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At least 163 records · Page 9

An LED Approach for Measuring the Photocatalytic Breakdown of Crystal Violet Dye

A simple technique to assess the reactivity of photocatalytic coatings sprayed onto transmissive glass surfaces was developed. This new method uses ultraviolet (UV) gallium nitride (GaN) light-emitting diodes (LEDs) to drive a photocatalytic reaction (the photocatalytic breakdown of a UV-resistant dye applied to a surface coated with the semiconductor titanium dioxide); and then a combination of a stabilized white light LED and a spectrometer to track the dye degradation as a function of time. Simple, standardized evaluation techniques that assess photocatalytic materials over a variety of environmental conditions, including illumination level, are not generally available and are greatly needed prior to in situ application of photocatalytic technologies. To date, much research pertaining to this aspect of photocatalysis has been limited and has focused primarily on laboratory experiments using mercury lamps. Mercury lamp illumination levels are difficult to control over large ranges and are temporally modulated by line power, limiting their use in helping to understand and predict how photocatalytic materials will behave in natural environmental settings and conditions. The methodology described here, using steady-state LEDs and time series spectroradiometric techniques, is a novel approach to explore the effect of UV light on the photocatalytic degradation of a UV resistant dye (crystal violet). GaN UV LED arrays, centered around 365 nm with an adjustable DC power supply, are used to create a small, spatially uniform light field where the steady state light level can be varied over three to four orders of magnitude. For this study, a set of glass microscope slides was custom coated with a thinly sprayed layer of photocatalytic titanium dioxide. Crystal violet was then applied to these titanium-dioxide coated slides and to uncoated control slides. The slides were then illuminated at various light levels from the dye side of the slide by the UV LED array. To monitor dye degradation on the slides over time, a temperature-stabilized white light LED was used to illuminate the opposite side of the slides. As the dye degraded, the amount of light from the white light LED transmitted through the slide was monitored with a spectrometer and subsequently analyzed to determine and compare the rate of dye degradation for photocatalytically coated versus uncoated slide surfaces. The long-term stability of the spectrometer/white light LED combination, which required only a single reference spectra to be taken for a time series sequence of several hours, enabled accurate measurements of transmitted light over time. Time series transmission curves were generated and results demonstrated that over time the transmission increased much more rapidly on the coated slides than on the control slides. This experimental configuration and methodology for photocatalytic activity measurement minimizes many external variable effects and allows low light level studies to be performed. This study also compares the advantages of this novel LED light source design to traditional mercury lamp systems and non-LED lamp approaches that have conventionally been used. The methodology and experimental design research summarized in this abstract is partly funded by the Department of Homeland Security, Science and Technology Directorate, and by the NASA Stennis Space Center Innovative Partnerships Program.

Ryan, Robert E.↗

Anchoring Groups for Dye-Sensitized Solar Cells

The dyes in dye-sensitized solar cells (DSSCs) require one or more chemical substituents that can act as an anchor, enabling their adsorption onto a metal oxide substrate. This adsorption provides a means for electron injection, which is the process that initiates the electrical circuit in a DSSC. Understanding the structure of various DSSC anchors and the search for new anchors are critical factors for the development of improved DSSCs. Traditionally, carboxylic acid and cyanoacrylic acid groupsare employed as dye anchors in DSSCs. In recent years, novel anchor groups have emerged, which make a larger pool of materials available for DSSC dyes, and their associated physical and chemical characteristics offer interesting effects at the interface between dye and metal oxide. This review focuses especially on the structural aspects of these novel dye anchors for TiO2-based DSSCs, including pyridine, phosphonic acid, tetracyanate, perylene dicarboxylic acid anhydride, 2-hydroxylbenzonitrile, 8-hydroxylquinoline, pyridine-N-oxide, hydroxylpyridium, catechol, hydroxamate, sulfonic acid, acetylacetanate, boronic acid, nitro, tetrazole, rhodanine, and salicylic acid substituents. We anticipate that further exploration and understanding of these new types of anchoring groups for TiO2 substrates will not only contribute to the development of advanced DSSCs, but also of quantum dot-sensitized solar cells, water splitting systems, and other self-assembled monolayer-based technologies.

