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Showing papers by "National Chemical Laboratory published in 2014"


Journal ArticleDOI
TL;DR: This report constitutes the first emergence of COFs as proton conducting materials.
Abstract: Two new chemically stable functional crystalline covalent organic frameworkds (COFs) (Tp-Azo and Tp-Stb) were synthesized using the Schiff base reaction between triformylphloroglucinol (Tp) and 4,4′-azodianiline (Azo) or 4,4′-diaminostilbene (Stb), respectively. Both COFs show the expected keto-enamine form, and high stability toward boiling water, strong acidic, and basic media. H3PO4 doping in Tp-Azo leads to immobilization of the acid within the porous framework, which facilitates proton conduction in both the hydrous (σ = 9.9 × 10–4 S cm–1) and anhydrous state (σ = 6.7 × 10–5 S cm–1). This report constitutes the first emergence of COFs as proton conducting materials.

499 citations


Journal ArticleDOI
TL;DR: In this paper, a comprehensive review deals with general information on cashew nut shell liquid (CNSL), its purification and separation methods, reactivity and applications in polymer chemistry.

358 citations


Journal ArticleDOI
TL;DR: This 3D metal-organic framework (MOF) with acid-base pairs in its coordination space that efficiently conducts protons under both anhydrous and humid conditions has now been developed.
Abstract: The development of solid-state proton-conducting materials with high conductivity that operate under both anhydrous and humidified conditions is currently of great interest in fuel-cell technology. A 3D metal–organic framework (MOF) with acid–base pairs in its coordination space that efficiently conducts protons under both anhydrous and humid conditions has now been developed. The anhydrous proton conductivity for this MOF is among the highest values that have been reported for MOF materials, whereas its water-assisted proton conductivity is comparable to that of the organic polymer Nafion, which is currently used for practical applications. Unlike other MOFs, which conduct protons either under anhydrous or humid conditions, this compound should represent a considerable advance in the development of efficient solid-state proton-conducting materials that work under both anhydrous and humid conditions.

352 citations


Journal ArticleDOI
TL;DR: In this paper, the authors reported non-templated synthesis of interconnected microporous carbon (IMPC) sheets having beehive morphology by direct pyrolysis of poly(acrylamide-co-acrylic acid) potassium salt in inert atmosphere without any activation.
Abstract: We report non-templated synthesis of interconnected microporous carbon (IMPC) sheets having beehive morphology by direct pyrolysis of poly(acrylamide-co-acrylic acid) potassium salt in inert atmosphere without any activation. The presence of the alkali metal in the selected polymer precursor results in a high specific surface area of 1327 m2 g−1. Importantly, 80% of the pore volume is contributed by micropores with pore size ranging from 1–2 nm which is ideal for use as an electrode for supercapacitors. Whereas the rest of the surface area was contributed by a small fraction of mesopores and macropores due to the interconnected structure. The presence of three different types of pores make the material ideal for supercapacitor electrodes. IMPC was tested as an electrode in both aqueous and non-aqueous supercapacitors. All the aqueous measurements were done in 1 M H2SO4 solution with a potential window 1 V. A specific capacitance of 258 F g−1 was realized at a constant charge–discharge current of 0.5 A g−1 and it maintained at a value of 150 F g−1 at 30 A g−1. A long cycle stability of 90% capacitance retention was observed after 5000 charge–discharge cycles at a current density of 2 A g−1. At the highest power density 13 600 W kg−1 the energy density was found to be 3.1 W h kg−1. Non aqueous performance was tested in the presence of 1 M LiPF6 in ethylene carbonate–di-methyl carbonate with 5 mg active material loading. A specific capacitance of 138 F g−1 was obtained at a current density of 0.25 A g−1 and it retained at a value of 100 F g−1 at 10 A g−1. The material can deliver an energy density of 31 W h kg−1 at its highest power density of 11 000 W kg−1 in a two electrode system based on active material loading.

334 citations


Journal ArticleDOI
TL;DR: In this paper, a review comprehensively summarizes the state of the art experimental work conducted on the storage of hydrogen as hydrogen clathrates both at the molecular level and macroscopic level and identifies future directions and challenges for this exciting area of research.

