Synergistic reduction of nitrophenols by Au-CDs nanoconjugates with NaBH4.

Developing sustainable and innovative approaches for the efficient reduction of nitrophenols is crucial for environmental remediation, for managing health concerns posed by their widespread presence as hazardous pollutants in industrial effluents and contaminated water. We report the use of 12.9 ± 1 nm (TEM data) sized gold carbon dot nanoconjugates (Au@CDs) for catalytic conversion of o, m, p-nitrophenols to aminophenols by sodium borohydride. A simple approach was followed to synthesize ultra-small and highly stable Au@CDs, using citric acid and PEG as reducing and stabilizing agents. X-ray diffraction analysis verified the formation of nano-crystalline nanoconjugates. These nanoconjugates showed a remarkable catalytic activity in the range of 0.22-0.33 s-1(varying with nanoconjugate concentration) which was much higher compared to conventional chemical methods of reduction. All the catalytic reaction experiments were performed at room temperature (27 ± 2 °C). Furthermore, an increase in rate constant was observed with increasing concentration of nanoconjugates. The catalytic activity of Au@CDs nanoconjugates was observed to be in order of m-nitrophenol > o-nitrophenol > p-nitrophenol with apparent rate constant (kaap) values of 0.068, 0.043 and 0.031, respectively. Comparative analysis with GNPs, CDs and Au@CDs nanoconjugates stated that the nanoconjugates had superior catalytic activity. The research can have significant implications in the development of new strategies for environmental remediation and biomedical applications.

Divergent Responses of Hydrophilic CdSe and CdSe@CdS Core-Shell Nanocrystals in Apoptosis and In Vitro Cancer Cell Imaging: A Comparative Analysis.

With their distinctive core-shell design, core-shell nanocrystals have drawn interest in catalysis, medicinal research, and nanotechnology. These nanocrystals have a variety of characteristics and possible uses. The application of core-shell nanocrystals offers significant potential in increasing diagnostic and therapeutic approaches for cancer research in apoptosis and in vitro cancer cell imaging. In the present study, we investigated the fluorescence behavior of hydrophilic CdSe (core-only) and CdSe@CdS (core-shell) nanocrystals (NCs) and their potential in cancer cell imaging. The addition of a CdS coating to CdSe NCs increased the fluorescence intensity tenfold. The successful fabrication of core-shell CdSe@CdS nanocrystals was proven by a larger particle size (evaluated via DLS and TEM) and their XRD pattern and surface morphology compared to CdSe (core-only) NCs. When these NCs were used for bioimaging in MCF-7 and HEK-293 cell lines, they demonstrated excellent cellular uptake due to higher fluorescence intensity within cancerous cells than normal cells. Comparative cytotoxicity studies revealed that CdSe NCs were more toxic to all three cell lines (HEK-293, MCF-7, and HeLa) than CdSe@CdS core-shell structures. Furthermore, a decrease in mitochondrial membrane potential and intracellular ROS production supported NCs inducing oxidative stress, which led to apoptosis via the mitochondria-mediated pathway. Increased cytochrome c levels, regulation of pro-apoptotic gene expression (e.g., p53, Bax), and down-regulation of Bcl-2 all suggested cellular apoptosis occurred via the intrinsic pathway. Significantly, at an equivalent dose of core-shell NCs, core-only NCs induced more oxidative stress, resulting in increased apoptosis. These findings shed light on the role of a CdS surface coating in reducing free radical release, decreasing cytotoxicity, and improving fluorescence, advancing the field of cell imaging.

Biocompatible gelatin/carbon dot nanocomposite based urea sensor and the effect of nitrogen ion implantation.

