Higher stability and better photoluminescence quantum yield of cesium lead iodide perovskites nanoparticles in the presence of CTAB ligand.

Inorganic halide perovskites, such as CsPbI3, have unique optoelectronic properties which made them promising candidates for several applications. Unfortunately, these perovskites undergo rapid chemical decomposition and transformation into yellow δ-phase. Thus, the synthesis of stable cesium lead iodide perovskites remains an actual challenging field and it is imperative to develop a stabilized black phase for photovoltaic applications. For this purpose, a surfactant ligand was used to control the synthesis of inorganic perovskite CsPbI3 nanoparticles. Herein we demonstrate a new avenue for lead halide perovskites with the addition of either hexadecyltrimethylammonium bromide (CTAB) or silica nanoparticles to maintain in the first place; the stability of the α-CsPbI3 phase, and later on to boost their photoluminescence quantum yield (PLQY). The prepared perovskites were characterized using UV-visible absorption spectroscopy, fluorescence spectroscopy, scanning electron microscopy, thermogravimetric analysis and X-Ray diffraction technique. Results show higher stability of α-CsPbI3 phase and improvement in PLQY % to reach 99% enhancement in presence of CTAB. Moreover, the photoluminescence intensity of CsPbI3 nanoparticles was higher and was maintained for a longer duration in the presence of CTAB.

Curcumin-PLGA based nanocapsule for the fluorescence spectroscopic detection of dopamine.

The main purpose of this paper is to design curcumin loaded PLGA nanocapsules for the selective detection of dopamine using fluorescence spectroscopy. In the present work curcumin loaded PLGA nanocapsules were synthesized using a solid-in-oil-in water (s/o/w) emulsion technique. The prepared nanocapsules were coated with a poly(diallyldimethylammonium)chloride (PDDA) polymer to increase the entrapment of curcumin into the core of PLGA polymer. PLGA-Cur-PDDA nanocapsules were characterized using different microscopic and spectroscopic techniques. Unlike free curcumin, the formed CUR-PLGA-PDDA NCs were established as nanoprobes for the selective detection of dopamine molecules. The selectivity and specificity of nanocapsules toward dopamine was achieved by measuring the fluorescence emission spectra of the NCs in the presence of other interference molecules such as tryptophan, melamine, adenine, etc. It was noticed that increasing the concentration of the different molecules had no significant change in the fluorescence signal of the nanocapsules. These results confirm the strong quenching between dopamine and curcumin in the nanocapsules. Hence, this fluorescence emission technique was found to be selective, easy and fast with low cost for the determination of dopamine in a concentration range up to 5 mM with a detection limit equal to 22 nM.

Interaction of Curcumin with Poly Lactic-Co-Glycolic Acid and Poly Diallyldimethylammonium Chloride By Fluorescence Spectroscopy.

Poly Lactic-Co-Glycolic Acid (PLGA) and Poly Diallyldimethylammonium Chloride (PDDA) are widely being used for drug delivery and curcumin is being studied as potential drug molecule for its anti-oxidant, anti-inflammatory and anti-cancer activities. The interaction between PLGA, PDDA and curcumin was investigated by fluorescence spectroscopy. The modified Stern-Volmer equation was used to estimate the value of the binding constant Ka and the van't Hoff equation was used to estimate the corresponding thermodynamic parameters (ΔHo, ΔSo, and ΔGo). The obtained results showed that the binding constant between PLGA and Curcumin is due to the formation of hydrogen bonds and van der Waals forces. However, PDDA interacts with curcumin through hydrophobic interactions. Moreover, zeta potential measurements were obtained for these polymers and the surface charge was compared in presence and absence of the negatively charged curcumin molecules. It was found that the results obtained by zeta potential measurements are in agreement with those obtained by fluorescence spectroscopy. It is also found that binding of curcumin with PDDA is further encouraged in the presence of PLGA.

Liposome-based nanocapsules for the controlled release of dietary curcumin: PDDA and silica nanoparticle-coated DMPC liposomes enhance the fluorescence efficiency and anticancer activity of curcumin.

