Distinction of Plasmonic Intrananoparticle and Internanoparticle Molecular Reaction Rates at the Three-Phase Contact Line of an Evaporating Sessile Droplet.

Molecular reactions on the surface of a plasmonic nanoparticle (intrananoparticle) and between nanoparticles (internanoparticle) may differ in kinetics, dynamics, and product selectivity. We report that the difficulty in distinguishing the kinetics in a dispersion medium could be overcome by probing the reactions at the three-phase contact line (TPCL) of an evaporating sessile droplet using surface-enhanced Raman spectroscopy (SERS). Thus, when an evaporating aqueous droplet on glass containing 4-aminothiophenol-stabilized Ag nanoparticles was monitored by SERS at the TPCL, dimerization into 4,4'-dimercaptoazobenzene followed two steps, each preceded by the loss of H-bonded water accordingly. On the basis of the results, we assigned the first step with a higher relative kinetic rate (∼3 times) to be an intrananoparticle reaction and the second one as an internanoparticle reaction. In D2O medium, the ratio of the rates was ∼1.8. The observed vibrational signatures of the losses of water molecules before reactions and product formations were accounted for by using density functional theoretical calculations.

Modulating the Photoluminescence of Europium through Crystalline Assembly Formation with Gold Nanoclusters and Then Phosphate Ions.

We report delayed fluorescence enhancement of europium (Eu3+) ions through complexation with ligand-stabilized gold nanoclusters (Au NCs). The different Eu3+-centric emissions following complexation with Au NCs exhibited selective augmentation in the spectral lines attributed to the 5D0 → 7FJ transitions. The photoluminescence (PL) properties, including delayed Eu emission, from each component could be modulated through further functionalization of phosphate ions (Pi), leading to crystallization. The assembled crystalline structure of europium-containing Au NCs (Eu Au NCs) was corroborated by selected area electron diffraction analyses and high-resolution transmission electron microscopy analyses. On the basis of PL measurements and other experimental evidence, the two different lifetimes arising from the components, prompt emission of Au NCs and delayed emission of Eu3+, were affected in the assembled nanostructure. Such a design offers the possibility of developing an optical system by conjugating molecular NCs and atomic luminescent probes that has potential uses.

Dimension-Dependent Magnetic Behavior of Manganese-Cysteine Inorganic Complex Nanoparticles.

A cysteine-based complex of Mn2+ led to the formation of nanoparticles in aqueous medium under ambient conditions. The formation and evolution of the nanoparticles in the medium were followed by ultraviolet-visible light (UV-vis) spectroscopy, circular dichroism, and electron spin resonance spectroscopy that also revealed a first-order process. The magnetic properties of the nanoparticles isolated as solid powders exhibited strong crystallite and particle size dependence. At low crystallite size, as well as particle size, the complex nanoparticles showed superparamagnetic behavior similar to other magnetic inorganic nanoparticles. The magnetic nanoparticles were found to undergo a superparamagnetic to ferromagnetic transition, and then to paramagnetic transition with a gradual increase in either their crystallite size or particle size. The discovery of dimension-dependent magnetic property of inorganic complex nanoparticles may usher in a superior option for tuning the magnetic behavior of nanocrystals, depending on the component ligands and metal ions.

Living Gut Bacteria Functionalized with Gold Nanoclusters and Drug for Facile Cancer Theranostics.

Bacbots are potent self-propelling vehicles for targeted therapy that can be guided by chemical and biochemical stimuli of the host. In addition, they can be guided externally by the use of magnetic field or other physical forces. The challenge is to incorporate drugs and diagnostic tools in living bacteria with retention of theranostic activity until reaching the targets and easy clearance of the remainder following the treatment. We report that living Lactobacillus rhamnosus, when functionalized with photoluminescent Au nanoclusters and the anticancer drug methotrexate, was cytotoxic to monolayer and spheroids of cancer cells (HeLa and HT29) even at a low dose of bacteria used (107 cfu/mL). The observed cell death was nearly 90% in HeLa spheroids and 70% in HT29 spheroids. Further, functionalization of the bacterial surface with the nanoclusters helped incorporate the drug onto their cell surfaces. The drug and nanocluster-loaded bacteria annihilated the cells and the spheroids in a rather short time (6 h) that revealed the specificity and effectiveness of the bacbots. The bacbots exhibited synergistic toxicity on the cells as their effect was more than the drug and the bacteria individually. This higher toxicity could be associated with elevated levels of reactive oxygen species generated in the bacbot-treated cells. The multifunctional bacbots reported here provide an option for guided therapy with the natural variant of the human gut-friendly living bacteria without the need for attenuation or genetic modification.

