Correction: An insight into the optical properties of a sub nanosize glutathione stabilized gold cluster.

Correction for 'An insight into the optical properties of a sub nanosize glutathione stabilized gold cluster' by Lakshmi V. Nair et al., Dalton Trans., 2016, 45, 11286-11291, https://doi.org/10.1039/C6DT01753C.

Electrochemical Approach for the Synthesis of Ultrasmall Cu13 Clusters and Their Application in the Detection of Endotoxin.

Ultrasmall metal nanoclusters are attractive for their size-dependent optical and electrochemical properties. Here, blue-emitting copper clusters stabilized with cetyltrimethylammonium bromide (CTAB) are synthesized using an electrochemical approach. The electrospray ionization (ESI) analysis reveals that the cluster has 13 copper atoms in the core. The clusters are then used for the electrochemical detection of endotoxin─a bacterial toxin in Gram-negative bacteria. Differential pulse voltammetry (DPV) is used to detect endotoxins with high selectivity and sensitivity. It shows a lower detection limit of 100 ag mL-1 with a linear range of 100 ag mL-1 to 10 ng mL-1. The sensor is efficient for detecting endotoxins from human blood serum samples.

Label-free detection of endotoxin and gram-negative bacteria from water using copper (I) oxide anchored reduced graphene oxide.

Bacterial contamination is a serious concern for health and environmental safety. The major toxic effect arises from the endotoxin or lipopolysaccharide (LPS) attached to the cell wall of the gram-negative bacteria. Ultrasensitive endotoxin detection is of supreme importance in sustaining food, clinical and pharmaceutical safety. Herein we report a simple electrochemical detection platform using reduced graphene oxide (rGO) combined with cuprous oxide nanoparticles for the ultrasensitive detection of LPS. The sensor uses polymyxin B (PmB) to achieve the selective response towards LPS. The sensor showed a lower detection limit (LOD) of 10 agmL-1 with linearity from 10 agmL-1 to 10 ngmL-1. Detection of LPS from whole blood is also carried out with excellent sensitivity. The sensor showed excellent recovery rates in whole blood, pointing to the capability of using the sensor in real-life clinical analysis. The sensor detects Gram-negative bacteria from sewage water with a rapid response time, indicating the effectiveness of the sensor in water quality analysis.

A nanoarchitecture of a gold cluster conjugated gold nanorod hybrid system and its application in fluorescence imaging and plasmonic photothermal therapy.

Engineering different nanomaterials into a single functional material can impart unique properties of the parental nanoparticles, especially in the field of bio imaging and therapy. Gold nanomaterials having different sizes, shapes and dimensionalities exhibit exceptional properties apart from their non-toxicity and hence are strong candidates in the biomedical field. Designing a hybrid nanomaterial of two gold nanostructures retaining the individual properties of the parental nanomaterials is challenging. Here, we demonstrate the synthesis of a hybrid nanomaterial (GQC@GNR), comprising an extremely small gold nanocluster and a representative of the asymmetric gold nanostructure, i.e., a gold nanorod, both having their own different exclusive optical properties like tuneable emission and NIR absorption characteristics, respectively. The hybrid system is designed to retain its emission and absorption in the NIR region to use it as an agent for simultaneous imaging and therapy. The formation of GQC@GNR and its architectonics heavily depend on the synthesis route and the parameters adopted which in turn have a direct influence on its properties. The architecture and its connection to the optical properties are explained using UV-Vis absorption and photoluminescence spectroscopy, zeta potential, transmission electron microscopy, etc. DFT-based computational modelling supports architectonics as explained by the experimental findings. The formation of the gold-gold hybrid system witnessed interesting science with a strong indication that materials with desired properties can be designed by appropriately modulating the architectonics of hybrid formation. Finally, folate conjugated GQC@GNR demonstrated its efficacy for targeted imaging and photothermal therapy in HeLa cells and tumor-bearing animal models. The detailed therapeutic efficacy of GQC@GNR is also explained based on Raman spectroscopy.

