One-Pot Synthesis of Carbon Nanodots in an Organic Medium with Aggregation-Induced Emission Enhancement (AIEE): A Rationale for "Enzyme-Free" Detection of Cholesterol.

Addressing the limitations associated with the detection of cholesterol, we present a one-pot synthesis of a carbon nanodot (CD) in an organic medium (CDorg) from a novel bile acid hydrazone-based organogel. Interestingly, CDorg possesses the aggregation-induced emission enhancement (AIEE) phenomenon, which rationally aids in the "enzyme-free" detection of cholesterol through a fluorescence turn-on mechanism. On dilution of the THF/water mixture of CDorg with its poor solvent (water), a 9.8-fold enhancement in its photoluminescence (PL) emission is witnessed. Such an enhancement in PL emission is credited to the occurrence of molecular restrictions due to the formation of nanoaggregates of CDorg, thereby initiating a radiative pathway for exciton decay. Excitingly on adding cholesterol to CDorg, we observed a similar enhancement in its PL emission without the use of any cholesterol oxidase (ChO x ) enzyme. The limit of detection and limit of quantification of cholesterol is found to be as low as 1.09 and 3.64 µM, respectively. Hence, this contribution highlights the enzyme-free fluorescence turn-on detection of cholesterol by a novel CD rationally designed to extend its applicability in an organic medium, where it is still considered a major restraint.

Carbon-Dot-Coated Alginate Beads as a Smart Stimuli-Responsive Drug Delivery System.

In this work, we report a smart stimuli-responsive drug delivery system (DDS) that can release drug depending upon the amount of pathogen (MRSA) present in the target. A greater amount of MRSA in the system will lead to more release of drug and vice versa. Carbon-dot-coated novel alginate beads (CA-CD) exhibiting superior stability was successfully used as smart drug delivery vehicle. Garlic extract (GE), which contains allicin, was taken as model drug system to demonstrate the phenomena. It was observed that GE loading was 19 and 78% with CA and CA-CD, respectively. CA-CD-GE shows pH-dependent controlled drug release, which results in increased therapeutic efficiency. CA-CD-GE is not only stimuli responsive but also a controlled drug release system as it releases drug according to the pathogen concentration (MRSA). All the three factors viz. drug release, MRSA concentration and pH of the medium are interdependent as when the cell divides, it produces secondary metabolites that lead to the decrease in pH of the medium. The drop in the pH value triggers drug release from the beads. And the effect of the drug is reflected by the MRSA cell death. Hence, we demonstrate a smart stimuli responsive DDS. However, such DDS will be useful in cases where increased amount of pathogen in the system will lead to reduction in pH.

Carbon dots rooted agarose hydrogel hybrid platform for optical detection and separation of heavy metal ions.

A robust solid sensing platform for an on-site operational and accurate detection of heavy metal is still a challenge. We introduce chitosan based carbon dots rooted agarose hydrogel film as a hybrid solid sensing platform for detection of heavy metal ions. The fabrication of the solid sensing platform is centered on simple electrostatic interaction between the NH3+ group present in the carbon dots and the OH- groups present in agarose. Simply on dipping the hydrogel film strip into the heavy metal ion solution, in particular Cr6+, Cu2+, Fe3+, Pb2+, Mn2+, the strip displays a color change, viz., Cr6+→yellow, Cu2+→blue, Fe3+→brown, Pb2+→white, Mn2+→tan brown. The optical detection limit of the respective metal ion is found to be 1 pM for Cr6+, 0.5 µM for Cu2+, and 0.5 nM for Fe3+, Pb2+, and Mn2+ by studying the changes in UV-visible reflectance spectrum of the hydrogel film. Moreover, the hydrogel film finds applicability as an efficient filtration membrane for separation of these quintet heavy metal ions. The strategic fundamental feature of this sensing platform is the successful capability of chitosan to form colored chelates with transition metals. This proficient hybrid hydrogel solid sensing platform is thus the most suitable to employ as an on-site operational, portable, cheap colorimetric-optical detector of heavy metal ion with potential skill in their separation. Details of the possible mechanistic insight into the colorimetric detection and ion separation are also discussed.

Green chitosan-carbon dots nanocomposite hydrogel film with superior properties.

In this work we report novel chitosan-carbon dots nanocomposite hydrogel films. A new green source "tea" was used as precursor for carbon dots (CDs). The electrostatic interaction of positive charge on chitosan and negative charge on CDs prepared from tea was used for the successful preparation of a stable and robust chitosan-carbon dots nanocomposite hydrogel film. The hydrogel films were characterized by UV-visible spectroscopy, X-ray diffraction (XRD), Fourier transformed infra-red spectroscopy (FTIR), scanning electron microscope (SEM), fluorescent microscopy, thermogravimetric analysis (TGA) and contact angle analysis. It was observed that chitosan-carbon dots hydrogel films are soft but tough with superior UV-visible blocking, swelling, thermal and mechanical properties in comparison to chitosan hydrogel film. Moreover chitosan-carbon dots films are more water repellent (hydrophobic) as indicated by their high contact angle values. Thus, fabrication of such green soft but tough biocompatible chitosan-carbon dots nanocomposite hydrogel films offers tremendous bio-medical and industrial applications.