Nanosystems with various compositions and biological properties are being extensively investigated for drug and gene delivery applications. Many nanotechnology methods use novel nanocarriers, such as liposomes, in therapeutically targeted drug delivery systems. However, liposome matrices suffer from several limitations, including drug leakage and instability. Therefore, the surface modification of liposomes by coating them or adding polymers has advanced their application in drug delivery. Hence, the prevention of drug release from the liposome bilayers was the main focus of this work. For this purpose, liposomes were synthesized according to a thin film hydration method by applying various surface modifications. Three different nanocapsules, N1, N2, and N3, were prepared using 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), poly(diallyldimethylammonium)chloride (PDAA) polymer, and silica nanoparticles. PDDA and silica nanoparticles were coated on the surface of liposomes using a layer-by-layer assembly method, completely encapsulating curcumin into the core of the liposome. Fluorescence spectroscopy, TGA, DLS, XRD, SEM, and zeta potential methods were used to characterize the prepared nanocapsules. Interestingly, the fluorescence of curcumin showed a blue shift and the fluorescence efficiency was extraordinarily enhanced ∼25-, ∼54-, and ∼62-fold in the N1, N2, and N3 nanocapsules, respectively. Similarly, encapsulation efficiency, drug loading, and the anticancer activity of dietary curcumin were investigated for the different types of DMPC nanocapsules. The drug efficiencies of the liposomes were established according to the release of curcumin from the liposomes. The results showed that the release of curcumin from the nanocapsules decreased as the number of layers at the surface of the liposomes increased. The release of curcumin follows the Higuchi model; thus, a slow rate of diffusion is observed when a number of layers is added. The better encapsulation and higher anti-cancer activity of curcumin were also observed when more layers were added, which is due to electrostatic interactions inhibiting curcumin from being released.

A Novel Study on the Self-Assembly Behavior of Poly(lactic-co-glycolic acid) Polymer Probed by Curcumin Fluorescence.

Understanding the self-assembly behavior of block copolymers is of great importance due to their usefulness in a wide range of applications. In this work, the physical properties of poly(lactic-co-glycolic acid) (PLGA polymer) are studied for the first time in solution using the fluorescence technique and curcumin as a molecular probe. First, curcumin at a concentration of 2 µM was added to different concentrations of PLGA, and the fluorescence of curcumin was tracked. It was found that the critical micellar concentration (CMC) was equal to 0.31 g/L and the critical micellar temperature (CMT) was obtained to be 25 °C. Furthermore, an insight on the effect of NaCl salt on the CMC value of PLGA is assessed through curcumin probing. A decrease in the CMC has been observed with the increase in the concentration of NaCl, which could be due to the salting out effect. Moreover, in order to understand the aggregation behavior of PLGA in different solutions, CMC experiments were investigated using chloroform as a solvent. Results showed that the solvent does not affect the CMC value of the polymer; however, it only affects the shape of the obtained micelle forming a reversed micelle. Finally, fluorescence quenching of curcumin with hydrophobic cetyl-pyridinium bromide (CPB) and hydrophilic KI quenchers was established, where it was proved that curcumin is located near the hydrophobic pocket of the Stern layer of the PLGA micelle.

Curcumin-embedded DBPC liposomes coated with chitosan layer as a fluorescence nanosensor for the selective detection of ribonucleic acid.

One of the limitations of fluorescence probe molecules during biomedical estimation is their lack of ability to selectively determine the targeted species. To overcome this there have been various approaches that involve attaching a functional group or aptamers to the fluorescence probe. However, encapsulating probe molecules in a matrix using nanotechnology can be a viable and easier method. Curcumin (Cur) as a fluorescence marker cannot distinguish DNA and RNA. This research reports a novel selective approach involving the use of nanocapsules composed of liposomal curcumin coated with chitosan for the selective detection of RNA molecules using a fluorescence method. The increase in RNA concentration enhanced the electrostatic interaction between the negatively charge surface of RNA and the positively charged nanocapsule, which was further verified by zeta potential measurement. This method had a low limit of detection (36 ng/ml) and higher linear dynamic ranges compared with other studies found in the literature. Moreover, the method was not affected by DNA and was selective for the detection of RNA molecules for which the site of interaction was confined only to uracil. The selectivity for RNA molecules towards other analogues species was also examined and recovery range found was between 99 and 100.33%.