Simultaneous Sensing of H2 O, D2 O and HOD through Peroxo Vibrations.

Detection of HOD simultaneously in the presence of a mixture of H2 O and D2 O is still an experimental challenge. Till date, there is no literature report of simultaneous detection of H2 O, D2 O and HOD based on vibrational spectra. Herein we report simultaneous quantitative detection of H2 O, D2 O and HOD in the same reaction mixture with the help of bridged polynuclear peroxo complex in absence and presence of Au nanoparticles on the basis of a peroxide vibrational mode in resonance Raman and surface enhanced resonance Raman spectrum. We synthesize bridged polynuclear peroxo complex in different solvent mixture of H2 O and D2 O. Due to the formation of different nature of hydrogen bonding between peroxide and solvent molecules (H2 O, D2 O and HOD), vibrational frequency of peroxo bond is significantly affected. Mixtures of different H2 O and D2 O concentrations produce different HOD concentrations and that lead to different intensities of peaks positioned at 897, 823 and 867 cm-1 indicating H2 O, D2 O and HOD, respectively. The lowest detection limits (LODs) were 0.028 mole fraction of D2 O in H2 O and 0.046 mole faction of H2 O in D2 O. In addition, for the first time the results revealed that the cis-peroxide forms two hydrogen bonds with solvent molecules.

The Potential of Gadolinium Ascorbate Nanoparticles as a Safer Contrast Agent.

There have been health concerns raised against the use of gadolinium (Gd)-based magnetic resonance imaging contrast agents. The primary observation is that Gd ions are prone to leaking into the bloodstream, causing nephrogenic systemic fibrosis as one of the side effects. In addition, such leakage of the ions inhibits easy clearance from the body. Herein we propose that Gd-ascorbate nanoparticles could be one of the safer choices as they are rather stable in aqueous dispersion and they do not get affected by Zn or Fe ions in the medium. The magnetic properties of the ions are preserved in the nanoparticles, and particles when sufficiently small may be amenable to renal clearance from the human body. Thus, when an aqueous solution of Gd-acetate and ascorbic acid was left to evolve with time, a Gd-ascorbate complex was formed that led to the formation of nanoparticles with time. The sizes of the nanoparticles increased with time, and when the particles were sufficiently large, they precipitated out of the medium. In addition, smaller nanoparticles were consistently present at all times of observations. UV-vis, photoluminescence and FTIR spectroscopy, mass spectrometry, and transmission electron microscopy analyses confirmed the formation of nanoparticles of Gd-ascorbate complex. In addition, magnetic measurements confirmed the high relaxivity of the nanoparticles as compared to the parent salt, indicating the effectiveness of the nanoparticles as contrast agents. Density functional theory-based calculations of the molecular complex-based nanoparticles accounted for the experimental observations.

Mannosylated Gold Nanoclusters Incorporated with a Repurposed Antihistamine Drug Promethazine for Antibacterial and Antibiofilm Applications.