ß-Cyclodextrin and calix[4]arene-25,26,27,28-tetrol capped carbon dots for selective and sensitive detection of fluoride.

In this work we have designed a novel system based on carbon dots prepared from chitosan gel capped with ß-cyclodextrin and calix[4]arene-25,26,27,28-tetrol for sensitive and selective detection of fluoride ions in aqueous media. Fluorescent carbon dots prepared from chitosan gel when capped with ß-cyclodextrin and calix[4]arene-25,26,27,28-tetrol results in quenching of its fluorescence intensity. Introduction of F(-) ions to carbon dots capped with ß-cyclodextrin and calix[4]arene-25,26,27,28-tetrol system results in enhancement and restoration of fluorescence intensity leading to detection of F(-) ion. Minimum detection limit was determined to be ∼6.6 µM. The detection is selective as with other halide ions i.e. Cl(-), Br(-) and I(-) and hydroxyl ion (OH(-)), there is observed decrease of fluorescence intensity. A possible mechanism to justify the observation is also discussed in the paper.

In-situ and ex-situ chitosan-silver nanoparticle composite: comparison of storage/release and catalytic properties.

In this work storage of silver nanoparticles (Ag NPs) in chitosan gel and its subsequent release for catalytic reduction processes is investigated. The generation of small sized metal nanoparticles which acts as catalyst is prerequisite to progress of a catalytic reaction. We show that Ag NPs extracted from chitosan gel are less than 5 nm so very effective in catalysis. Chitosan-Ag nanocomposite gels were prepared from two different approaches. The first approach involves in-situ incorporation of Ag nanoparticles into the reaction mixture while preparing the chitosan hydrogel and termed as chitosan-Ag-in-situ (CH-Ag-I) nanocomposite gel. And, in second approach already prepared chitosan hydrogel was placed in Ag NPs solutions, resulting in adsorption of Ag NPs and thus forming chitosan-Ag-ex-situ (CH-Ag-E) nanocomposite gel. The prepared gels were characterized by UV-Visible spectroscopy, Fourier transformed infra-red spectroscopy (FTIR), Thermogravimetric analysis (TGA) and Scanning electron microscopy (SEM). Swelling studies showed that the CH-Ag-E exhibits efficient water absorption property compared to that of CH-Ag-I. In addition to efficient swelling properties the CH-Ag-E can also act as store house of Ag NPs that can be used to catalyze the reduction of 4-Nitrophenol (4-NP) to 4-Aminophenol (4-AP) as Ag NPs of this composite can be easily extracted just by treating with sodium borohydride which is not possible in case of CH-Ag-I. The rate of the reaction increases upto 10 fold when CH-Ag-E nanocomposite gel is used as catalyst in comparison to CH-Ag-I. The reduction reaction catalyzed by such Ag NPs follow zero order kinetics and dependent on the size of the Ag NPs loaded in the gel (CH-Ag-E) as well as on the amount of the gel used. We found that smaller is the size of the loaded Ag NPs in CH-Ag-E, more effective it is in catalyzing the reduction reaction. The CH-Ag-E gel also showed reusability with efficient catalysis.

Novel carbon dot coated alginate beads with superior stability, swelling and pH responsive drug delivery.

Novel carbon dot coated alginate beads (CA-CD) exhibiting superior stability and swelling properties have been successfully prepared. CA-CD show exceptional stability in ambient condition and are stable at room atmosphere and temperature even after 60 days. Moreover, CA-CD show excessive swelling in comparison to calcium alginate (CA) beads. The beads were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and optical microscopy. The CA and CA-CD beads were investigated for their use as pH dependent sustained drug delivery vehicles taking tetracycline (TC) and tetracycline associated with ß-cyclodextrin (ß-TC) as model drug systems. It was observed that TC loading was 35% and 77% with CA and CA-CD, respectively. Tetracycline associated with ß-cyclodextrin (ß-TC) shows 48% loading for CA and much greater loading (as high as 90%) for CA-CD. At pH 1, CA-CD and CA beads show maximum drug release with TC cumulative release of 70% and 37% at 96 h, respectively. However, the delivery rates at pH 1 were slower in case of tetracycline associated with ß-cyclodextrin (ß-TC) loading showing 61% release for CA-CD and 22% for CA after 96 h. Thus, CA-CD can be suitably used as an effective drug delivery vehicle with maximum release obtained at pH 1 emphasizing its use in the gastrointestinal tract where pH is low. Also, the use of ß-cyclodextrin with the drug as an inclusion complex renders the CA and CA-CD beads useful for slow and long-term drug administration.

Capped fluorescent carbon dots for detection of hemin: role of number of -OH groups of capping agent in fluorescence quenching.

We have successfully demonstrated the use of capped carbon dot systems, namely, CDs/ ß -cd, CDs/LMH, and CDs/Suc, as fluorescent sensors for the detection of hemin. The capped carbon dot systems showed quenching of PL intensity in the presence of hemin. The minimum detection limit was determined to be ~1 µ M. The PL response with free Fe(II) and Fe(III) was also studied. It was observed that PL quenching of capped carbon dot systems in the presence of hemin is dependent on the number of -OH groups in the capping agent. The order of quenching towards hemin was determined to be CDs/ ß -cd > CDs/LMH = CDs/Suc > CDs. A possible mechanism to account for the observation is also discussed in the paper.