-complexes with CA125 as analyte can exhibit efficient oxidative-reduction ECL around 695 nm under physiological conditions with the presence of tri-n-propylamine (TPrA). The ECL intensity from the AgInS2/ZnS NCs immobilized in sandwich-typed immuno-complexes increases linearly and selectively with an increased concentration of CA125 from 5 × 10-6 to 5 × 10-3 U/mL, and limit of detection (LOD) was 1 × 10-6 U/mL (S/N = 3). This reliable platform can provide an effective detection method in the early diagnosis and treatment of ovarian cancer.

Dendritic TiO2 /ln2 S3 /AgInS2 trilaminar core-shell branched nanoarrays and the enhanced activity for photoelectrochemical water splitting.

Hierarchical TiO2 /ln2 S3 /AgInS2 trilaminar core-shell branched nanorod arrays (T-CS BNRs) have been fabricated directly on conducting glass substrates (FTO) via a facile, versatile and low-cost hydrothermal and successive ionic layer adsorption and reaction (SILAR) for photoelectrochemical (PEC) water splitting. On the basis of optimal thickness of AgInS2 shell, such TiO2 /ln2 S3 /AgInS2 T-CS BNRs exhibit a higher photocatalytic activity, the photocurrent density and efficiency for hydrogen generation are up to 22.13 mA·cm(-2) and 14.83%, which is, to the best of our knowledge, the highest value ever reported for similar nanostructures. The trilaminar architecture is able to suppress carrier recombination and increase electron collection efficiency via (i) increasing the photon absorption through the lager specific surface area of TiO2 BNRs and a sensitizer layer (AgInS2 ), (ii) a buffer layer (ln2 S3 ), (iii) a better energy level alignment.

Antibacterial Activity and Cytotoxicity Screening of Acyldepsipeptide-1 Analogues Conjugated to Silver/Indium/Sulphide Quantum Dots.

The continuous rise in bacterial infections and antibiotic resistance is the driving force behind the search for new antibacterial agents with novel modes of action. Antimicrobial peptides (AMPs) have recently gained attention as promising antibiotic agents with the potential to treat drug-resistant infections. Several AMPs have shown a lower propensity towards developing resistance compared to conventional antibiotics. However, these peptides, especially acyldepsipeptides (ADEPs) present with unfavorable pharmacokinetic properties, such as high toxicity and low bioavailability. Different ways to improve these peptides to be drug-like molecules have been explored, and these include using biocompatible nano-carriers. ADEP1 analogues (SC005-8) conjugated to gelatin-capped Silver/Indium/Sulfide (AgInS2) quantum dots (QDs) improved the antibacterial activity against Gram-negative (Escherichia coli and Pseudomonas aeruginosa), and Gram-positive (Bacillus subtilis, Staphylococcus aureus and Methicillin-resistant Staphylococcus aureus) bacteria. The ADEP1 analogues exhibited minimum inhibition concentrations (MIC) between 63 and 500 µM, and minimum bactericidal concentrations (MBC) values between 125 and 750 µM. The AgInS2-ADEP1 analogue conjugates showed enhanced antibacterial activity as evident from the MIC and MBC values, i.e., 1.6-25 µM and 6.3-100 µM, respectively. The AgInS2-ADEP1 analogue conjugates were non-toxic against HEK-293 cells at concentrations that showed antibacterial activity. The findings reported herein could be helpful in the development of antibacterial treatment strategies.

Near-infrared light-driven lab-on-paper cathodic photoelectrochemical aptasensing for di(2-ethylhexyl)phthalate based on AgInS2/Cu2O/FeOOH photocathode.

Di(2-ethylhexyl)phthalate (DEHP) is commonly released from plastics in aqueous environment, which can disrupt endocrine system and cause adverse effects on public health. There is a pressing need to highly sensitive detect DEHP. Herein, a near-infrared (NIR) light-driven lab-on-paper cathodic photoelectrochemical aptasensing platform integrated with AgInS2/Cu2O/FeOOH photocathode and "Y"-like ternary conjugated DNA nanostructure-mediated "ON-OFF" catalytic switching of hemin monomer-to-dimer was established for ultrasensitive DEHP detection. Profiting from the collaborative roles of the effective photosensitization of NIR-response AgInS2 and the fast hole extraction of FeOOH, the NIR light-activated AgInS2/Cu2O/FeOOH photocathode generated a markedly enhanced photocathodic signal. The dual hemin-labelled "Y"-like ternary conjugated DNA nanostructures made the hemin monomers separated in space and they maintained highly active to catalyze in situ generation of electron acceptors (O2). The hemin monomers were relocated in close proximity with the help of target-induced allosteric change of DNA nanostructures, which could spontaneously dimerize into catalytically inactive hemin dimers and fail to mediate electron acceptors generation, resulting in a decreased photocathodic signal. Therefore, the ultrasensitive DEHP detection was realized with a linear response range of 1 pM-500 nM and a detection limit of 0.39 pM. This work rendered a promising prototype to construct powerful paper-based photocathodic aptasensing system for sensitive and accurate screening of DEHP in aqueous environment.