In this study, we have fabricated a novel platform for sensing of urea using gelatin/carbon dots nanocomposite system. The sensor electrode was created by depositing the nanocomposite gel onto thin glass plates coated with indium tin oxide (ITO) using the drop casting technique. The behavior of these electrodes was investigated against a number of bioanalytes in the concentration range of 2-20 mM by cyclic voltammetry. The system was observed to be highly selective for urea with a sensitivity of 1.65 µA/mM/cm in the experimental linear range of 2-20 mM. Furthermore, the gelatin/CD-ITO electrode were also subjected to 50 KeV N2+ ion beam irradiation with varying fluence in the range of 1012 to 1016 ions/cm2. Sensing profile of the irradiated samples for urea suggested enhancement in sensitivity to 2 µA/mM cm2, when the ion fluence was 5 × 1015 ions/cm2. This enhancement after irradiation suggests a clear dependence of detection on the fluence of the ion beam. The observed excellent sensitivity of radiation processed nanocomposite material can be used as an enzyme-free platform for urea detection. Additionally, the CDs showed fluorescence quenching on treatment with mere 50 µM urea suggesting the high sensitivity of the platform.

Bioaccumulation of CdSe Quantum Dots Show Biochemical and Oxidative Damage in Wistar Rats.

Cadmium selenium quantum dots (CdSe QDs) with modified surfaces exhibit superior dispersion stability and high fluorescence yield, making them desirable biological probes. The knowledge of cellular and biochemical toxicity has been lacking, and there is little information on the correlation between in vitro and in vivo data. The current study was carried out to assess the toxicity of CdSe QDs after intravenous injection in Wistar male rats (230 g). The rats were given a single dose of QDs of 10, 20, 40, and 80 mg/kg and were kept for 30 days. Following that, various biochemical assays, hematological parameters, and bioaccumulation studies were carried out. Functional as well as clinically significant changes were observed. There was a significant increase in WBC while the RBC decreased. This suggested that CdSe quantum dots had inflammatory effects on the treated rats. The various biochemical assays clearly showed that high dose induced hepatic injury. At a dose of 80 mg/kg, bioaccumulation studies revealed that the spleen (120 g/g), liver (78 g/g), and lungs (38 g/g) accumulated the most. In treated Wistar rats, the bioretention profile of QDs was in the following order: the spleen, liver, kidney, lungs, heart, brain, and testis. The accumulation of these QDs induced the generation of intracellular reactive oxygen species, resulting in an alteration in antioxidant activity. It is concluded that these QDs caused oxidative stress, which harmed cellular functions and, under certain conditions, caused partial brain, kidney, spleen, and liver dysfunction. This is one of the most comprehensive in vivo studies on the nanotoxicity of CdSe quantum dots.

Role of Nanomedicines in Controlling Malaria: A Review.

Malaria has created havoc since time immemorial. It has actually become a major health concern due to its high prevalence in developing countries where poor sanitary conditions facilitate the seasonal breeding of the vector, the female Anopheles mosquito. Even after tremendous advancements in pest control and pharmacology science, managing this disease has not been successful, and the cure for this deadly infection has not proven effective lately. The various conventional drugs used are chloroquine, primaquine, mefloquine, atovaquone, quinine, artemisinin etc. All of these have one or other major disadvantages like multi-drug resistance, high dose requirements, aggravated toxicity, non-specificity of conventional drugs, and the emergence of drug-resistant parasites. Therefore, it is necessary to surpass these limitations and look for an alternative to curb the spread of this disease using an emerging technology platform. Nanomedicine is showing promise as an effective alternative tool for the management of malaria. The idea of this tool resonates well with David J. Triggle's outstanding suggestion "The chemist is as the astronaut, searching for biologically useful space in the chemical universe. This review presents a detailed discussion on various nanocarriers, their mode of action and future perspective in treating malaria. Nanotechnology-based drug delivery methods are highly specific, require a lower dose, offer more bioavailability with prolonged drug release and stay in the body longer. Recent nano drug encapsulation and delivery vehicles comprise nanocarriers like liposomes, and organic and inorganic nanoparticles, emerging as promising alternatives for malaria management.

Gold-carbon dot (Au@Cd) nanoconjugates based electrochemical sensing of cholesterol and effect of nitrogen ion implantation on sensitivity.