Adsorption↗

Lights on: Dye dequenching reveals polymersome fusion with polymer, lipid and stealth lipid vesicles

In this study, we develop a quantitative dye dequenching technique for the measurement of polymersome fusion, using it to characterize the salt mediated, mechanically-induced fusion of polymersomes with polymer, lipid, and so-called stealth lipid vesicles. While dye dequenching has been used to quantitatively explore liposome fusion in the past, this is the first use of dye dequenching to measure polymersome fusion of which we are aware. In addition to providing quantitative results, dye dequenching is ideal for detecting fusion in instances where DLS results would be ambiguous, such as low yield levels and size ranges outside the capabilities of DLS. The dye chosen for this study was a cyanine derivative, 1,1'-dioctadecyl-3,3,3',3'-tetramethylindotricarbocyanine iodide (DiR), which proved to provide excellent data on the extent of polymersome fusion. Using this technique, we have shown the limited fusion capabilities of polymersome/liposome heterofusion, notably DOPC vesicles fusing with polymersomes at half the efficiency of polymersome homofusion and DPPC vesicles showing virtually no fusion. In addition to these key heterofusion experiments, we determined the broad applicability of dye dequenching in measuring kinetic rates of polymersome fusion; and showed that even at elevated temperatures or over multiple weeks' time, no polymersome fusion occurred without agitation. Stealth liposomes formed from DPPC and PEO-functionalized lipid, however, fused with polymersomes and stealth liposomes with relatively high efficiency, lending support to our hypothesis that the response of the PEO corona to salt is a key factor in the fusion process. This last finding suggests that although the conjugation of PEO to lipids increases vesicle biocompatibility and enables their longer circulation times, it also renders the vesicles subject to destabilization under high salt and shear (e.g. in the circulatory system) that may lead to, in this case, fusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic Structure and Optical Properties of Designed Photo-Efficient Indoline-Based Dye-Sensitizers with D–A–π–A Framework

Seven D–A–π–A-based indoline (IND) dyes that were designed via quantitative-structure–property relationship modeling have been comprehensively investigated using computational approaches to evaluate their prospect of application in future dye-sensitized solar cells (DSSCs). An array of optoelectronic properties of the isolated dye and dyes adsorbed on a TiO 2 cluster that simulates the semiconductor were explored by density functional theory (DFT) and time-dependent DFT methods. Light absorption spectra, vertical dipole moment, shift of the conduction band of semiconductor, excited state lifetime, driving force of electron injection, photostability of the excited state, and exciton binding energy were computed. Our study showed that the presence of an internal acceptor such as pyrido[3,4-b]pyrazine (pyrazine) would influence greater the open circuit voltage (VOC), compared to the benzothiadiazole moiety. Considering the balance between the VOC and J SC (short circuit current) along with the all calculated characteristics, the IND3, IND5, and IND10 are the most suited among the designed dyes to be used as potential candidates for the photo-efficient DSSCs. Finally, the present study provides the results of rational molecular design followed by exploration of photophysical properties to be used as a valuable reference for the synthesis of photo-efficient dyes for DSSCs.

14 SOLAR ENERGY↗

Preferred Molecular Orientation of Coumarin 343 on TiO 2 Surfaces: Application to Dye-Sensitized Solar Cells

The dye…TiO2 interfacial structure in working electrodes of dye-sensitized solar cells (DSCs) is known to influence its photovoltaic device performance. Despite this, direct and quantitative reports of such structure remain sparse. This case study presents the application of X-ray reflectometry to determine the preferred structural orientation and molecular packing of the organic dye, coumarin 343, adsorbed onto amorphous TiO2. Results show that the dye molecules are, on average, tilted by 61.1° relative to the TiO2 surface, and are separated from each other by 8.2 Å. These findings emulate the molecular packing arrangement of a monolayer of coumarin 343 within its crystal structure. This suggests that the dye adsorbs onto TiO2 in one of its lowest energy configurations, i.e. dye…TiO2 self assembly is driven more by thermodynamic rather than kinetic means. Complementary DSC device tests illustrate that this interfacial structure compromises photovoltaic performance, unless a suitably sized co-adsorbant is interdispersed between the coumarin 343 chromophores on the TiO2 surface.