Detection of enrofloxacin residues in dairy products based on their fluorescence quenching effect on AgInS2 QDs.

Water-soluble AgInS2 (AIS) quantum dots (QDs) were successfully prepared through the one-pot water phase method with thioglycolic acid (TGA) as the stabilizing agent. Because enrofloxacin (ENR) effectively quenches the fluorescence of AIS QDs, a highly-sensitive fluorescence detection method is proposed to detect ENR residues in milk. Under optimal detection conditions, there was a good linear relationship between the relative fluorescence quenching amount (ΔF/F0) of AgInS2 with ENR and ENR concentration (C). The detection range was 0.3125-20.00 µg/mL, r = 0.9964, and the detection limit (LOD) was 0.024 µg/mL (n = 11). The average recovery of ENR in milk ranged from 95.43 to 114.28%. The method established in this study has advantages including a high sensitivity, a low detection limit, simple operation and a low cost. The fluorescence quenching mechanism of AIS QDs with ENR was discussed and the dynamic quenching mechanism of light-induced electron transfer was proposed.

Photoelectrochemical biosensing platform based on in situ generated ultrathin covalent organic framework film and AgInS2 QDs for dual target detection of HIV and CEA.

In this work, a new photoelectrochemical (PEC) biosensing platform based on an ordered two-dimensional (2D) ultrathin covalent organic framework (COF) film and AgInS2 quantum dots (QDs) has been developed to enable dual-target detection of HIV and CEA. The porous COF film was firstly in situ generated on ITO, displaying super-stable and intense photocurrent with excellent repeatability. Moreover, an effective PEC quenching probe was specifically designed by loading large number of AgInS2 QDs on Au nanoparticles (NPs). After target HIV-induced cyclic amplification process to generate abundant DNA S0, the Au NPs-AgInS2 QDs probe was binded to the COF film through DNA hybridization, enabling PEC signal of the COF film to turn "off" for ultra-sensitive detection of HIV. Furthermore, when CEA as the second target specifically binded to its aptamer, the Au NPs-AgInS2 QDs quenching probe was released, achieving PEC signal "on" of the T-DA COF film for ultra-sensitive detection of CEA. This work opened a unique 2-D COF film-based PEC biosensing platform with excellent signal for rapid detection of dual targets, which can effectively avoid false positives and negatives and shows promising application for early prevention and detection of cancer diseases.

Polyvinylpyrrolidone as a Stabilizer in Synthesis of AgInS2 Quantum Dots.

A synthesis protocol of polyvinylpyrrolidone-capped AgInS2 quantum dots in aqueous solution is reported. Nanoparticle morphology and chemical composition were studied by means of TEM, XRD, XPS, and FTIR. The obtained quantum dots were luminescent in the visible range. The photoluminescence intensity dependence on the polyvinylpyrrolidone amount was demonstrated. The wavelength of the emission maximum varied with changing the [Ag]:[In] molar ratio. The temperature dependence of the photoluminescence intensity of the polyvinylpyrrolidone-capped AgInS2 quantum dots was investigated within the temperature range of 11-294 K.

Accurate and Real-Time Detection Method for the Exothermic Behavior of Enzymatic Nano-Microregions Using Temperature-Sensitive Amino-AgInS2 Quantum Dots.

The thermal behavior of enzymes in nanoscale is of great significance to life phenomena. This nonequilibrium state real-time thermal behavior of enzymes at nanoscale cannot be accurately detected by existing methods. Herein, a novel method is developed for the detection of this thermal behavior. The enzyme-quantum dot (QD) conjugates can be obtained by chemically grafting temperature-sensitive amino-AgInS2 QDs to the enzyme, where the QDs act as nanothermometers with a sensitivity of -2.82% °C-1 . Detecting the photoluminescence intensity changes of the enzyme-QD conjugates, the real-time thermal behavior of enzymes can be obtained. The enzyme-QD conjugates show a temperature difference as high as 6 °C above ambient temperature in nano-microregions with good reproducibility (maximum error of 4%) during catalysis, while solution temperature hardly changed. This method has a temperature resolution of ≈0.5 °C with a detection limit of 0.02 mg mL-1 of enzyme, and spatially ensured that the amino-AgInS2 QDs are quantitatively bound to the enzyme; thus, it can accurately detect the exothermic behavior of the enzyme and can be extended to other organisms' detection. This method has high sensitivity, good stability, and reliability, indicating its great potential application in investigating the thermal behavior of organisms in nanoscale and related life phenomena.