Serum cholesterol dysregulation is associated with prognosis and diagnosis of many diseases and effective biosensor will improvise their management. A novel electrochemical biosensor was fabricated based on gelatin-Au@CD nanoconjugate films for cholesterol detection. Initially, the surface of indium titanium oxide (ITO) coated glass was modified by drop casting of gelatin-Au@CD nanoconjugates to prepare the electrodes. Electrochemical studies for detection of bioanalytes(such as urea (U), ascorbic acid (AA), oxalic acid (OA), gallic acid (GA), cholesterol (Chox), dextrose (D), l-cysteine (Cys) and citric acid (CA)) were performed using cyclic voltammetry. The presence of nanoconjugates provided an appropriate environment for enhanced electrochemical response for cholesterol. These electrodes exhibited a linear response towards the presence of cholesterol in the linear concentration range of 2-20 mM with a correlation coefficient of 0.95, and the superior sensitivity of 1.36 µA/mM/cm2. Additionally, enhanced sensitivity (2.99 µA/mM/cm2) of nitrogen ion irradiated films up to a fluence of 1016 ions/cm2 was noticed because of morphological changes in the electrode surface brought about by irradiation. Approximately 54% enhancement was found when the ion fluence was 1016 ions/cm2. The designed nanoconjugate electrode showed excellent response towards cholesterol sensing and eliminates the requirement of any enzymes making the overall process simpler, cost-effective and allows for room temperature storage.

Boron-doped carbon quantum dots: a 'turn-off' fluorescent probe for dopamine detection.

Boron-doped carbon quantum dots (size 2.3 nm) were fabricated by a modified hydrothermal carbonization one-pot synthesis protocol using 4-hydroxy phenylboronic acid as the common precursor that provided seed for the formation of carbon quantum dots as well as the dopant. These quantum dots exhibited excellent properties, namely good aqueous dispersion, strong fluorescence emission, good environmental stability, high selectivity and sensitivity towards the neurochemical dopamine even in the absence of any linker, functionalizing agents or enzyme. It is shown that this material can be used as a 'turn-off' fluorescent probe for the detection of even low concentrations of dopamine with a limit of detection (3σ/S) of about 6 µM. The simplicity of the synthesis protocol and the ease of dopamine detection define the novelty of this approach.

Boron Doped Carbon Quantum Dots: Turn-Off Fluorescent Probe for Dopamine Detection.

In this report, Boron-doped carbon quantum dots (BCQD, size = 2.3 nm) were fabricated by modified hydrothermal carbonization method by one-pot synthesis using phenyl boronic acid as the common precursor that provided seed for the formation of carbon quantum dots as well as the dopant. These quantum dots exhibited excellent properties including aqueous dispersibility, strong fluorescence emission, good environmental stability, highselectivity and sensitivity towards the neurochemical, dopamine even in the absence of any linker or functionalizing agents. It is shown that this material can be used as a "turn off" fluorescent probe for the detection of even low concentration of dopamine with a minimum detection limit of ~6 µM. The simplicity of synthesis protocol and the easiness of dopamine detection define the novelty of this approach.

Multifunctional, fluorescent DNA-derived carbon dots for biomedical applications: bioimaging, luminescent DNA hydrogels, and dopamine detection.

Here, we describe the synthesis of 2-3 nm, hydrophilic, blue fluorescence-emitting carbon dots (C-Dots, made using a DNA precursor) by the hydrothermal route from the gelling concentration of 2% (w/v) DNA. These dots exhibited highly efficient internalization in pathogenic fungal cells, negligible cytotoxicity, good PL stability, and high biocompatibility, thus demonstrating their potential as nanotrackers in microbial studies. Bioimaging was performed using Candida albicans as the representative for microbial pathogens. The novelty of these dots is that they formed fluorescent nanocomposite hydrogels with the same DNA much below the gelation concentration (1% w/v) and the tunable gels possessed strength between 20 and 80 Pa with the corresponding gelation temperature Tgel between 40 to 50 °C. The network density and gelation free energy data supported the superior crosslinking ability of these dots. The as-prepared hydrogels can replace the existing toxic quantum dot-based hydrogels for drug delivery. We also demonstrated the use of a DNA hydrogel-fabricated working electrode (DNA-C-Dot/ITO electrode) for the biosensing of dopamine. Our electrochemical biosensor had a detection limit of 5 × 10-3 mM for dopamine. These multifunctional, fluorescent C-Dots and hydrogel after suitable conjugation or loading with molecules and drugs hold promising potential for further exploitation in bioimaging, targeted drug delivery, wound healing, and biosensing applications.

pH responsive doxorubucin loaded zein nanoparticle crosslinked pectin hydrogel as effective site-specific anticancer substrates.