coumarin 343↗

Phonon-Mediated Ultrafast Hole Transfer from Photoexcited CdSe Quantum Dots to Black Dye

We have applied non-adiabatic molecular dynamics (NAMD) and Fewest Switching surface hopping (FSSH) method to simulate the energy dissipation and charge transfer processes in the CdSe quantum dot (QD) functionalized by the Black dye. Our calculations reveal ultrafast hole transfer from the photoexcited QD to the dye, despite a significant energy splitting between QD’s and dye’s occupied states. The mechanism of such ultrafast QD-to-dye hole transfer is rationalized by strong non-adiabatic couplings between the delocalized surface orbitals of the QD and the high-frequency vibrations of isothiocyanate ligands of the Black dye. Here, this mechanism is also confirmed by a very rapid lose of coherency of the excitation due to strong electronic couplings with vibrational modes of the dye.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Disentangling the Physical Processes Responsible for the Kinetic Complexity in Interfacial Electron Transfer of Excited Ru(II) Polypyridyl Dyes on TiO 2

Interfacial electron transfer at titanium dioxide (TiO 2 ) is investigated herein for a series of surface bound ruthenium-polypyridyl dyes whose metal-to-ligand charge-transfer state (MLCT) energetics are tuned through chemical modification. The 12 complexes are of the form Ru II (bpy-A)(L) 2 2+ , where bpy-A is a bipyridine ligand functionalized with phosphonate groups for surface attachment to TiO 2 . Functionalization of ancillary bipyridine ligands (L) enables the potential of the excited state Ru III/ * couple, E + / *, in 0.1 M perchloric acid (HClO 4 (aq)) to be tuned from –0.69 to –1.03 V vs NHE. Each dye is excited by a 200 fs pulse of light in the visible region of the spectrum and probed with a time-delayed supercontiuum pulse (350–800 nm). Decay of the MLCT excited-state absorption at 376 nm is observed without loss of the ground-state bleach, which is a clear signature of electron injection and formation of the oxidized dye. The dye-dependent decays are biphasic with time constants in the 3–30 and 30–500 ps range. The slower injection rate constant for each dye is exponentially distributed relative to E + / *. The correlation between the exponentially diminishing density of TiO 2 sub-band acceptor levels and injection rate is well described using Marcus–Gerischer theory, with the slower decay components being assigned to injection from the thermally equilibrated state and the faster components corresponding to injection from higher energy states within the 3 MLCT manifold. These results and detailed analyses incorporating molecular photophysics and semiconductor density of states measurements indicate that the multiexponential behavior that is often observed in interfacial injection studies is not due to sample heterogeneity. Rather, this work shows that the kinetic heterogeneity results from competition between excited-state relaxation and injection as the photoexcited dye relaxes through the 3 MLCT manifold to the thermally equilibrated state, underscoring the potential for a simple kinetic model to reproduce the complex kinetic behavior often observed at the interface of mesoporous metal oxide materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dye-coated europium monosulfide

Nanoparticles of EuS were synthesized using europium dithiocarbamate complexes. The resulting nanoparticles were coated with the dye, 1-pyrene carboxylic acid and the resulting material was characterized using X-ray powder diffraction, TEM, and UV-visible spectroscopy. Fluorescence spectroscopy was used to determine the relative energy of the conduction band edge to the excited state energy of the dye. -- Graphical abstract: Dye sensitized magnetic semiconductor materials were prepared by synthesizing EuS nanoparticles using single source precursors and coating with the dye, 1-pyrene carboxylic acid. Display Omitted highlights: > Synthesized EuS nanoparticles, 11{+-}2.4 nm characterized using XRD, TEM, and UV-vis. spect. > Grafted a dye to the surface and characterized the product using XRD, FTIR, UV-vis., and TEM. > Studied the photophysical properties using fluorescence spectroscopy. > Determined the relative dye excited state to the conduction band of the semiconductor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of adsorption in decomposition of dyes on TiO{sub 2} and N-modified TiO{sub 2} photocatalysts under UV and visible light irradiations