319 citations


Journal ArticleDOI
TL;DR: In this paper, a single-layer MoSe2-based gas sensor device was proposed to detect NH3 gas down to 50 ppm using the Raman spectra before and after exposure to NH3.
Abstract: High performance chemical sensor is highly desirable to detect traces of toxic gas molecules. Two dimensional (2D) transition metal dichalcogenides (TMDC) semiconducting materials has attracted as high performance gas sensor device applications due to unique properties such as high surface to volume ratio. Here, we describe the utilization of single-layer MoSe2 as high-performance room temperature NH3 gas sensors. Our single-layer MoSe2 based gas sensor device shows comprehensible detection of NH3 gas down to 50 ppm. We also confirmed gas sensing measurement by recording the Raman spectra before and after exposing the device to NH3 gas, which subsequently shows the shift due to charger transfer and analyte gas molecule adsorption on surface of single-layer MoSe2 nanosheet. Our investigations show the potential use of single-layer and few layer thick MoSe2 and other TMDC as high-performance gas sensors.

307 citations


Journal ArticleDOI
TL;DR: Gold [Au(0)] nanoparticles immobilized into a stable covalent organic framework (COF) have been synthesized via the solution infiltration method and shows high recyclability and superior reactivity for nitrophenol reduction reaction than HAuCl4·3H2O.

289 citations


Journal ArticleDOI
TL;DR: Cadmium sulfide quantum dots have been successfully synthesized in situ without any capping agent in a Zn(II)-based low-molecular-weight metallohydrogel (ZAVA) and have been utilized as a catalyst for water splitting under visible light.
Abstract: Cadmium sulfide (CdS) quantum dots (<10 nm in size) have been successfully synthesized in situ without any capping agent in a Zn(II)-based low-molecular-weight metallohydrogel (ZAVA). Pristine ZAVA hydrogel shows blue luminescence, but the emission can be tuned upon encapsulation of the CdS quantum dots. Time-dependent tunable emission (white to yellow to orange) of the CdS incubated gel (CdS@ZAVA gel) can be attributed to sluggish growth of the quantum dots inside the gel matrix. Once CdS quantum dots are entrapped, their augmentation can be stopped by converting the gel into xerogel, wherein the quantum dots remains embedded in the solid xerogel matrix. Similar size stabilization of CdS quantum dots can be achieved by means of a unique room-temperature conversion of the CdS incubated ZAVA gel to CdS incubated MOF (CdS@ZAVCl) crystals. This in turn arrests the tunability in emission owing to the restriction in the growth of CdS quantum dots inside xerogel and MOF. These CdS embedded MOFs have been utiliz...

263 citations


Journal ArticleDOI
TL;DR: General and modern synthetic strategies to prepare MOFs are covered, and their structural diversity and properties with respect to application perspectives are discussed.
Abstract: Metal-organic frameworks (MOFs) are a class of hybrid network supramolecular solid materials comprised of organized organic linkers and metal cations. They can display enormously high surface areas with tunable pore size and functionality, and can be used as hosts for a range of guest molecules. Since their discovery, MOFs have experienced widespread exploration for their applications in gas storage, drug delivery and sensing. This article covers general and modern synthetic strategies to prepare MOFs, and discusses their structural diversity and properties with respect to application perspectives.

240 citations


Journal ArticleDOI
TL;DR: It is shown that the contrasting temperature dependence of the Raman-active mode A(1g) in MoS2 and MoSe2 arises essentially from the difference in their strain-phonon coupling.
Abstract: We report the temperature-dependent Raman spectra of single- and few-layer MoSe2 and WSe2 in the range 77–700 K. We observed linear variation in the peak positions and widths of the bands arising from contributions of anharmonicity and thermal expansion. After characterization using atomic force microscopy and high-resolution transmission electron microscopy, the temperature coefficients of the Raman modes were determined. Interestingly, the temperature coefficient of the A22u mode is larger than that of the A1g mode, the latter being much smaller than the corresponding temperature coefficients of the same mode in single-layer MoS2 and of the G band of graphene. The temperature coefficients of the two modes in single-layer MoSe2 are larger than those of the same modes in single-layer WSe2. We have estimated thermal expansion coefficients and temperature dependence of the vibrational frequencies of MoS2 and MoSe2 within a quasi-harmonic approximation, with inputs from first-principles calculations based on density functional theory. We show that the contrasting temperature dependence of the Raman-active mode A1g in MoS2 and MoSe2 arises essentially from the difference in their strain–phonon coupling.