Photoluminescent and visual determination of ibandronic acid using a carbon dots/AgInS2 quantum dots ratiometric sensing platform.

A sensing platform combining carbon dots (CDs, with blue emission) and thiomalic acid (TMA)-capped AgInS2 quantum dots (QDs, with orange emission) was developed aiming the photoluminescence (PL) ratiometric determination of ibandronic acid (IBAN), a bisphosphonate pharmaceutical. The ternary AgInS2 QDs were used for IBAN probing, undergoing a concentration-related PL quenching in its presence, whilst the PL of CDs remained practically unaffected due to its chemical inertness towards the antiresorptive drug, provided an intrinsic self-reference fluorophore. In addition, a visual sensing approach was also proposed, employing for the first time ternary QDs. This relied on RGB images acquired by means of a digital camera and seek the development of a rapid IBAN screening test. The developed sensing platforms were employed for IBAN determination in samples with pharmaceutical interest providing good results, in accordance to the reported IBAN levels, and obtaining recovery values between 98 and 103%.

Mn2+ doped AgInS2 photocatalyst for formaldehyde degradation and hydrogen production from water splitting by carbon tube enhancement.

In this work, AgInS2 and Mn2+ doped AgInS2 (Mn-AgInS2) with different Mn2+: (Ag+ + In3+) ratios were synthesized via a low temperature liquid method. The photocatalytic activity of the obtained samples was followed by taking formaldehyde as the target pollutant under visible light irradiation. The photocatalysts were passed through various characterization procedures to investigate their morphological, structural and photophysical characteristics. The optimal proportion sample [with the ratio n (Mn2+): n (Ag+ + In3+) = 1:100] photodegraded about 79% formaldehyde in 150 min. These upgraded activities are attributed to the enhanced visible light absorption and superior charge separation due to the presence of Mn2+ as confirmed site from charge separation measurements. In addition, a possible mechanism for the photodegradation of formaldehyde is proposed based on the experimental results. Furthermore, the photocatalytic water splitting performance of Mn-AgInS2 and multi-walled carbon nanotubes (MWCNTs) modified Mn-AgInS2 is investigated and compared under simulated sunlight irradiation, and remarkable hydrogen production is achieved (105 µmol h-1 g-1) by using the latter.

Luminescence-Tunable ZnS-AgInS2 Nanocrystals for Cancer Cell Imaging and Photodynamic Therapy.

A highly luminescent I-III-VI group of semiconductor nanocrystals (NCs) has attracted considerable attention for applications in biomedical engineering and design of novel optoelectronic devices. In this work, high quality ZnS-AgInS2 (ZAIS) solid solution NCs were synthesized by thermal decomposition of a organometallic diethyldithiocarbamate precursor complex of (AgIn)xZn2(1-x) (S2CN(C2H5)2)4 in the presence of specific stabilizing and structure directing agents. By changing the composition of the precursor complex (value of x), the structure and optical property could easily be adjustable, thus leading to the formation of nanowire, nanorod, and tetrapod-like NCs and highly luminescent green to yellow to red color tunable NCs. The ZAIS NCs were further transferred to aqueous medium by 3-mercaptopropionic acid (MPA) capping without losing any optical properties. The color-tunable, water-soluble, and biocompatible ZAIS NCs were utilized for the in vitro cellular imaging of human cervical cancer cells (HeLa cells) and showed intense localization in the cell cytoplasm after 6 h of incubation. In addition, the inherent photocatalytic property of ZAIS NCs under light illumination showed promising photodynamic therapy of cancer cells, and thus, ZAIS NCs could be a promising candidate for future biomedical applications.

Cathode-Anode Spatial Division Photoelectrochemical Platform Based on a One-Step DNA Walker for Monitoring of miRNA-21.