Herein, we report pH-responsive hydrogels of hierarchically self-assembled protein (zein, in the form of its nanoparticles of size 80-120 nm) and polysaccharide (pectin), where gelation occurred below pH 3 in the absence of crosslinkers, which we used for encapsulation and release of anticancer drug, Doxorubicin (DOX) in the cell nucleus. These nanoparticles, spherical in shape, in addition to helping in the formation of gel network also encapsulate the drug and pectin layer adsorbed on the surface of these nanoparticle allows for the drying, redispersion and enhanced swelling. A monovalent salt-dependent study performed in the concentration range of 1-100 mM clearly showed the associative interaction between the zein nanoparticles and pectin chains were hydrophobic in nature. FTIR results confirmed the loading of the drug inside the nanoparticles. Melting profile studies of these gels revealed that encapsulation of drug did not change the thermo-physical properties. Doxorubicin drug loaded hydrogels exhibited superior cytotoxicity towards cervical cancer cell lines by inducing intracellular-antioxidative stress-based apoptosis. Confocal microscopy revealed that the hydrogels required quite less time of 4 h to completely penetrate the cells assisted by the charge specific electrostatic interaction between the negatively charged HeLa cells and positively charged crosslinks. The data, further revealed that these pH specific hydrogels were suitable for release of the drug in cell nucleus is assisted by the acidic environment of cellular organelles, and hence have a potential in cancer therapy with minimal collateral damage to healthy cells.

Dual-probe (colorimetric and fluorometric) detection of ferritin using antibody-modified gold@carbon dot nanoconjugates.

A dual-mode assay is described for immunological determination of the anemia biomarker ferritin. It is based on the use of a gold@carbon dot (Au@CD) nanoconjugate as a colorimetric and fluorescent probe. Au@CD is hydrophilic, easily surface modified and stable in aqueous solution. The Au@CD have a red color with blue-green fluorescence and were modified with antibody against ferritin. This allows bi-modal detection of ferritin. Assays can be performed in phosphate buffer and were also analyzed in (Bovine Serum Albumin) BSA and (Fetal Bovine Serum) FBS. Detection is based on antigen-antibody interaction underlying the classical sandwich model. Response to ferritin can be detected by spectrophotometry (at 570 nm) or fluorescence (at excitation/emission maxima of 354/454 nm). Under optimal conditions, the assay has a linear response in the 1 to 120 ngmL-1 ferritin concentration range and detection limits of 20 ng (colorimetrically) and 64 ng (fluorometrically). Graphical abstract Schematic representation of the function of the designed nanoprobe. The Au@CD nanoconjugates are functionalized with ferritin antibody in the initial step which specifically interacts with ferritin molecules leading to aggregation and subsequent changes in the optical and fluorescence signals.

Fluorescent complex coacervates of agar and in situ formed zein nanoparticles: Role of electrostatic forces.

Herein, the complex coacervation between in situ formed spherical fluorescent zein nanoparticles and polyanion agar as function of mixing ratio (R=[Agar]/[Zein]) was investigated. This interaction yielded two distinguishable regions (at pH 5.4): Region I (R < 0.2), where fully charge neutralized soluble complexes with protein denaturation was noticed, and Region II (R > 0.2), where overcharged complexes were formed, with R = 0.2 defining the optimum binding. Small angle neutron scattering studies demonstrated that in the low-q region, nanoparticles formed the crosslink junctions and in the persistence regime of high-q region, the data captured the cross-sectional radius ( = 3.5 nm) for agar-zein complexes. The coacervates became more viscoelastic in salt-free samples because both the low frequency storage modulus and crosslink density were found to decrease with mixing ratio. Systematic decrease in storage modulus with ionic strength (0-0.01 M) implied screened Coulomb interaction was responsible for the observed coacervation. Further, we seek to find universality in complex coacervation of zein nanoparticle with biopolymers, and polysaccharides in particular.