Graphical abstract: Influence of pH and zeta potential of TiO{sub 2} based photocatalysts on the adsorption and degradation of MB under UV irradiation. Highlights: ► Adsorption of dyes on TiO{sub 2}/N accelerated their decomposition under visible light. ► pH of solution and the PZC of the TiO{sub 2} surface influence the adsorption of dyes. ► Under UV irradiation oxidation of pollutants with OH radicals is the most powerful. -- Abstract: Photoactivities of TiO{sub 2} based photocatalysts towards dyes decomposition was studied by consider their adsorption abilities. It was proved that zeta potential and PZC (point zero charge) of photocatalyst surface as well as pH of solution strongly influenced adsorption of tested dyes, Methylene Blue (MB) and Reactive Red 198 (RR198). These dyes underwent the photocatalytic decomposition by two ways, OH radicals attack and direct oxidation with photogenerated holes. The latter one is more efficient in case of better contact of pollutant with the photocatalysts surface and is dominant under visible light irradiation, where insignificant amount of OH radicals is formed. The former one is powerful under UV irradiation and is a key factor in decomposition of dyes regardless of their adsorption abilities.

36 MATERIALS SCIENCE↗

Photocatalytic degradation of methyl orange dye in water solutions in the presence of MWCNT/TiO{sub 2} composites

Highlights: ► MWCNTs/TiO{sub 2} composites were obtained to degrade organic dyes in water. ► MWCNT/TiO{sub 2} composites were analyzed by photocatalysis and structural characterization. ► The photocatalytic shows efficient method for the degradation of dyes from aqueous effluents. - Abstract: The textile and dyestuff industries are the primary sources of the release of synthetic dyes into the environment and usually there are major pollutants in dye wastewaters. Because of their toxicity and slow degradation, these dyes are categorized as environmentally hazardous materials. In this context, carbon nanotubes/TiO{sub 2} (CNTs/TiO{sub 2}) composites were prepared using multi-walled CNTs (MWCNTs), titanium (IV) propoxide and commercial TiO{sub 2} (P25{sup ®}) as titanium oxide sources, to degrade the methyl orange dye in solution through photocatalyst activity using UV irradiation. The composites were prepared by solution processing followed by thermal treatment at 400, 500 and 600 °C. The heterojunction between nanotubes and TiO{sub 2} was confirmed by XRD, specific surface area. The coating morphology was observed with SEM and TEM.

36 MATERIALS SCIENCE↗

All-vanadium photoelectrochemical storage cells using dye sensitized geometry-enhanced TiO{sub 2} nanobelts

Highlights: • Dye-sensitized photoelectrode using nanostructured anatase TiO{sub 2} nanobelts was studied in photoelectrochemical storage cells. • An intricate balance between a series of charge-transfer processes related to the dye sensitizer, redox species, and photoelectrode was discovered. • Under AM1.5 illumination rapid charge transfer in the 1D nanobelts enhances photocurrent. • Large specific surface area of the photoelectrode dominates the performance under visible light. - Abstract: Photoelectrochemical (PEC) devices, which use solar energy to drive charge transfer, have been considered as a low cost and effective approach to harvest energy from the sun. Dye sensitization designs are promising alternative to traditional semiconductor-based cells, as they can absorb a wide spectrum of light and provide free energy for PEC reactions. However, an intricate balance exists between a number of series charge-transfer processes related to the dye sensitizer, redox species, and photoelectrode. Here, we study a dye-sensitized photoelectrode using nanostructured anatase TiO{sub 2} nanobelts (TNBs) in the newly developed all-vanadium PEC storage cell (all-V PESC) to understand the performance dominating factor as well as to enhance photoexcitation and charge transfer, thus the solar energy storage efficiency. Preliminary results show enhanced photocurrent and reduced charge transfer resistance under AM1.5 illumination upon dye sensitization. Under visible light, however, large specific surface area of the photoelectrode seems to dominate the PEC performance.