Drug repurposing presents a workable strategy in tackling antibiotic resistance. Many known drugs have been repurposed for their applications against different targets. Antihistamines that are usually used to treat allergy symptoms can be combined with nanoscale materials to enhance their efficiency. Herein, we explored the antimicrobial properties of a common antihistamine drug, promethazine, in Gram-positive and Gram-negative bacteria. Being positively charged, promethazine was easily incorporated into the mannose-conjugated bovine serum albumin-stabilized promethazine hydrochloride gold nanoclusters. Capping with d-mannose helped in targeting the bacteria by inhibiting their adhesive appendage called pili. Following their uptake, drugs released inside the bacteria caused reactive oxygen species production and membrane permeability alteration, ultimately resulting in bacterial inhibition. Additionally, they were also explored for biofilm eradication. As observed through staining assays, the number of dead cells increased with increasing concentration of drug-loaded gold nanoclusters in the biofilm mass. Therefore, the as-synthesized mannosylated gold nanoclusters incorporated with promethazine were analyzed for potential antibacterial and antibiofilm applications.

Enhanced Chemical Stability in the Twisted Dodecagonal Stacking of Two-Dimensional Copper Nanocluster Assemblies.

Deterministic chemical stacking of two-dimensional materials with controlled symmetry is a synthetic chemistry challenge that deserves attention. It is plausible that depending on the angle of stacking the material properties of the assembly could be tuned. Herein, we report 30° twisted stacking of two-dimensional nanosheets of a hexagonal assembly of organic ligand-stabilized Cu nanoclusters formed through a Zn2+-mediated complexation reaction. Electron diffraction in transmission electron microscopy revealed the presence of regions of dodecagonal symmetry with the apparent loss of translation symmetry. Photoluminescence measurements indicated the formation of the stacked assembly in the liquid medium. The as-synthesized twisted stacking structure exhibited superior delayed photoluminescence and chemical stability─in the presence of molecular iodine─as compared to the hexagonal crystal. The discovery can lead to a bright future in exploring new chemical and physical properties through the design of stacked assemblies of luminescent or other materials.

In Vitro Therapeutic Attributes of Luminescent Hydroxyapatite Nanoparticles in Codelivery Module.

Imminent prospects of clinical importance have been accomplished through divergent treatment modalities implemented using nanoscale platforms. In the present study, hydroxyapatite nanoparticles doped with copper nanoclusters (HAPs) were explored for codelivery of a hydrophobic drug, namely, norfloxacin (NX), and a hydrophilic photosensitizer, such as methylene blue (MB). NX and MB were successfully homed into HAPs (MB-NX-HAPs), which further exhibited a pH-dependent release of both. With the objective of attaining an enhanced effect, MB-NX-HAPs were evaluated for combination therapy, involving chemotherapy and photodynamic therapy (PDT) with irradiation at 640 nm. The combinatorial therapy approach was initially applied for antibacterial therapy, which suggested a considerable reduction in bacterial growth of Gram-negative strain Pseudomonas aeruginosa MTCC 2488. Thereafter, the antiproliferative study performed in cancer cell lines (HeLa and MCF-7) revealed the efficiency of MB-NX-HAPs in bestowing a combinatorial effect through chemotherapy and PDT (irradiation at 640 nm). The combined effect exerted through MB-NX-HAPs subsequently induced reactive oxygen species (ROS) generation, cell cycle alteration, and apoptosis activation in cancer cells. The biocompatible nature of MB-NX-HAPs was appreciably shown through their minimal effect on the normal cell line (HEK-293). Additionally, HAPs through luminescence of copper nanoclusters were suggested to aid in bioimaging of cancer cell lines.

Hierarchical Passage of Gold Nanoclusters in Living Bacteria.

Gold (Au) nanoclusters chemically synthesized on the cell surface of living Lactobacillus rhamnosus rendered them photoluminescent. Importantly, the bacteria were viable and the clusters were passed down the generations with the loss of luminescence in the first subculture onward. The clusters were agglomerated into spherical structures of 100-200 nm, without being converted to plasmonic Au nanoparticles, on the cell surfaces of the bacteria of all six subcultures studied. The results indicated the role of cell wall remodeling in transforming the Au nanoclusters into larger aggregates down the generations. This may hold important implications for using nanoparticle-studded bacteria in theranostics.

Surface Engineering of Quantum Dots for Self-Powered Ultraviolet Photodetection and Information Encryption.