Effect of organic and inorganic salt environment on the complex coacervation of in situ formed protein nanoparticles and DNA.

Complex coacervation was noticed between in situ formed protein (a primarily hydrophobic Zein protein with pI = 6.2) nanoparticles (size 80-120 nm) and ds-DNA (a high charge density polyanion), in the ionic liquid (IL) solutions of 1-ethyl-3-methyl imidazolium chloride [C2mim][Cl], and 1-octyl-3-methyl imidazolium chloride [C8mim][Cl], in the studied ionic strength range of I = 10-4 to 6 × 10-1 M, which was extended to strong monovalent 1:1 electrolyte (NaCl) to explore the commonality between the organic and inorganic salt (ionic) environment on coacervation. The salt dependent coacervation profile was monitored from the measured turbidity of the interacting solution, and zeta potential, (ζ) and apparent hydrodynamic radius (Rh) of interpolymer complexes, which depicted the following three discernible interaction regimes common to all the salts: (i) Region-I: I = 0.0001-0.01 M, primary binding, (ii) Region-II, I = 0.01-0.1 M, secondary binding, and (iii) Region-III, I = 0.1-0.6 M, saturation binding. The free-energy and the network density calculations favored preferential coacervation in [C2mim][Cl] samples. Nonetheless, commonality in the overall ionic strength dependent coacervation profiles could still be observed.

Mixing ratio dependent complex coacervation versus bicontinuous gelation of pectin with in situ formed zein nanoparticles.

We report on the competitive phenomenon of complex coacervation versus bicontinuous gelation between pectin (P, a polyanionic carbohydrate, [P] = 0.01-2% (w/v)) and zein nanoparticles (Z, a hydrophobic protein and a weak polyampholyte, [Z] = 0.1 and 0.5% (w/v), in an ethanolic solution of effective concentration 4 and 27% (v/v)), which was studied below (pH ≈ 4), and above (pH ≈ 7.4) the pI (≈ 6.2) of zein at room temperature, 25 °C. The uniqueness of this study arises from the interaction protocol used, where the pectin used was in the extended polyelectrolyte (persistence length ≈ 10 nm) conformation while zein was used as a charged globular nanoparticle (size ≈ 80-120 nm) that was formed in situ. Their mixing ratio, r = [P] : [Z] (w/w), was varied from 0.02 to 4.0 (for [Z] = 0.5% (w/v)), and from 0.1 to 7.5 (for [Z] = 0.1% (w/v)) in the ionic strength range 10-4 to 10-2 M NaCl. Zeta potential data revealed that at pH ≈ 4, the complementary binding condition, r = 1 : 1 (equivalent to 1 : 5 molecule/nanoparticle) demarcated the coacervate from the gel region. The measured rigidity (G0, low frequency storage modulus) of these materials revealed the following: for r < 1, (low pectin content samples, coacervate region) the material had lower values of Gcoac0, whereas for r > 1, an excess of pectin facilitated gelation with Ggel0 ≫ Gcoac0. Above pI, surface patch binding caused associative interactions and complex coacervation though both biopolymers had similar net charge. The network density was used as a descriptor to distinguish between the coacervate and gel samples. Their microstructures were probed by small angle neutron scattering (SANS), and viscoelastic properties by rheology. Simple modeling shows that formation of the interpolymer complex was favored in higher protein containing samples. Mixing ratio dependent selective coacervation (a kinetic process) and bicontinuous gelation (a thermodynamic process) are rarely seen to coexist in biopolymer interactions.

Bandgap Tunable AgInS based Quantum Dots for High Contrast Cell Imaging with Enhanced Photodynamic and Antifungal Applications.