36 MATERIALS SCIENCE↗

Generation of a fluorescent short-lifetime oxygen nanosensor by coupling of an exciplex forming dye pair

Typical oxygen-sensitive dyes have lifetimes in the μs-ms regime for sensitive oxygen detection based on molecular quenching. Due to the long triplet-state lifetimes and poor quenching efficiency of these probes, it has been difficult to develop short lifetime probes. We have developed oxygen sensors using a short-lifetime dye (∼30–60 ns) that forms an anthracene-aniline exciplex, which is quenched by molecular oxygen through an excited-state charge transfer mechanism. To achieve measurements in aqueous systems, we have tethered the dyes together via a C3 alkyl linker to facilitate greater exciplex formation at low dye concentration (20 μg mL −1 ) and encapsulated the resulting compound into polymeric nanoparticles to form an aqueous-dispersible short-lifetime oxygen nanosensor. The sensors emit at 420 nm (unfolded dye) and 500 nm (exciplex), and the ratiometric Stern-Volmer Constant is 1.52 ± 0.02 L mol −1 , showing good sensitivity from 0 % to 40 % dissolved oxygen without the tradeoff of a long lifetime needed for direct molecular quenching. In this paper, we characterize this sensor for both lifetime-based measurements using time-correlated single-photon counting and ratiometric intensity-based measurements using the unfolded dye emission as an internal reference peak.

Biological and medical sciences↗

DNA-Templated Aggregates of Strongly Coupled Cyanine Dyes: Nonradiative Decay Governs Exciton Lifetimes

Molecular excitons are used in a variety of applications including light harvesting, optoelectronics, and nanoscale computing. Controlled aggregation via covalent attachment of dyes to DNA templates is a promising aggregate assembly technique that enables the design of extended dye networks. Yet, there are few studies of exciton dynamics in DNA-templated dye aggregates. Here we report time-resolved excited-state dynamics measurements of two cyanine-based dye aggregates, a J-like dimer and an H-like tetramer, formed through DNA-templating of covalently attached dyes. Time-resolved fluorescence and transient absorption indicate that nonradiative decay, in the form of internal conversion, dominates the aggregate ground state recovery dynamics, with singlet exciton lifetimes on the order of tens of picoseconds for the aggregates versus nanoseconds for the monomer. These results highlight the importance of circumventing nonradiative decay pathways in the future design of DNA-templated dye aggregates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, Characterization, and Utilization of a Lignin-Based Adsorbent for Effective Removal of Azo Dye from Aqueous Solution

How to effectively remove toxic dyes from the industrial wastewater using a green low-cost lignocellulose-based adsorbent, such as lignin, has become a topic of great interest but remains quite challenging. In this study, cosolvent-enhanced lignocellulosic fractionation (CELF) pretreatment and Mannich reaction were combined to generate an aminated CELF lignin which is subsequently applied for removal of methylene blue and direct blue (DB) 1 dye from aqueous solution. 31P NMR was used to track the degree of amination, and an orthogonal design was applied to determine the relationship between the extent of amination and reaction parameters. The physicochemical, morphological, and thermal properties of the aminated CELF lignin were characterized to confirm the successful grafting of diethylenetriamine onto the lignin. The aminated CELF lignin proved to be an effective azo dye-adsorbent, demonstrating considerably enhanced dye decolorization, especially toward DB 1 dye (>90%). It had a maximum adsorption capacity of DB 1 dye of 502.7 mg/g, and the kinetic study suggested the adsorption process conformed to a pseudo-second-order kinetic model. The isotherm results also showed that the modified lignin-based adsorbent exhibited monolayer adsorption. The adsorbent properties were mainly attributed to the incorporated amine functionalities as well as the increased specific surface area of the aminated CELF lignin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser photolysis of fluorone dyes in a chitosan matrix