Cu2+-Mediated Aggregation of Gold Nanoparticles as an Optical Probe for the Detection of Endotoxin.

Endotoxins or lipopolysaccharides (LPS) present in the outer layer of Gram-negative bacteria (GNB) are responsible for bacterial toxicity. It is an environmental hazard that everyone is exposed to daily to various extents. Due to its potent toxicity, quantitative detection with very high sensitivity is essential in the food, medical, and pharmaceutical industries. Herein, we report an optical nanosensor for the rapid and sensitive detection of LPS and GNB based on the Cu2+-mediated aggregation of gold nanoparticles (Cu@AuNPs). The sensor detects LPS within a linear range of 20 ag/mL to 20 ng/mL with a lower detection limit of 0.2 ag/mL. The sensor could successfully recover spiked endotoxin in grape juice with a percentage error of ±0.2, confirming its application in the food industry. The sensor could also distinguish Gram-negative bacteria from Gram-positive bacteria, and the selectivity of the Cu@AuNP sensor toward GNB is utilized to detect Escherichia coli in wastewater. The rapid detection of E. coli without any pretreatment is a promising strategy in water analysis.

A dual signal on-off fluorescent nanosensor for the simultaneous detection of copper and creatinine.

The transition of conventional medicine to personalized medicine has paved the way for sensing new biomolecules. Consequently, this field attracted wide interest due to its capability to provide information on point of care basis. Multi-analyte sensors that emerged recently can perform quick and affordable analysis with minimum quantity of blood samples compared to traditional sensing of individual analytes. The present study focuses on the development of a quantum dot (Qd) based nanosensor for the simultaneous detection of copper and creatinine; two biologically relevant molecules. The sensor was designed by forming a complex of Qd with 1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and picric acid through carboxylic bond formation of Qd-EDC with picric acid. The dual independent emissions of the Qd-EDC complex was used for the simultaneous detection of creatinine and copper by a turn on/turn off method and was successfully demonstrated with a sensitivity of nanomolar to millimolar, and micromolar to millimolar range respectively. The multianalyte sensor thus developed has quick response and works well under normal conditions of temperature and pH. It is also shown to work in cellular environment and blood serum. A simple image based detection of creatinine using the sensor strips has also been attempted by means of a mobile camera and validated with human blood samples.

Luminescent Gold Nanorods To Enhance the Near-Infrared Emission of a Photosensitizer for Targeted Cancer Imaging and Dual Therapy: Experimental and Theoretical Approach.

Strong plasmon absorption in the near-infrared (NIR) region renders gold nanorods (GNRs) amenable for biomedical applications, particularly for photothermal therapy. However, these nanostructures have not been explored for their imaging potential because of their weak emission profile. In this study, the weak fluorescence emission of GNRs is tuned to match that of the absorption of a photosensitizer (PS) molecule, and energy transfer from the GNR to PS enhances the emission profile of the GNR-PS combination. GNR complexes generally quench the fluorescence emission of nearby chromophores. However, herein, the complex retains or rather enhances the fluorescence through competition in energy transfer. Excitation-dependent energy transfer has been explained experimentally and theoretically by using DFT calculations, the CIE chromaticity diagram, and power spectrum. The final GNR-PS complex modified for tumor specificity serves as an excellent organ-specific theranostic probe for bioimaging and dual therapy both in vitro and in vivo. Principal component analysis designates photodynamic therapy a better candidate than that of photothermal therapy for long-term efficacy in vivo.

Real Time Imaging and Dynamics of Hippocampal Zn2+ under Epileptic Condition Using a Ratiometric Fluorescent Probe.