Herein, we report a facile microwave-assisted synthesis of cadmium-free water-soluble silver indium sulfide (AgInS2 or AIS) and AgInS@ZnS (or AIS@ZnS) core-shell quantum dots (QDs) using glutathione (GSH) as stabilizer. The core and core-shell nanocrystals exhibit tunable bandgap ranging of 2.3-3.1 and 2.4-3.5 eV, mean particle size of 2.5 and 3.25 nm, quantum yield of 26% and 49%, and fluorescence lifetimes of 326 and 438 ns, respectively. The core-shell QDs exhibit color-tunable emission in the visible region (500 to 600 nm), where the tunability was achieved by varying the molar ratio of Ag:In in the precursors. In vitro evaluation of antifungal activity of these water/ buffer stable QDs against the fungal pathogen, Candida albicans demonstrated that these were not toxic to the fungal cells upto a concentration of 100 µg/ml for 16 hours of incubation. Confocal imaging and spectrofluorometric studies showed enhanced fluorescence inside the microbial cells suggesting that AIS@ZnS particles had the capability to easily penetrate the cells. The increased generation of reactive oxygen species was evaluated for the core-shell QDs (photosensitizers) by using 9, 10-anthracenediyl-bis(methylene)dimalonic acid (ABMDMA) as singlet oxygen (1O2) scavenger molecule. These QDs have the potential for use as high contrast cell imaging, photodynamic and antifungal agents.

Antifungal efficacy of Au@ carbon dots nanoconjugates against opportunistic fungal pathogen, Candida albicans.

In the current study, we have investigated the toxicological effect of a novel hydrophilic nanoconjugate gold@carbon dot (Au@CD) and carbon dots (CDs) on the opportunistic fungal pathogen, Candida albicans. A homogenous experimental analysis was conducted for determining the toxicity of Au@CDs nanoconjugates of five different sizes ranging from 22 ±â€¯2 to 35 ±â€¯3 nm prepared using the carbon dots of mean hydrodynamic radius 12 ±â€¯1 nm. The smallest size of nanoconjugate was synthesized using 0.3 mg ml-1 HAuCl4 precursor. Our study for the first time, conclusively establishes the size-dependent toxicity effect of these characterized nanoconjugates against the abovementioned fungal pathogen. The MIC80 value of smaller sized Au@CDs nanoconjugates, S1-S3 samples were 250, 500 and 500 µg ml-1, respectively, while nanoconjugates of Rh diameter greater than 30 nm (S4 and S5 samples) did not show any toxicity. The results thus demonstrate that alteration in composition (carbon vs Au@CDs) exhibits a profound effect on the susceptibility of Candida albicans cells. While a size-dependent toxicity was observed for the nanoconjugates, CDs were found to be quite toxic owing to their small size which facilitated their entry into the cells and challenged the biocompatibility of carbon allotropes.

Complex coacervation in charge complementary biopolymers: Electrostatic versus surface patch binding.

In this review, a number of systems are described to demonstrate the effect of polyelectrolyte chain stiffness (persistence length) on the coacervation phenomena, after we briefly review the field. We consider two specific types of complexation/coacervation: in the first type, DNA is used as a fixed substrate binding to flexible polyions such as gelatin A, bovine serum albumin and chitosan (large persistence length polyelectrolyte binding to low persistence length biopolymer), and in the second case, different substrates such as gelatin A, bovine serum albumin, and chitosan were made to bind to a polyion gelatin B (low persistence length substrate binding to comparable persistence length polyion). Polyelectrolyte chain flexibility was found to have remarkable effect on the polyelectrolyte-protein complex coacervation. The competitive interplay of electrostatic versus surface patch binding (SPB) leading to associative interaction followed by complex coacervation between these biopolymers is elucidated. We modelled the SPB interaction in terms of linear combination of attractive and repulsive Coulombic forces with respect to the solution ionic strength. The aforesaid interactions were established via a universal phase diagram, considering the persistence length of polyion as the sole independent variable.

Folic acid supramolecular ionogels.