Kinetics of laser-induced photobleaching of fluorone dyes (fluorescein, dibromofluorescein, eosin Y, erythrosin B, Rose Bengal) is studied in a chitosan matrix. For all dyes the bleaching kinetics at the intensities of laser radiation 0.7 - 11.9 W cm{sup -2} demonstrates quasi-monomolecular behaviour. The results are analysed using a kinetic model, based on the four-level (S{sub 0}, S{sub 1}, T{sub 1}, T{sub n}) scheme of the dye with chemically active triplet states taken into account. It is shown that the rate constants of the chemical reaction involving higher triplet states in the dyes studied amount to (3.9 - 18.6) Multiplication-Sign 10{sup 6} s{sup -1} and exceed the analogous values for the reaction involving the first lower triplet states by nine orders of magnitude. The rate of reaction involving the first triplet states appeared to be higher by one - two orders of magnitude than that in the case of higher triplet states involved because of low population of the latter. The possible mechanism of dye bleaching with participation of chitosan that consists in reduction of the dye to the leuco form by transfer of hydrogen from the chitosan matrix is discussed. (interaction of laser radiation with matter. laser plasmas)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurement of atmospheric OH by titration of near-IR fluorescent dyes

Recent research has shown that certain polymethine dyes can be detected at ultratrace levels (greater than or equal to 6x10(exp -14) M) in solution by fluorimetry. These detection limits are possible because of the inherent sensitivity of fluorescence techniques, because the dyes fluoresce in the near infrared region where background interference is negligible, and because powerful infrared diode lasers are now available to improve the signal to noise ratio. Other work has shown that the hydroxyl radical destroys the ability of polymethine dyes to fluoresce. These observations form the basis for a new hydroxyl radical detector that is essentially a fluorometric titrator. Theoretically, the detector should show an acceptable sensitivity and response time. Assuming that the atmospheric HO concentration is about 10(exp -11) moles m(exp -3) (i.e. 10(exp 6) molecules cm(exp -3)), then 10 L of air 'titrated' with 20 mL of 10(exp -11) M dye solution (an easily detected concentration) should result in a drop in the fluorescent signal of 50 percent - a readily detectable change. At a flow rate of 3 L min(exp -1) the sampling time would be 3 minutes. The biggest potential problem is selectivity: other oxidants may also cause the fluorescence signal to be lost. The chemistry of polymethine dyes has not been studied in detail and so no quantitative data are available. However, a survey of the literature suggests that in general HO should react up to six orders of magnitude faster than HO2 and other radicals such as RO2 and RO. It should also react much more rapidly than H2O2 and O3. Thus it may be possible to discriminate kinetically against potential interfering substances. It was shown in the laboratory that 10(exp -4) M H2O2 has little effect on the absorption spectrum of the dye IR125 over a period of hours but that the band at 780 nm is slowly lost in water over a period of days even under argon in the dark. By contrast, DMSO solutions of IR125 are stable.

Betterton, Eric A.↗

Synthesis and photovoltaic properties of new thieno[3,2-b]indole-based dyes

New dyes of the 3-[5-(4-alkyl-4H-thieno[3,2-b]indol-2-yl)thiophen-2-yl]-2-cyanoacrylic acid series were prepared based on 2-(thien-2-yl)-substituted thieno[3,2-b]indole by its sequential N-alkylation, formylation, and condensation of the resulting aldehydes with cyanoacetic acid. The possible application of these dyes as sensitizers of mesoporous titanium dioxide thin films in dye-sensitized solar cells (DSSC) was shown. It was established that the efficiency of DSSC based on the dye IS 4 is superior to that of a similar element based on the commercial dye N3 [cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)ruthenium(II)].

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Synthesis of a novel building block for the preparation of multi-chromophoric sensitizers for panchromatic dye-sensitized solar cells

For this study, a simple 3-step synthesis of a novel pyrazine-containing heteroaromatic building block for use as a scaffold for producing multi-chromophoric sensitizers for use in dye sensitized solar cells has been developed. This moiety features two esterified carboxylic acid groups whose hydrolysis provides moieties for anchoring to nanoparticulate metal oxides and two bromine atoms that facilitate attachment of chromophores via palladium mediated cross-coupling methods. The utility of the building block for the synthesis of complex dye motifs is demonstrated by the preparation of a novel panchromatic dye featuring a BODIPY chromophore and a strongly electron donating porphyrin chromophore using both Suzuki and copper-free Sonogashira cross-coupling methods. The building block could be used either to attach two different or identical dye moieties to the metal oxide, or to attach an electron injection dye plus an auxiliary absorber, photoprotective agent, secondary redox moiety, etc.

14 SOLAR ENERGY↗