239 citations


Journal ArticleDOI
TL;DR: It is demonstrated here that miR156 is a potential graft-transmissible signal that affects plant architecture and tuberization in potato (Solanum tuberosum) and found thatMiR156-resistant SPL9 overexpression lines exhibited increased miR172 levels under a short-day photoperiod, supporting miR 172 regulation via the miR 156-SPL9 module.
Abstract: MicroRNA156 (miR156) functions in maintaining the juvenile phase in plants. However, the mobility of this microRNA has not been demonstrated. So far, only three microRNAs, miR399, miR395, and miR172, have been shown to be mobile. We demonstrate here that miR156 is a potential graft-transmissible signal that affects plant architecture and tuberization in potato (Solanum tuberosum). Under tuber-noninductive (long-day) conditions, miR156 shows higher abundance in leaves and stems, whereas an increase in abundance of miR156 has been observed in stolons under tuber-inductive (short-day) conditions, indicative of a photoperiodic control. Detection of miR156 in phloem cells of wild-type plants and mobility assays in heterografts suggest that miR156 is a graft-transmissible signal. This movement was correlated with changes in leaf morphology and longer trichomes in leaves. Overexpression of miR156 in potato caused a drastic phenotype resulting in altered plant architecture and reduced tuber yield. miR156 overexpression plants also exhibited altered levels of cytokinin and strigolactone along with increased levels of LONELY GUY1 and StCyclin D3.1 transcripts as compared with wild-type plants. RNA ligase-mediated rapid amplification of complementary DNA ends analysis validated SQUAMOSA PROMOTER BINDING-LIKE3 (StSPL3), StSPL6, StSPL9, StSPL13, and StLIGULELESS1 as targets of miR156. Gel-shift assays indicate the regulation of miR172 by miR156 through StSPL9. miR156-resistant SPL9 overexpression lines exhibited increased miR172 levels under a short-day photoperiod, supporting miR172 regulation via the miR156-SPL9 module. Overall, our results strongly suggest that miR156 is a phloem-mobile signal regulating potato development.

Journal ArticleDOI
TL;DR: In this article, the authors investigated the temperature dependent Raman spectroscopy behavior of a few layered MoS2 and WS2 nanosheets synthesized using simple hydrothermal method.
Abstract: We have systematically investigated the temperature dependent Raman spectroscopy behavior of a few layered MoS2 and WS2 nanosheets synthesized using simple hydrothermal method. Our result reveals A1g and E12g modes soften as temperature increases from 77 K to 623 K. This behavior can be explained in terms of a double resonance process which is active in single- and few layer thick nanosheets. The frequency shifts and peak broadening can provide unambiguous, nondestructive, and accurate information of a few layered MoS2 and WS2. This mechanism can also be applicable in characterizing the structural, optical, electronic, and vibrational properties of other emerging layered materials.

Journal ArticleDOI
TL;DR: In vitro and in vivo studies on MG-Gd-pDBI revealed its low blood toxicity and highest drug loading of anticancer drug doxorubicin in MOFs reported to date with pH-responsive cancer-cell-specific drug release.
Abstract: AG d III -based porous metal-organic framework (MOF), Gd-pDBI, has been synthesized using fluorescent linker pDBI (pDBI = (1,4-bis(5-carboxy-1H-benzimidazole-2- yl)benzene)), resulting in a three-dimensional interpenetrat- ed structure with a one-dimensional open channel (1.9 � 1.2 nm) filled with hydrogen-bonded water assemblies. Gd- pDBI exhibits high thermal stability, porosity, excellent water stability, along with organic-solvent and mild acid and base stability with retention of crystallinity. Gd-pDBI was trans- formed to the nanoscale regime (ca. 140 nm) by mechanical grinding to yield MG-Gd-pDBI with excellent water dispersi- bility (> 90 min), maintaining its porosity and crystallinity. In vitro and in vivo studies on MG-Gd-pDBI revealed its low blood toxicity and highest drug loading (12 wt %) of anti- cancer drug doxorubicin in MOFs reported to date with pH- responsive cancer-cell-specific drug release.