Herein, we report on folic acid (FA, a low molecular weight gelator) thermoreversible supramolecular organo (in 1 : 1 (v/v) water-DMSO binary solvent), and ionogels made in 1-ethyl-3-methyl imidazolium chloride, [C2mim][Cl], and 1-octyl-3-methyl imidazolium chloride, [C8mim][Cl], solutions with 0.1 ≤ [IL] ≤ 5% (w/v). The self-assembled fibrils of folic acid were largely formed due to secondary forces, such as π-π stacking, H-bonding, and hydrophobic interactions above a gelator concentration of 0.2% (w/v) at room temperature, 20 °C. Fragile gels (FGs) having a low frequency storage modulus G0 ≈ 4-6 Pa were formed when 0.2 ≤ [FA] ≤ 0.5% (w/v) in the binary solvent, and at higher gelator concentration (0.5 ≤ [FA] ≤ 2.5% (w/v)) formation of strong gels (SGs) with a G0 value of 140 Pa-5 kPa was noticed. In the IL environment, for a given gelator concentration of [FA] = 1% (w/v), SG formation (with G0 ≈ 2-5 kPa) was noticed when 0.1 ≤ [IL] ≤ 0.5% (w/v), whereas very strong gels (VSGs) with remarkably high gel strengths were formed with G0 ≈ 11-15 kPa. Gelation temperature Tgel could be varied from 45 to 75 °C by varying the FA concentration in the binary solvent, whereas the ionogels exhibited an almost 10 °C rise in gelation temperature. The information obtained from the relative network density νr (ratio of network density in iono- to organo gel), differential free-energy and enthalpy of gelation, ΔGW-IL and ΔHW-IL (difference in free-energy and enthalpy of organo to ionogel), implied that [C2mim][Cl] ionogels had enhanced homogeneity, and higher crosslink density and gel strength. A 3-D plot of Tgel and G0versus gelator concentration clearly defines a phase diagram that describes the contour of the gelation domains of this biologically important gelator.

Solvent hydrophobicity induced complex coacervation of dsDNA and in situ formed zein nanoparticles.

Zein, a predominantly hydrophobic protein, was sustained as a stable dispersion in ethanol-water (80 : 20, % (v/v)) binary solvent at room temperature (25 °C). Addition of aqueous dsDNA solution (1% (w/v)) to the above dispersion prepared with the protein concentration of Czein = 0.01-0.5% (w/v) caused a concomitant change in ethanol content from 14-35% (v/v), which in turn generated zein nanoparticles in situ of size 80-120 nm increasing with water content. The subsequent associative interaction between DNA (polyanion; 2000 bps) and the positively charged zein nanoparticles, (at pH = 4) was driven by Coulombic forces, and by the solvent hydrophobicity due to the ethanol content of the binary solvent. Experimentally, two interesting regions of interaction were observed from turbidity, zeta potential, particle sizing, and viscosity data: (i) for Czein < 0.2% (w/v), zein nanoparticles of size 80 nm bind to dsDNA (primary complex) causing its condensation (apparent hydrodynamic size decreased from ≈2100 to 560 nm), and (ii) for 0.2% < Czein < 0.5% (w/v) larger nanoparticles (>80 nm) were selectively bound to primary complexes to form partially charge neutralized interpolymer soluble complexes (secondary complexes), followed by complex coacervation. During this process, there was depletion of water in the vicinity of the nucleic acid, which was replaced by hydration provided by the ethanol-water binary solvent. Equilibrium coacervate samples were probed for their microstructure by small angle neutron scattering, and for their viscoelastic properties by rheology. The interplay of solvent hydrophobicity, electrostatic interaction, and zein nanoparticle size dependent charge neutralization had a commensurate effect on this hitherto unexplored coacervation phenomenon.

Au@carbon dot nanoconjugates as a dual mode enzyme-free sensing platform for cholesterol.

In this report, we present a novel application of gold-carbon dot nanoconjugates (Au@CDs) of an average size of around 12.6 nm as a sensor for the detection of cholesterol. The Au particles perform the dual function of displaying colorimetric sensing, and fluorescence quenching in response to cholesterol in the concentration range of 10-100 ppm (0.208-2.08 mM), wherein the carbon dots act as the fluorescent entity. Interestingly, the nanoconjugates were observed to show a high specificity to cholesterol resulting in their precipitation. A visible change in colour of the assay mixture along with fluorescence quenching was seen in the reaction mixture on treatment with cholesterol. The synthesized nanoconjugates had high selectivity towards cholesterol, even in the presence of interfering analytes, and a minimum detection limit of 0.12 ppm (0.0025 mM) in the linear range of 50-300 ppm (1-6.25 mM). We anticipate that these Au@CDs can be employed for the fabrication of enzyme-free strip-based biosensors for the detection of cholesterol.