Photoelectrochemical (PEC) biosensors carried out the whole reaction process in the same solution, which would limit the sensitivity and selectivity of detection in the sensing system. Herein, we reported a promising new cathode-anode spatial division PEC platform based on the two-electrode synergistic enhancement strategy. With the photoanode and photocathode integrated in the same current circuit, the platform exhibited an increased photocurrent response, as well as an improved anti-interference ability led by separating the two electrodes spatially. In this proposal, red light-driven AgInS2 nanoparticles (NPs) served as the photoanode to build biometric steps and amplify the signal, whereas p-type PbS quantum dots were selected as the photocathode to increase the signal. With the participation of alkaline phosphatase (ALP) labeled on Au NPs-DNA, ascorbic acid 2-phosphate was catalyzed to produce ascorbic acid as an electron donor, resulting in the enhancement of the PEC signal. Interestingly, in the presence of miRNA-21 and T7 Exo, the one-step DNA walker amplification can be triggered to reduce the PEC signal by releasing ALP-Au NP-DNA. The constructed PEC biosensor exhibited a detection limit of as low as 3.4 fM for miRNA-21, which was expected to be applied to early clinical diagnosis. Also, we believe that the proposed cathode-anode spatial division PEC platform can open up a new view for the establishment of other types of PEC biosensors.

Lab-on-Microsphere-FRET-Based Multiplex Sensor Platform.

Here we report on the development and investigation of a novel multiplex assay model based on polymer microspheres (PMS) encoded with ternary AIS/ZnS quantum dots (QDs). The system was prepared via layer-by-layer deposition technique. Our studies of Förster resonance energy transfer (FRET) between the QD-encoded microspheres and two different cyanine dyes have demonstrated that the QD photoluminescence (PL) quenching steadily increases with a decrease in the QD-dye distance. We have found that the sensitized dye PL intensity demonstrates a clear maximum at two double layers of polyelectrolytes between QDs and Dye molecules on the polymer microspheres. Time resolved PL measurements have shown that the PL lifetime decreases for the QDs and increases for the dyes due to FRET. The designed system makes it possible to record spectrally different bands of FRET-induced dye luminescence with different decay times and thereby allows for the multiplexing by wavelength and photoluminescence lifetimes of the dyes. We believe that PMS encoded with AIS/ZnS QDs have great potential for the development of new highly selective and sensitive sensor systems for multiplex analysis to detect cell lysates and body fluids' representative biomarkers.

Chemometric-assisted kinetic determination of oxytetracycline using AgInS2 quantum dots as PL sensing platforms.

In this work a kinetic fluorometric methodology relying on the time-based monitoring of the photoluminescence quenching of AgInS2 ternary quantum dots induced by oxytetracycline, was developed. The kinetic approach allowed not only to reduce the LOD and improve sensitivity and selectivity but also to collect second-order data that was explored for the quantification of the target analyte in the presence of uncalibrated interfering species. Upon processing the acquired second-order kinetic PL data by unfolded partial least-squares (U-PLS), oxytetracycline was quantified in commercially available pharmaceutical formulations. The obtained results, namely an R2P higher than 0.99 and RE lower than 8%, proved the suitability and accuracy of the developed approach.

Constructing defect-related subband in silver indium sulfide QDs via pH-dependent oriented aggregation for boosting photocatalytic hydrogen evolution.

Surface engineering of quantum dots (QDs) plays critical roles in tailoring carriers' dynamics of I-III-VI QDs via the interplay of QDs in aggregates or assembly, thus influencing their photocatalytic activities. In this work, an aqueous synthesis and the followed pH tuned oriented assembly method are developed to prepare network-like aggregates, dispersion, or sheet-like assembly of GSH-capped Silver Indium Sulfide (AIS). FTIR, DLS, and HRTEM investigation revealed that surface protonation or deprotonation of QDs occurred at pH < 6 or pH > 12 favors the formation of network-like aggregates with various defects or sheet-like assembly with perfect crystal lattice, respectively, via the surface charge induced interaction among AIS QDs. Further UV-vis, steady and transient PL investigation confirm the narrowed band gaps and the prolonged PL lifetime of the acidic network-like aggregates. As a result, the optimized network-like aggregates (3.0-AIS) exhibits superior photocatalytic H2 evolution (PHE) rates (5.2 mmol·g-1·h-1), about 113 times that of alkaline sheet-like assembly (13.0-AIS) or 2.7 times higher than that of dispersed AIS QDs (AIS-8.0). The formation of defects and their roles in PHE mechanisms are discussed. This work is expected to give some new insight for designing efficient non-cadmium/non-novel metal I-III-VI photocatalysts for boosting PHE.