Efficient removal of Congo red using curcumin conjugated zinc oxide nanoparticles as new adsorbent complex.

Congo red is one of the common organic dyes that is found in water as waste of the industrial work. The use of congo red has long been of great concern, primarily because of its carcinogenic properties. Congo red can be isolated and removed from water by adsorption using nanoparticles. The use of zinc curcumin oxide, also known as curcumin conjugated zinc oxide, nanoparticles was elaborated for the first time in this work for this purpose. The optimization of the synthesis reaction of zinc curcumin oxide nanoparticles was established by modifying the flow rate of KOH, pH of the medium, different temperature, and in the presence or absence of chitosan polymer. These nanoparticles were characterized through SEM, UV-Visible absorption Spectroscopy, fluorescence spectroscopy, TGA, and XRD. It is found that during synthesis, addition of KOH dropwise in alkaline media improved the stability of the formed nanoparticles. Similarly, addition of chitosan has further increased their stability with only 10% mass loss. The importance of the formed nanoparticles was investigated by analyzing their efficiency in the adsorption of congo red where Zn(Cur)O had an adsorption capacity equal to 89.85 mg/g, which is one of the highest reported in literature, following the pseudo second order model. Nevertheless, negative surface charge of congo red and positive surface charge of Zn(Cur)O may also get supported by π-π interaction between curcumin and congo red that encourages adsorption in zinc curcumin oxide which is obstructed in the presence of chitosan.

Interaction of curcumin with diarachidonyl phosphatidyl choline (DAPC) liposomes: Chitosan protects DAPC liposomes without changing phase transition temperature but impacting membrane permeability.

The developing public interest in traditional medicine, especially plants-based drug, has prompted extensive research on the potential of naturally existing compounds. Among these compounds, curcumin is currently one of the most studied substances. In this study, we elaborate the physical properties of diarachidonyl phosphatidyl choline (DAPC) liposome using fluorescence method, where curcumin at low concentration was used as a probe molecule. In the first place, the phase transition temperature of DAPC was determined by following the fluorescence intensity of curcumin as a function of temperature, along with evaluating the effect of concentration of curcumin in the presence or absence of chitosan oligosaccharide lactate as an additional protective layer. On the other hand, quenching reactions using CPB and KI as quenchers reflected the ease of entry of different concentrations of these quenchers to the curcumin located in the hydrophobic core of the liposome which give new insight about the lipophilicity and permeability of the DAPC membrane. Finally, the partition coefficient analysis was investigated. It was concluded that curcumin has a higher partition coefficient at a temperature above the phase transition temperature of DAPC liposomes where the liposome is in the fluid liquid crystalline phase. Modulation of liposomes properties in the presence of chitosan oligosaccharide lactate layer was for the first time investigated. Chitosan oligosaccharide lactate acts as protecting layer without changing the phase transition temperature, but it affects the membrane permeability depending on solid gel and liquid crystalline phase.

Introducing Principal Coordinate Analysis (PCoA) Assisted EEMF Spectroscopic Based Novel Analytical Approach for the Discrimination of Commercial Gasoline Fuels.

In the present work, a novel analytical procedure by integrating principal coordinate analysis (PcoA) with excitation-emission matrix fluorescence (EEMF) spectroscopy was introduced for discriminating the commercial gasoline fuels. The PcoA technique involved analysis of the distance matrices containing the dissimilarity information and it can serve as an efficient tool for capturing the major as well as subtle compositional differences among the analyzed commercial gasoline samples. The utility of the proposed PcoA assisted EEMF analytical procedure was successfully tested by discriminating gasoline fuel samples belonging to five different industrial brands. The obtained results clearly showed that combination of PcoA and EEMF could provide a simple, sensitive and economical analytical procedure to carry out the rapid analyses of the gasoline samples belonging to different brands.

Glutathione-capped CuO nanoparticles for the determination of cystine using resonance Rayleigh scattering spectroscopy.