Journal ArticleDOI
TL;DR: The presence of a π-conjugated backbone, high surface area, and occurrence of abundant 2D hetero-interface highlight the usage of COF as an effective support for stabilizing the generated photoelectrons, thereby resulting in an efficient and high photocatalytic activity.
Abstract: CdS nanoparticles were deposited on a highly stable, two-dimensional (2D) covalent organic framework (COF) matrix and the hybrid was tested for photocatalytic hydrogen production. The efficiency of CdS-COF hybrid was investigated by varying the COF content. On the introduction of just 1 wt% of COF, a dramatic tenfold increase in the overall photocatalytic activity of the hybrid was observed. Among the various hybrids synthesized, that with 10 wt% COF, named CdS-COF (90:10), was found to exhibit a steep H2 production amounting to 3678 μmol h(-1) g(-1), which is significantly higher than that of bulk CdS particles (124 μmol h(-1) g(-1)). The presence of a π-conjugated backbone, high surface area, and occurrence of abundant 2D hetero-interface highlight the usage of COF as an effective support for stabilizing the generated photoelectrons, thereby resulting in an efficient and high photocatalytic activity.

Journal ArticleDOI
TL;DR: It is shown that the E(1)2g and A1g modes of single-layer WS2 soften as temperature increases from 77 to 623 K, and the double resonance process which is active in atomically thin nanosheet can be largely applicable in other emerging single- layer materials.
Abstract: Atomically thin two-dimensional tungsten disulfide (WS2) sheets have attracted much attention due to their potential for future nanoelectronic device applications. We report first experimental investigation on temperature dependent Raman spectra of single-layer WS2 prepared using micromechanical exfoliation. Our temperature dependent Raman spectroscopy results shows that the E12g and A1g modes of single-layer WS2 soften as temperature increases from 77 to 623 K. The calculated temperature coefficients of the frequencies of 2LA(M), E12g, A1g, and A1g(M) + LA(M) modes of single-layer WS2 were observed to be −0.008, −0.006, −0.006, and −0.01 cm–1 K–1, respectively. The results were explained in terms of a double resonance process which is active in atomically thin nanosheet. This process can also be largely applicable in other emerging single-layer materials.

Journal ArticleDOI
TL;DR: In this paper, high dispersed Pd(0) nanoparticles were successfully immobilized into a stable, crystalline and porous covalent organic framework (COF), TpPa-1, by a solution infiltration method using NABH4 as a reducing agent.
Abstract: Highly dispersed Pd(0) nanoparticles were successfully immobilized into a stable, crystalline and porous covalent organic framework (COF), TpPa-1, by a solution infiltration method using NABH4 as a reducing agent. High resolution and dark field TEM images confirmed the uniform loading of the Pd(0) nanoparticles into the TpPa-1 matrix without aggregation. This hybrid material exhibited excellent catalytic activity towards the Cu free Sonogashira, Heck and sequential one pot Heck–Sonogashira cross-coupling reactions under basic conditions, and with superior performance compared to commercially available Pd supported on activated charcoal (i.e., 1, 5 and 10 wt%). Additionally, the precursor Pd(II)-doped COF also displayed competitive catalytic activity for the intramolecular oxidative biaryl synthesis under acidic conditions. Both catalysts were found to be highly stable under the reaction conditions showing negligible metal leaching, non-sintering behavior, and good recyclability. To the best of our knowledge, the organic support used in this work, TpPa-1, constitutes the first COF matrix that can hold both Pd(0) nanoparticles and Pd(II) complex without aggregation for catalytic purposes under both highly acidic and basic conditions.

Journal ArticleDOI
TL;DR: Fe(III) complexes of biuret-modified tetra-amidomacrocyclic ligands (Fe-TAML) that catalyze fast, homogeneous, photochemical WO to give O2, with moderate efficiency, represents the first example of a molecular iron complex catalyzing photochemistry WO through a Fe(V)(O) intermediate.
Abstract: Water splitting, leading to hydrogen and oxygen in a process that mimics natural photosynthesis, is extremely important for devising a sustainable solar energy conversion system. Development of earth-abundant, transition metal-based catalysts that mimic the oxygen-evolving complex of photosystem II, which is involved in oxidation of water to O2 during natural photosynthesis, represents a major challenge. Further, understanding the exact mechanism, including elucidation of the role of active metal-oxo intermediates during water oxidation (WO), is critical to the development of more efficient catalysts. Herein, we report FeIII complexes of biuret-modified tetra-amidomacrocyclic ligands (Fe-TAML; 1a and 1b) that catalyze fast, homogeneous, photochemical WO to give O2, with moderate efficiency (maximum TON = 220, TOF = 0.76 s–1). Previous studies on photochemical WO using iron complexes resulted in demetalation of the iron complexes with concomitant formation of iron oxide nanoparticles (NPs) that were respon...