We demonstrate fabrication of photodetectors in the UVC and UVA regions, based on surface engineering of Mn2+-doped ZnS Qdot. Mn2+-doped ZnS Qdot exhibited UVC detection with a responsivity of 0.3 ± 0.02 A·W-1 and detectivity of 1.7 ± 0.2 1011 Jones. Following this, the Qdot was surface modified with 8-hydroxyquinoline 5-sulfonic acid ligand, which resulted in the formation of a bluish green zinc quinolate complex (Zn(QS)2) at the Qdot surface (defined as the quantum dot complex, QDC) exhibiting overall white photoluminescence. The detector developed with QDC as the photoactive material exhibited a responsivity of 0.2 ± 0.02 A·W-1 and detectivity of 1.2 ± 0.2 1011 Jones in the UVA band. This shift in the detection band from UVC in Qdot to UVA in QDC, through the surface complexation mechanism, is a new approach for tuning spectral detection featured in this work. Besides, the self-powered response of both the detectors exhibited attractive photoelectric characteristics. The detectors were incorporated in a portable prototype to show their potential application toward selective UVC and UVA spectral detection. Additionally, the dual-mode emission of the QDC was used for data encryption and decryption.

Enhanced solid-state plasmon catalyzed oxidation and SERS signal in the presence of transition metal cations at the surface of gold nanostructures.

The effect of several metal cations (Mn2+, Co2+, Ni2+, Cu2+ and Zn2+) on the photochemical conversion of 4-aminothiophenol (4-ATP) into 4,4'-dimercaptoazobenzene (DMAB) is probed using surface enhanced Raman scattering (SERS). The coupling reaction is carried out on the surface of Au nanoparticles and Au nanorods using 532 nm and 632.8 nm laser excitations, respectively, in the absence and presence of metal cations. Here, we report that DMAB formation on the surface of Au nanostructures - when carried out in the solid state - is augmented significantly (by a factor of 1.98 to 4.07 and 3.34 to 5.74 for Au nanoparticle and Au nanorod substrates, respectively, and depending on the metal). Furthermore, the SERS signal is also markedly enhanced. Thus, the results underpin a new way of carrying out a photochemical reaction with a higher yield along with a higher SERS signal.

A Ratiometric and Visual Sensing of Phosphate by White Light Emitting Quantum Dot Complex.

Ratiometric and visual sensing of phosphate by using a white light emitting quantum dot complex (WLE QDC) is reported herein. The WLE QDC comprised of Mn2+-doped ZnS quantum dot (with λem = 585 nm) and surface zinc quinolate (ZnQS2) complex (with λem= 480 nm). The limit of detection was estimated to be of 5.9 nM in the linear range of 16.6-82.6 nM. This was accomplished by monitoring the variations in the photoluminescence color, intensity ratio (I480/I585), chromaticity and hue of the WLE QDC in the presence of phosphate. The high selectivity and sensitivity of WLE QDC toward phosphate was observed. The chemical interaction of ZnQS2 (present in WLE QDC) with phosphate might have led to the observed specificity in photoluminescence changes. The presented WLE QDC was successfully employed for the quantification of phosphate in samples prepared using environmental water and commercial fertilizer.

An ambient complexation reaction of zinc acetate and ascorbic acid leads to a new form of nanoscale particles with emergent optical properties.

We report the formation of nanoscale particles from the complexation reaction between zinc acetate and ascorbic acid under ambient conditions and in an aqueous medium. The reaction led to the formation of a molecular complex with the formula Zn x (AA) y (OAc) z (x, y, and z = possible smallest positive integer) with AA meaning ascorbate, based on the mass spectrometry results. Following this, the formation of luminescent nanoscale particles - the size of which increased with time - was observed. During 24 h of observation, the sizes increased to about 50 nm in the presence of different sizes at all times. Transmission electron microscopy results also indicated the formation of polycrystalline as well as amorphous nanoparticles in the medium. Further, the appearance of a UV absorption peak at 380 nm and photoluminescence peak at 473 nm marked the formation of the nanoparticles. The luminescence was also observed to be wavelength tuneable. FTIR and NMR spectroscopy results also supported the formation of a molecular complex with the above formula. The present work highlights the importance of emergent properties of nanoscale molecular materials for crystallization. Also, the present discovery is expected to contribute to the development of safe nanomaterials.