Ascorbic acid was used to reduce cystine to cysteine that induces the aggregation of glutathione-capped copper oxide nanoparticles. The aggregation of CuO NPs was optimized through resonance Rayleigh scattering and dynamic light scattering measurements. The high specificity toward cysteine from other amino acids and biomolecules was due to its mercapto group that binds to the surface of CuO NPs and the electrostatic interaction between the cysteine zwitterions on the surface of CuO NPs. Accordingly, glutathione-capped copper oxide nanoparticles was used as a sensing probe for cystine based on resonance Rayleigh scattering (RRS) technique. Increase in the RRS signal of CuO NPs was observed with increasing cystine concentration. A linear calibration plot was obtained in the range 2-20 µM with a limit of detection of 4.55 ± 0.5 nM, which is lower than literature value. The applicability of the proposed sensing strategy toward cystine was established, and the recovery percentage was between 99.8 ± 0.4 and 101.0 ± 2.1 for n = 3. Graphical Abstract .

Fluorescence Sensing of Nucleic Acid by Curcumin Encapsulated Poly(Ethylene Oxide)-Block-Poly(Propylene Oxide)-Block-Poly(Ethylene Oxide) Based Nanocapsules.

In a novel approach, curcumin has been encapsulated inside Poly(Ethylene Oxide)-Block-Poly(Propylene Oxide)-Block-Poly(Ethylene Oxide) (F108) nanocapsules. FTIR spectra have indicated a type of hydrogen bonding and dipole interaction between curcumin and F108. Fluorescence and UV-visible absorption profiles of curcumin in nanocapsules have indicated location of curcumin in more hydrophobic microenvironment. The relative fluorescence yield has increased by 6 times in the nanocapsules, which renders them as more sensitive probes to be used later on in sensing study. Therefore, based on the functionality of curcumin as a fluorescent transducer, encapsulated curcumin is used in biomedical application as DNA and RNA sensing. Detection limits are detected as 50 µM and 60 µM for DNA and RNA respectively. Linear dynamic concentration range obtained in this proposed method is much higher than reported in literature. The interaction between the nanocapsules and targeted DNA/RNA molecules is further approved by zeta potential studies. Furthermore, the real interaction of DNA with the encapsulated curcumin is confirmed by the interaction of the adenine and cytosine nucleotides. This has been verified through zeta potential measurements. Moreover, our prepared nanocapsules has presented a high percentage recovery of DNA and RNA (96-101%). Finally, stability results have illustrated a high photostability of encapsulated curcumin, indicating that proposed nanocapsules can be considered as a stable sensor during measurement time.

Gold and silver nanoparticles in resonance Rayleigh scattering techniques for chemical sensing and biosensing: a review.

This review (with 116 refs.) summarizes the state of the art in resonance Rayleigh scattering (RRS)-based analytical methods. Following an introduction into the fundamentals of RRS and on the preparation of metal nanoparticles, a first large section covers RRS detection methods based on the use of gold nanoparticles, with subsections on proteins (albumin, bovine serum albumin and ovalbumin, glycoproteins, folate receptors, iron binding-proteins, G-proteins-coupled receptors, transmembrane proteins, epidermal growth factor receptors), on pesticides, saccharides, vitamins, heavy metal ions (such as mercury, silver, chromium), and on cationic dyes. This is followed by a section on RRS methods based on the use of silver nanoparticles, with subsections on the detection of nucleic acids and insecticides. Several Tables are presented where an RRS method is compared to the performance of other methods. A concluding section summarizes the current status, addresses current challenges, and gives an outlook on potential future trends. Graphical Abstract Change in the resonance Rayleigh scattering (RRS) intensity when mixing the nanoparticles with the specific analyte.

Nanosensing of ATP by fluorescence recovery after surface energy transfer between rhodamine B and curcubit[7]uril-capped gold nanoparticles.