Zinc, the essential trace element in human body exists either in the bound or free state, for both structural and functional roles. Insights on Zn2+ distribution and its dynamics are essential in view of the fact that Zn2+ dyshomeostasis is a risk factor for epileptic seizures, Alzheimer's disease, depression, etc. Herein, a bipyridine bridged bispyrrole (BP) probe is used for ratiometric imaging and quantification of Zn2+ in hippocampal slices. The green fluorescence emission of BP shifts towards red in the presence of Zn2+. The probe is used to detect and quantify the exogenous and endogenous Zn2+ in glioma cells and hippocampal slices. The dynamics of chelatable zinc ions during epileptic condition is studied in the hippocampal neurons, in vitro wherein the translocation of Zn2+ from presynaptic to postsynaptic neuronal bodies is imaged and ratiometrically quantified. Raman mapping technique is used to confirm the dynamics of Zn2+ under epileptic condition. Finally, the Zn2+ distribution was imaged in vivo in epileptic rats and the total Zn2+ in rat brain was quantified. The results favour the use of BP as an excellent Zn2+ imaging probe in biological system to understand the zinc associated diseases and their management.

Gold nanorods decorated with a cancer drug for multimodal imaging and therapy.

Cancer, a condition with uncontrolled cell division, is the second leading cause of death worldwide. The currently available techniques for the imaging and treatment of cancer have their own limitations and hence a combination of more than one modality is expected to increase the efficacy of both diagnosis and treatment. In the present study, we have developed a multimodal imaging and therapeutic system by incorporating a chemotherapeutic drug, mitoxantrone (MTX) onto PEG coated gold nanorods (GNR). Strong absorption in the near-infrared (NIR) and visible regions qualifies GNR as an efficient photothermal (PTT) agent upon irradiation with either a NIR or visible laser. Additionally, the enhanced electric field of GNR makes it a suitable substrate for surface enhanced Raman scattering (SERS). Modification of GNR with amino PEG offers biocompatibility without affecting its optical property. In order to achieve tumor specificity, GNR-PEG was conjugated with tumor specific marker that can target cancer cells, leaving the normal cells unaffected. The incorporation of fluorescent chemotherapeutic drug mitoxantrone onto GNR-PEG facilitates chemotherapy as well as fluorescence imaging. The therapeutic efficacy of the developed GNR based system is tracked using fluorescence imaging and Raman imaging. The careful design of the system also facilitates the controlled release of the drug by photothermal triggering. Likewise, the imaging modality could be chosen as either Raman or fluorescence to monitor drug release in accordance with irradiation. The physico-chemical properties, and drug release profiles under different physiological conditions have been well studied. Finally, the developed system was tested for its therapeutic efficacy using cancer cells, in vitro. The receptor mediated cell uptake was more effective in folate receptor over-expressing cancer cells than in the normal and low-expressing cells. Accordingly the percentage of cell death was higher in folate receptor over-expressing cancer cells, which was further enhanced due to the effect of the dual therapeutic approach. The cell uptake and treatment efficacy was monitored using fluorescence microscopy and SERS. In conclusion, the developed GNR-PEG-MTX system is found to be an efficient multimodal therapeutic agent against cancer which could be tracked using two different techniques.

An insight into the optical properties of a sub nanosize glutathione stabilized gold cluster.

In this study, gold quantum clusters with distinct fluorescence properties were developed and their structural and physical behaviour was evaluated. The clusters were prepared by etching gold nanoparticles with glutathione. Three different Au33 clusters with emission profiles in the NIR region and one blue emitting cluster, Au8 were developed by varying the geometrical arrangement of atoms within the cluster. These clusters having sizes in the range of 0.7 to 2 nm were synthesized by choosing different reaction temperatures from 0 °C to 70 °C and pH between 1.5 and 10. In the three cases, formation of self assembled atoms within the cluster and the corresponding changes in optical properties were observed. A detailed evaluation of the number of atoms and the core-ligand ratio using MALDI-MS and a change in the binding energy as seen in the XPS study confirmed this finding. The study demonstrates that the self assembly of atoms and their arrangement is an important factor in determining the characteristics of the cluster. In this communication, we put forward a new concept where the number of atoms and their arrangement within the clusters play a crucial role in tuning their optical properties.