Journal ArticleDOI
TL;DR: Graphene quantum dots are synthesized from bio-waste and are further modified to produce amine-terminated GQDs (Am-GQDs) which have higher dispersibility and photoluminescence intensity than those of G QDs.
Abstract: Graphene quantum dots (GQDs) are synthesized from bio-waste and are further modified to produce amine-terminated GQDs (Am-GQDs) which have higher dispersibility and photoluminescence intensity than those of GQDs. A strong fluorescence quenching of Am-GQDs (switch-off) is observed for a number of metal ions, but only for the Ag(+) ions is the original fluorescence regenerated (switch-on) upon addition of L-cysteine.

Journal ArticleDOI
TL;DR: Field electron emission investigations on pulsed laser-deposited molybdenum disulfide (MoS2) thin films on W-tip and Si substrates hold great promise for the development of PLD MoS2 films in application domains such as field emitters and heterostructures for novel nanoelectronic devices.
Abstract: We report field electron emission investigations on pulsed laser-deposited molybdenum disulfide (MoS2) thin films on W-tip and Si substrates. In both cases, under the chosen growth conditions, the dry process of pulsed laser deposition (PLD) is seen to render a dense nanostructured morphology of MoS2, which is important for local electric field enhancement in field emission application. In the case of the MoS2 film on silicon (Si), the turn-on field required to draw an emission current density of 10 μA/cm2 is found to be 2.8 V/μm. Interestingly, the MoS2 film on a tungsten (W) tip emitter delivers a large emission current density of ∼30 mA/cm2 at a relatively lower applied voltage of ∼3.8 kV. Thus, the PLD-MoS2 can be utilized for various field emission-based applications. We also report our results of photodiode-like behavior in (n- and p- type) Si/PLD-MoS2 heterostructures. Finally we show that MoS2 films deposited on flexible kapton substrate show a good photoresponse and recovery. Our investigations t...

Journal ArticleDOI
TL;DR: This is the first report on rapid and efficient synthesis of AgNPs, AuNPs and AgAuNPs from P. zeylanica and their effect on quantitative inhibition and disruption of bacterial biofilms.
Abstract: BACKGROUND: Nanoparticles (NPs) have gained significance in medical fields due to their high surface-area-to-volume ratio. In this study, we synthesized NPs from a medicinally important plant - Plumbago zeylanica. MATERIALS AND METHODS: Aqueous root extract of P. zeylanica (PZRE) was analyzed for the presence of flavonoids, sugars, and organic acids using high-performance thin-layer chromatography (HPTLC), gas chromatography-time of flight-mass spectrometry (GC-TOF-MS), and biochemical methods. The silver NPs (AgNPs), gold NPs (AuNPs), and bimetallic NPs (AgAuNPs) were synthesized from root extract and characterized using ultraviolet-visible spectra, X-ray diffraction (XRD), energy-dispersive spectrometry (EDS), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The effects of these NPs on Acinetobacter baumannii, Staphylococcus aureus, and Escherichia coli biofilms were studied using quantitative biofilm inhibition and disruption assays, as well as using fluorescence, scanning electron microscopy, and atomic force microscopy. RESULTS: PZRE showed the presence of phenolics, such as plumbagin, and flavonoids, in addition to citric acid, sucrose, glucose, fructose, and starch, using HPTLC, GC-TOF-MS, and quantitative analysis. Bioreduction of silver nitrate (AgNO₃) and chloroauric acid (HAuCl₄) were confirmed at absorbances of 440 nm (AgNPs), 570 nm (AuNPs), and 540 nm (AgAuNPs), respectively. The maximum rate of synthesis at 50°C was achieved with 5 mM AgNO₃ within 4.5 hours for AgNPs; and with 0.7 mM HAuCl4 within 5 hours for AuNPs. The synthesis of AgAuNPs, which completed within 90 minutes with 0.7 mM AgNO₃ and HAuCl₄, was found to be the fastest. Fourier-transform infrared spectroscopy confirmed bioreduction, while EDS and XRD patterns confirmed purity and the crystalline nature of the NPs, respectively. TEM micrographs and DLS showed about 60 nm monodispersed Ag nanospheres, 20-30 nm Au nanospheres adhering to form Au nanotriangles, and about 90 nm hexagonal blunt-ended AgAuNPs. These NPs also showed antimicrobial and antibiofilm activity against E. coli, A. baumannii, S. aureus, and a mixed culture of A. baumannii and S. aureus. AgNPs inhibited biofilm in the range of 96%-99% and AgAuNPs from 93% to 98% in single-culture biofilms. AuNPs also showed biofilm inhibition, with the highest of 98% in S. aureus. AgNPs also showed good biofilm disruption, with the highest of 88% in A. baumannii. CONCLUSION: This is the first report on rapid and efficient synthesis of AgNPs, AuNPs and AgAuNPs from P. zeylanica and their effect on quantitative inhibition and disruption of bacterial biofilms.