The authors describe a method for functionalization of gold nanoparticles (AuNPs) with the supramolecular host molecule, curcubit[7]uril (CB[7]) which can bind rhodamine B (RhB). The fluorescence of RhB is quenched by the AuNPs via surface energy transfer. On addition of ATP, a dimeric RhB-ATP complex is formed and RhB is pushed out of CB[7]. Hence, fluorescence increases by a factor of 8. This fluorescence recovery effect has been utilized to develop a new detection scheme for ATP. The assay, measured at fluorescence excitation and emission wavelengths of 500 nm and 574 nm respectively, works in the 0.5-10 µM concentration range and has a 100 nM detection limit. The method is not interfered by UTP, GTP, CTP, TTP, ascorbic acid and glutathione. Graphical abstract Schematic of a method for determination of ATP in the 500 nM to 10 µM concentration range by using fluorescence recovery after surface energy transfer (SET) between rhodamine B (RhB) and gold nanoparticles capped with curcubit[7]uril (CB[7]).

Random initialisation of the excitation-emission matrix fluorescence spectral variables in constraint fashion for subsequent multivariate curve resolution alternating least square analysis on a peculiarly designed calibration set: Simultaneous sensing of nine polycyclic aromatic hydrocarbons in water samples.

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic and mutagenic in nature therefore their sensing in water sample is an important analytical task. In the present work, a novel approach that is based on the random initialisation of the excitation-emission matrix fluorescence (EEMF) spectral variables in constraint fashion for subsequent multivariate curve resolution alternating least Square (MCR-ALS) analysis is introduced for simultaneously sensing the complex dilute aqueous mixture of PAHs. The usefulness of the proposed analytical approach is successfully demonstrated by applying it intentionally on a calibration set that is peculiar in many senses. The peculiarity mainly arises because the designed (i) the calibration set consist of nine PAHS having significant spectral overlap, (ii) the concentration of each PAH in different samples are kept constant and (iii) any two samples differ only in the presence and absence of the PAHs. The proposed approach is found to make precise and accurate estimation of each of the nine PAHs without involving any pre-separation. In summary, the proposed approach provides a simple and cost-effective procedure for simultaneous sensing of several PAHs in water samples. The proposed approach could be very useful in developing countries.

Gold nanoparticles functionalized with Pluronic are viable optical probes for the determination of uric acid.

The authors describe the preparation of gold nanoparticles (AuNPs) coated with poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (Pluronic F-108) by reducing Au3+ to Au0 using curcumin, a natural and non-toxic food spice, in water of pH ~7 in the presence of F-108 and Ag+ ion. The coated AuNPs display strong resonance Rayleigh scattering (RRS) and fluorescence that results from the functionalization of the gold surface with curcumin and Pluronic F-108. The molar mass of Pluronic F-108 affects the particle size of the AuNPs formed, and small AuNPs are formed when using low molar weight F-108 that was purified by centrifugation or dialysis. The coated AuNPs were employed in an optical method for the determination of uric acid. The combination of uric acid with the AuNPs boosts both the RRS signal and the fluorescence of the AuNPs. However, higher concentrations of uric acid shift the fluorescence peak to shorter wavelengths. The method is simple, and fluorescence, best measured at excitation/emission wavelengths of 425/534 nm, increases linearly in the 50 µM to 50 mM uric acid concentration range, with a 0.14 µM detection limit which is lower than reported for other methods in the literature. Graphical abstract Pluronic F-108 capped gold nanoparticles prepared by reducing Au3+ to Au0 using curcumin can estimate uric acid in 50 µM to 50 mM concentration range.

Tuning the surface of Au nanoparticles using poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol): enzyme free and label free sugar sensing in serum samples using resonance Rayleigh scattering spectroscopy.

Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (F-108) functionalized gold nanoparticles (Au NPs) have been successfully synthesized. During synthesis it is found that an increase in the F-108 concentration contributes to agglomeration in the media, increasing the size of the Au particles, and boosting the curcumin concentration leads to a higher density of functional groups, resulting in smaller Au NPs. FT-IR analysis reveals that the hydroxyl and phenolic groups of curcumin and F-108 are involved during the functionalization of Au surfaces. Enhancement in the fluorescence/RRS intensity is due to the combination of the influence of the shape/size of the Au NPs as well as the extent of curcumin conjugation at the interface of the Au NP surface and F-108. The presence of sugar molecules remarkably boosts the RRS intensity without significantly affecting the fluorescence and surface plasmon absorbance of the Au NPs; in contrast, the RRS intensity of standard CTAB functionalized Au NPs is unaffected by glucose molecules indicating that the functionalization of F-108 at Au surfaces is crucial. Interestingly, no interference from other potential interferents and antioxidant substances like ascorbic acid, creatinine and acetaminophen is observed. This method is simple and fast, and offers a wider linear dynamic range, 0-10 mM, that is applicable under physiological conditions and in serum samples. It is stable and provides an excellent recovery for serum samples, thus, potentially it can be useful in this field due to its low energy consumption, enzyme free assay, fast response time, better selectivity and sensitivity.