Nanometer-Thick Superhydrophobic Coating Renders Cloth Mask Potentially Effective against Aerosol-Driven Infections.

The advent of COVID-19 pandemic has made it necessary to wear masks across populations. While the N95 mask offers great performance against airborne infections, its multilayered sealed design makes it difficult to breathe for a longer duration of use. The option of using highly breathable cloth or silk masks especially for a large populace is fraught with the danger of infection. As a normal cloth or silk mask absorbs airborne liquid, it can be a source of plausible infection. We demonstrate the chemical modification of one such mask, Eri silk, to make it hydrophobic (contact angle of water is 143.7°), which reduces the liquid absorption capacity without reducing the breathability of the mask significantly. The breathability reduces only 22% for hydrophobic Eri silk compared to the pristine Eri silk, whereas N95 shows a 59% reduction of breathability. The modified hydrophobic silk can repel the incoming aqueous liquid droplets without wetting the surface. The results indicate that a multilayered modified silk mask to make it hydrophobic can be an affordable and breathable alternative to the N95 mask.

Quercetin-Loaded Luminescent Hydroxyapatite Nanoparticles for Theranostic Application in Monolayer and Spheroid Cultures of Cervical Cancer Cell Line In Vitro.

Nanoscale materials have been explored as better alternatives to conventional therapeutic agents in cancer theranostics in the recent period due to efficacy in overcoming biological, biomedical, and biophysical barriers. Analysis on the ability of copper nanocluster (CuNC)-doped hydroxyapatite nanoparticles (Cu-HXNPs) as suitable nanocarriers for anticell proliferative application was carried out. Having high adsorption capacity, the Cu-HXNPs could be loaded with the anticancer drug quercetin, which is a polyphenolic flavonoid compound, and were used as nanocarriers to be applied on HeLa (cancer cells) and HEK-293 (normal cells). The drug release profile was found to be pH-dependent, where maximum release of quercetin from quercetin-loaded Cu-HXNPs was observed in acidic pH as compared to physiological pH. The Cu-HXNPs could release quercetin, which could effectively decline proliferation of cancer cells via generation of reactive oxygen species. Moreover, the released quercetin significantly altered the cell cycle pattern and triggered the cells to undergo apoptosis. Additionally, the efficacy of Cu-HXNPs as a nanocarrier to release quercetin on 3D spheroids of HeLa had been checked, which demonstrated significant reduction in the viability of 3D spheroids. The luminescent CuNCs used for doping HXNPs endowed the nanocarrier with the imaging property, which was an excellent feature in confirming their uptake by the cells. Thus, the study suggested Cu-HXNPs to be a beneficial nanocarrier for both bioimaging and therapeutic purpose in the field of cancer theranostics.

Toward Controlling Evaporative Deposition: Effects of Substrate, Solvent, and Solute.

Understanding evaporative deposition from a colloidal suspension and on-demand control over it are important due to its industrial and biomedical applications. In particular, it is known that interactions among substrate, solute, and solvent have important consequences on evaporative depositions; however, how these are affecting the deposition patterns and at which conditions these interactions are prominent need detailed investigations. Here we report that the total time of deposition (td) and the geometric shape of the droplet (Lc = initial footprint diameter/height) have a significant role in determining the evaporative deposition patterns. We have identified four zones based on td and Lc, and found that with longer deposition time (high td) and larger available space for particle motion within a liquid droplet (high Lc), deposition patterns were governed by the interactions among the substrate, solute, and solvent. We also experimentally demonstrated that the pinned contact line is indispensable for the "coffee ring" effect by comparing the deposition on surfaces with and without hysteresis. The effect of the Marangoni flow is also discussed, and it is shown that by controlling Marangoni flow, one can manipulate the droplet deposition from uniform disk-like to coffee ring with a central deposition.