Journal ArticleDOI
TL;DR: In this paper, a review of the use of Hg2+ ion scavengers can be found, where the authors discuss various methods to detect Hg 2+ in environmental samples, as well as for use as an imaging reagent.
Abstract: Adverse influences of mercury on living organisms are well known. Despite efforts from various regulatory agencies, the build-up of Hg2+ concentration in the environment is of serious concern. This necessitates the search for new and efficient reagents for recognition and detection of Hg2+ in environmental samples as well as for application in diagnostics. Among various detection processes adopted for designing such reagents, generally methodologies that allow associated changes in spectra properties are preferred for the obvious ease in the detection process. Significant changes in the electronic spectral pattern in the visible region of the spectrum also induce detectable changes in solution colour for naked-eye detection and are useful for developing reagents for in-field sample analysis with yes–no type binary responses. However, reagents that allow detection of Hg2+ with associated fluorescence on response are useful for detection of Hg2+ in environmental samples, as well as for use as an imaging reagent, for detection of cellular uptake. High spin–orbit coupling constant for Hg2+ along with its high solvation energy in aqueous medium poses a challenge in developing efficient reagents with fluorescence on response that work in aqueous medium/physiological condition. To get around this problem, several methodologies, like conversion of rhodamine derivative spirolactam to strongly fluorescent xanthenes that form on binding to Hg2+, chemodosimetric reaction for generation of a new luminescent derivative, have been adopted. Apart from these, modified charge transfer processes on binding to Hg2+ have also been utilized for designing reagents for optical detection of Hg2+. Immobilization of such reagents on solid surfaces also led to the development of self-indicating Hg2+ ion scavengers. All such examples are discussed in the present review.

Journal ArticleDOI
TL;DR: In this article, the challenges in constructing a C P bond with a special emphasis on metal catalysed (asymmetric) hydrophosphination are highlighted, and the state-of-the-art developments in catalytic hydrophophosphination of alkenes and alkynes are reviewed.

Journal ArticleDOI
TL;DR: Very high surface area 3D carbon cuboids synthesized from a metal-organic framework (MOF) as a cathode material with Li₄Ti₅O₁₂ as the anode for high performance Li-HECs shows good cyclic performance and indicates that MOF-DC is a very promising candidate for future P-HEVs in a Li- HEC configuration.
Abstract: Lithium ion hybrid capacitors (Li-HECs) have attracted significant attention for use in next generation advanced energy storage technologies to satisfy the demand of both high power density as well as energy density. Herein we demonstrate the use of very high surface area 3D carbon cuboids synthesized from a metal–organic framework (MOF) as a cathode material with Li4Ti5O12 as the anode for high performance Li-HECs. The energy density of the cell is ∼65 W h kg−1 which is significantly higher than that achievable with commercially available activated carbon (∼36 W h kg−1) and a symmetric supercapacitor based on the same MOF-derived carbon (MOF-DC ∼20 W h kg−1). The MOF-DC/Li4Ti5O12 Li-HEC assembly also shows good cyclic performance with ∼82% of the initial value (∼25 W h kg−1) retained after 10 000 galvanostatic cycles under high rate cyclic conditions. This result clearly indicates that MOF-DC is a very promising candidate for future P-HEVs in a Li-HEC configuration.