Amplification of resonance Rayleigh scattering of gold nanoparticles by tweaking into nanowires: Bio-sensing of α-tocopherol by enhanced resonance Rayleigh scattering of curcumin capped gold nanowires through non-covalent interaction.

Tuning optical properties by controlling size and shape of the metallic nanoparticles has been of great interest to design novel bio-sensing techniques. Here, as a first example we illustrate that resonance Rayleigh scattering (RRS) signal of Au nanoparticles (NPs) can be amplified >10-fold by growing into Au nanowires (NWs). These thin and long NWs of ~20-25nm diameter and >1µm length can be achieved by suitably manipulating the temperature during green synthesis using curcumin. Interestingly, mixture of Au NWs and NPs or shorter NWs gives a moderate increase in RRS signal suggesting formation of longer NWs is crucial for optimal enhancement of RRS signal. Curcumin along with CTAB act as capping and stabilizing agent for Au NWs/NPs in different temperatures, which is confirmed by XRD, TGA, DSC, EDX and FT-IR data. This amplified RRS signal of Au NWs has been employed to design a new optical biosensor for α-tocopherol (α-TOH), which is among the most biologically active form of vitamin E. Association of α-TOH with Au NWs further enhances the RRS signal of Au NWs, ~10 fold through non-covalent interaction. No interference from other antioxidant substances like ascorbic acid and 6-O-Palmitoyl-L-ascorbic acid is observed. The sensing method is simple, fast and offers remarkable linear dynamic ranges, 12.8-1004µmolL-1, which is larger than reported values. The detection limit for α-TOH estimation has been found to be 50nmolL-1. The biosensor is found to be stable both in the absence and presence of α-TOH and provides an excellent recovery for synthetic samples.

The role of OH- in the formation of highly selective gold nanowires at extreme pH: multi-fold enhancement in the rate of the catalytic reduction reaction by gold nanowires.

There is a quest to understand the mechanism governing the morphology and geometry control of the particle growth of nanomaterials for their optical and catalytic applications. In the available literature, the role of OH- in dictating the size and shape of Au nanowires is unknown. As one of the first examples, herein, we explore how excess OH- ions in CTAB micelles play a significant role during the highly selective formation of gold nanowires having controlled diameters of ∼20-25 nm and length >1 µm, by reducing Au3+ to Au0 in a one pot, simple synthesis procedure in the presence of Ag+ ions. At pH 4-11, the same procedure does not harvest Au NWs, but Au NPs of diameter 50-70 nm, indicating that excess OH- is needed for nanowire formation. XRD, TGA, DSC, EDX, FT-IR and fluorescence spectroscopic analysis confirm that both CTAB and curcumin act as capping and stabilizing agents for Au NWs as well as Au NPs - there is no remarkable difference in the curcumin/CTAB content between Au NWs and NPs prepared in different pH environments. However, changing the CTAB micellar media to DPPC liposome media inhibits the formation of nanowires at pH ∼13; the growth of the Au NPs diminishes in DPPC liposomes, offering smaller NPs of diameter ∼25 to 30 nm, suggesting that the role of CTAB is necessary in nanowire formation. The rate of NW formation has been found to be 0.13 h-1 and the growth mechanism advocates elongation in the [110] facet of Au [110] as opposed to the [100] or [111] facets. Curcumin capped Au nanowires serve as excellent nano-catalysts for the reduction of nitro-compounds and the rate of reduction of 4-nitrophenol, a model compound, by curcumin capped Au NWs is found to be ∼10 fold higher, compared to Au NPs, which signifies that catalytic activities can be dictated by the size and shape of Au NPs.