Integration of a Nonsteroidal Anti-Inflammatory Drug with Luminescent Copper for in Vivo Cancer Therapy in a Mouse Model.

A facile, process of fabrication of a luminescent bovine serum albumin-copper nanocluster (BSA-CuNC) customized ibuprofen nanodrug (BSA-CuNC-Ibf), encapsulating the ibuprofen was developed. Ibuprofen, which is commonly used to treat inflammation, was utilized here as a model drug. The formation of BSA-CuNC initiated by encapsulation of the Cu ions within the protein moiety followed by gradual reduction of the Cu ions by certain amino acid residues like tyrosine and tryptophan at alkaline pH resulted in the formation of BSA-CuNC within the protein template. Heat treatment and lowering the pH fitted the ibuprofen in the center by hydrogen bonding, hydrophobic and electrostatic interactions, and resulted in the formation of nanoparticles. The nanodrug (BSA-CuNC-Ibf) thus formed was characterized by transmission electron microscopy (TEM), dynamic and static light scattering (DLS), and zeta potential. The spherical shaped nanodrug has a hydrodynamic diameter of about 100.4 ± 28.9 nm. The encapsulation efficiency was found to be 94% which corresponds to 1880 µg/mL of ibuprofen in the BSA-CuNC-Ibf nanodrug. The as synthesized BSA-CuNC-Ibf exhibited cytotoxicity on both human cervical cancer cells (HeLa) and human lung cancer cells (A549). The present nanodrug when explored for its tumor preventive role on Daltons lymphoma ascites (DLA) bearing Swiss albino mice, exemplified sizable inhibition of tumor growth by reactive oxygen species mediated apoptosis and by modulating prostaglandin (PGE2) levels. It also inhibited metastasis of the cancer cells, thus enhancing the life expectancy of the mice.

Complexation Reaction-Based Two-Dimensional Luminescent Crystalline Assembly of Atomic Clusters for Recyclable Storage of Oxygen.

In this work, we report storage of oxygen in two-dimensional (2D) crystalline nanosheets comprising luminescent gold nanoclusters (Au NCs). Complexation reaction between Au NCs (stabilized by l-phenylalanine and mercaptopropionic acid) and zinc ions led to the formation of crystalline assembly of Au NCs. The crystalline nature of the assembly of Au NCs was confirmed through transmission electron microscopy (TEM), high-resolution TEM, and selected area electron diffraction (SAED) analysis. Atomic force microscopy (AFM) analysis, in conjunction with field emission scanning electron microscopy (FESEM) analysis, confirmed the 2D nature of the assembly of the Au NCs. The 2D crystalline nanosheets formed out of reaction between Au NCs and Zn2+ were found to be of near-uniform thickness, with an average value of 3.8 ± 1.65 nm. These 2D nanosheets constituting of hierarchically organized Au NCs were further used for reversible storage of oxygen at ambient conditions of 20 °C and 20 bar pressure.

Smartphone controlled interactive portable device for theranostics in vitro.

In this work, a smartphone controlled interactive theranostic device has been developed to perform in vitro photodynamic therapy (PDT) and diagnostic assays for treatment assessment on a single platform. Further, silver nanorod (Ag NR) was identified as a photosensitizer and its effect was studied in three different cell lines. PDT was achieved with Ag NRs using low irradiation (1.4 mW/cm2 at 632 nm) from light emitting diodes (LEDs) in the device. Specifically, PDT in conjugation with widely used chemotherapeutic drug doxorubicin (Dox) proved effective in killing of HeLa cancer cells and multicellular tumor spheroids at a minimum dose of Ag (2.5 µg/mL). The MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) and LDH (lactate dehydrogenase) assays performed with the device indicated the therapeutic success of the delivered PDT. The device is portable and can be adapted for different wavelength irradiations and radiation doses. Additionally, wireless operation using a custom designed smartphone application makes it convenient to use in complex environments without much of human intervention.