Journal ArticleDOI
TL;DR: A facile solution-processed fabrication of a self-powered organic-inorganic hybrid photodetector using n-type oriented ZnO nanorods and p-type Spiro-MeOTAD semiconductor is reported, showing that the latter has far less toxicity than the toxic elements stated above.
Abstract: Organic–inorganic hybrid photo-detectors with a self-sufficient mode of operation represent a research area of great current interest. In most efficient photodetectors and optoelectronic devices compound semiconductors containing toxic elements such as Cd, As, Te, S, Se etc. are used and these are also expensive. Hence there is also a rapidly growing interest in replacing these with environmentally friendly and earth-abundant materials. Herein, we report a facile solution-processed fabrication of a self-powered organic–inorganic hybrid photodetector using n-type oriented ZnO nanorods and p-type Spiro-MeOTAD semiconductor. ZnO is eco-friendly and earth-abundant, and Spiro-MeOTAD is non-hazardous. We show that the latter has far less toxicity than the toxic elements stated above. This visible blind UV photodetector shows high sensitivity (102) and a UV/visible rejection ratio of 300. It also exhibits fast response times of τrise ∼ 200 μs and τfall ∼ 950 μs. Importantly, with a small modification of nitrogen incorporation in ZnO one can also realize a highly-sensitive self-powered visible light photodetector with at least 1000% (or higher) improvements in quality factors (photocurrent/sensitivity/response time) as compared to previously reported organic–inorganic hybrid photo-detectors based on metal-chalcogenides (CdS–PANI or CuInSe2–P3HT). Interestingly, the broadband sensitivity of such N:ZnO–Spiro-MeOTAD photodiode enables sensing of low intensity (∼28 μW cm−2) ambient white light with a high photocurrent density of 120 nA cm−2 making it an efficient ambient white light detector.

Journal ArticleDOI
TL;DR: In this paper, a simple way to produce an efficient metal-free oxygen reduction electrocatalyst from graphene by generating nanopores in the matrix and subsequently establishing nitrogen-doped active sites along the pore openings is demonstrated.
Abstract: A simple way to produce an efficient metal-free oxygen reduction electrocatalyst from graphene by generating nanopores in the matrix and subsequently establishing nitrogen-doped active sites along the pore openings is demonstrated. Well-structured nanoporous graphene (pGr) and photoluminescent graphene quantum dots (GQDs) could be simultaneously generated by a chemically assisted oxidative treatment of graphene. The process helped to knock out small pieces of Gr through epoxide formation, which subsequently resulted in the generation of GQD and pGr simultaneously. A longer oxidation time increased the quantity of GQDs and also resulted in a higher photoluminescent (PL) quantum yield. The PL quantum yield of GQD formed after 72 h of the oxidative treatment (GQD-72) was 15.8%, which is greater than the previous reported values. The TEM images showed matching sizes for GQDs and the pores present in pGr, implying that the pores are generated by the removal of GQDs from graphene during the oxidative treatment. Since pore openings are expected to give higher levels of unsaturation and defect sites in the system and are thus being treated as fertile regions for heteroatom doping, pGr-72 was further subjected to nitrogen (NpGr-72). NpGr-72 displayed excellent activity towards the electrochemical oxygen reduction reaction (ORR) compared to nitrogen-doped non-porous graphene (NGr) and many other reported nitrogen-doped carbon materials. A distinct 50 mV gain in the overpotential and 2.5 times increment in the kinetic current density (jk) have been achieved in the case of NpGr-72 compared to NGr. Interestingly, unlike NGr, NpGr-72 effectively reduced the oxygen molecule with a greater involvement of the preferred four-electron pathway. Additionally, the overpotential difference of NpGr-72 with respect to 20 wt% Pt/C is only 60 mV. Additionally, in a single cell evaluation under anion exchange membrane fuel cell (AEMFC) conditions, NpGr-72 exhibited a maximum power density of 27 mW cm−2, which is significantly higher than the corresponding value of 10 mW cm−2 obtained for NGr. Thus, the overall enhancement in the performance characteristics of NpGr-72 is attributed to the higher content of nitrogen (7.8 wt%) and its large proportion of desired chemical environment, which could be established by utilizing the high level of carbon unsaturation around the pore openings.

Journal ArticleDOI
TL;DR: A supercapacitor electrode is fabricated with Co0.85Se hollow nanowires (HNW) array as cathode and activated carbon as anode (asymmetric configuration) promising results are obtained.
Abstract: A supercapacitor electrode is fabricated with Co0.85Se hollow nanowires (HNW) array, which is synthesized by wet chemical hydrothermal selenization of initially grown cobalt hydroxyl carbonate nanowires on conductive CFP. The dense self-organized morphology of Co0.85Se HNWs is revealed by scanning/transmission electron microscopy. The as-synthesized Co0.85Se HNWs possess high pseudocapacitive property with high capacitance retention and high durability. The areal capacitance value is seen to vary from 929.5 to 600 mF cm–2 (60% retention) as the current density is increased from 1 to 15 mA cm–2, an increase of a factor of 15. Based on mass loading, this corresponds to a very high gravimetric capacitance of 674 (for 2 mA cm–2 or 1.48 Ag–1) and 444 Fg1– (for 15 mA cm–2 or 11 A g–1) in a full-cell configuration with the Co0.85Se HNWs as cathode and activated carbon as anode (asymmetric configuration) promising results are obtained.

Journal ArticleDOI
TL;DR: Gemcitabine, the most preferred drug for pancreatic cancer treatment, was encapsulated in albumin nanoparticles, and it was observed that the GQD-mediated bioimaging was excellent and enhanced the efficacy of the system as a drug delivery vehicle.
Abstract: Pancreatic cancer is considered to be the deadliest of all cancers due to its poor prognosis and resistance to conventional therapies. In this study, the potential of hyaluronic acid functionalized and green fluorescent graphene quantum dot (GQD)-labeled human serum albumin nanoparticles for pancreatic cancer specific drug delivery and bioimaging was explored. GQDs with tunable fluorescence properties and biocompatibility have attracted much more interest in recent years as compared to their metal semiconductor counterparts. We adopted lawsone (2-hydroxy-1,4-naphthoquinone) as a novel reducing agent for the synthesis of quantum dots and, in addition to excellent fluorescence of the synthesized GQDs, a good quantum yield of ∼14% was also obtained. Gemcitabine, the most preferred drug for pancreatic cancer treatment, was encapsulated in albumin nanoparticles, and it was observed that our nanoformulation significantly enhanced the bioavailability and sustained release property of the drug to pancreatic cancer cells in vitro. Moreover, the GQD-mediated bioimaging was excellent and enhanced the efficacy of our system as a drug delivery vehicle.

Journal ArticleDOI
TL;DR: Transneuronal propagation of mHTT was blocked by two different botulinum neurotoxins, each known for specifically inactivating a single critical component of the synaptic vesicle fusion machinery.
Abstract: In Huntington's disease (HD), whether transneuronal spreading of mutant huntingtin (mHTT) occurs and its contribution to non-cell autonomous damage in brain networks is largely unknown. We found mHTT spreading in three different neural network models: human neurons integrated in the neural network of organotypic brain slices of HD mouse model, an ex vivo corticostriatal slice model and the corticostriatal pathway in vivo. Transneuronal propagation of mHTT was blocked by two different botulinum neurotoxins, each known for specifically inactivating a single critical component of the synaptic vesicle fusion machinery. Moreover, healthy human neurons in HD mouse model brain slices displayed non-cell autonomous changes in morphological integrity that were more pronounced when these neurons bore mHTT aggregates. Altogether, our findings suggest that transneuronal propagation of mHTT might be an important and underestimated contributor to the pathophysiology of HD.

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TL;DR: This study uses MARTINI coarse-grained molecular-dynamics simulations to explore dimerization of the β2-adrenergic receptor in lipid bilayers containing cholesterol and indicates that dimer plasticity is relevant not just as an organizational principle but also as a subtle regulatory principle for GPCR function.

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TL;DR: The material shows excellent ORR activity with an onset potential of 0.035 V in alkaline medium apart from high durability and strong disinclination towards methanol crossover.