Microscopic, chemical and spectroscopic investigations on emeralds of various origins

In dieser Arbeit werden die mikroskopischen, chemischen und spektroskopischen Charakteristika von 260 natürlichen Smaragden und 66 synthetischen „Smaragden“ untersucht. Die Konzentrationen der chemischen Elemente von Smaragden wurden mit Hilfe der LA-ICP-MS und EMS bestimmt. Ergänzende Raman- und IR spektroskopische Methoden ermöglichen es, die Herkunft der verschiedenen Smaragde und ihrer synthetischen Analoga zu bestimmen. Auf Grund der verschiedenen Gehalte von Si, Al und Be können synthetische „Smaragde“ von natürlichen getrennt werden. Die Smaragde von Malipo, Chivor und auch synthetische „Smaragde“ können von allen anderen natürlichen Smaragden wegen der unterschiedlichen Cr-, V-, und Fe-Gehalte von einander getrennt werden. Wegen der unterschiedlichen Mg-, Na-, K-Gehalte lassen sich eher „schiefer-gebundene“ Smaragde identifizieren. Dabei wird festgestellt, dass die Unterscheidung in „schiefer-„ und „nichtschiefer-gebundene“ Smaragd-Vorkommen im Wesentlichen nur die Endglieder einer offensichtlich kristallchemisch sehr variablen Mineralchemie der Berylle, bzw. Smaragde beschreibt, dass damit aber keinesfalls eine petrologisch vertretbare Trennung belegbar ist, sondern dass Smaragde nur das jeweils regierende chemische Regime unter geeigneten Druck-Temperatur-Bedingungen widerspiegeln. Einschlussmerkmale spielen eine große Rolle bei der Unterscheidung verschiedener Lagerstätten und Herstellungsmethoden. Zum Beispiel können die Smaragde der drei Lagerstätten Santa Terezinha, Chivor, und Kafubu mit Hilfe ihrer charakteristischen Pyriteinschlüsse identifiziert werden. Die Band-Positionen und FWHM -Werte der Raman-Bande bei 1068 cm-1 und der IR-Bande bei 1200 cm-1 ermöglichen eine Differenzierung zwischen synthetischen und natürlichen Smaragden, und können darüber hinaus auch Auskunft geben über die Lagerstätte. Zusammen mit chemischen Messwerten kann bewiesen werden, dass diese Banden von Si-O Schwingungen verursacht werden. Die Raman- und IR-Banden im Bereich der Wasserschwingungen und insbesondere das IR-Band um 1140 cm-1 führen zur Trennung von Flux-Synthesen, Hydrothermal-Synthesen und natürlichen Smaragden.

IR/Raman spectroscopy and DFT calculations of cyclic di-amino acid peptides. Part III: comparison of solid state and solution structures of cyclo(L-Ser-L-Ser)

B3-LYP/cc-pVDZ calculations of the gas-phase structure and vibrational spectra of the isolated molecule cyclo(L-Ser-L-Ser), a cyclic di-amino acid peptide (CDAP), were carried out by assuming C-2 symmetry. It is predicted that the minimum-energy structure is a boat conformation for the diketopiperazine (DKP) ring with both L-Beryl side chains being folded slightly above the ring. An additional structure of higher energy (15.16 kJ mol(-1)) has been calculated for a DKP ring with a planar geometry, although in this case two fundamental vibrations have been calculated with imaginary wavenumbers. The reported X-ray crystallographic structure of cyclo(L-Ser-L-Ser), shows that the DKP ring displays a near-planar conformation, with both the two L-Beryl side chains being folded above the ring. It is hypothesized that the crystal packing forces constrain the DKP ring in a planar conformation and it is probable that the lower energy boat conformation may prevail in the aqueous environment. Raman scattering and Fourier-transform infrared (FT-IR) spectra of solid state and aqueous solution samples of cyclo(L-Ser-L-Ser) are reported and discussed. Vibrational band assignments have been made on the basis of comparisons with the calculated vibrational spectra and band wavenumber shifts upon deuteration of labile protons. The experimental Raman and IR results for solid-state samples show characteristic amide I vibrations which are split (Raman:1661 and 1687 cm(-1), IR:1666 and 1680 cm(-1)), possibly due to interactions between molecules in a crystallographic unit cell. The cis amide I band is differentiated by its deuterium shift of ~ 30 cm(-1), which is larger than that previously reported for trans amide I deuterium shifts. A cis amide II mode has been assigned to a Raman band located at 1520 cm(-1). The occurrence of this cis amide II mode at a wavenumber above 1500 cm(-1) concurs with results of previously examined CDAP molecules with low molecular weight substituents on the C-alpha atoms, and is also indicative of a relatively unstrained DKP ring.

Ecosystem relevance of variable jellyfish biomass in the Irish Sea between years, regions and water types

Monitoring the abundance and distribution of taxa is essential to assess their contribution to ecosystem processes. For marine taxa that are difficult to study or have long been perceived of little ecological importance, quantitative information is often lacking. This is the case for jellyfish (medusae and other gelatinous plankton). In the present work, 4 years of scyphomedusae by-catch data from the 2007-2010 Irish Sea juvenile gadoid fish survey were analysed with three main objectives: (1) to provide quantitative and spatially-explicit species-specific biomass data, for a region known to have an increasing trend in jellyfish abundance; (2) to investigate whether year-to-year changes in catch-biomass are due to changes in the numbers or in the size of medusa (assessed as the mean mass per individual), and (3) to determine whether inter-annual variation patterns are consistent between species and water masses. Scyphomedusae were present in 97% of samples (N=306). Their overall annual median catch-biomass ranged from 0.19 to 0.92gm-3 (or 8.6 to 42.4gm-2). Aurelia aurita and Cyanea spp. (Cyanea lamarckii and Cyanea capillata) made up 77.7% and 21.5% of the total catch-biomass respectively, but species contributions varied greatly between sub-regions and years. No consistent pattern was detected between the distribution and inter-annual variations of the two genera, and contrasting inter-annual patterns emerged when considering abundance either as biomass or as density. Significantly, A.aurita medusae were heavier in stratified than in mixed waters, which we hypothesize may be linked to differences in timing and yield of primary and secondary productions between water masses. These results show the vulnerability of time-series from bycatch datasets to phenological changes and highlight the importance of taking species- and population-specific distribution patterns into account when integrating jellyfish into ecosystem models.

Over-determined charbonate chemstry dataset from different kinds of manipulation (TA, DIC) and water types (natural and artificial seawater)

The growing field of ocean acidification research is concerned with the investigation of organism responses to increasing pCO2 values. One important approach in this context is culture work using seawater with adjusted CO2 levels. As aqueous pCO2 is difficult to measure directly in small-scale experiments, it is generally calculated from two other measured parameters of the carbonate system (often AT, CT or pH). Unfortunately, the overall uncertainties of measured and subsequently calculated values are often unknown. Especially under high pCO2, this can become a severe problem with respect to the interpretation of physiological and ecological data. In the few datasets from ocean acidification research where all three of these parameters were measured, pCO2 values calculated from AT and CT are typically about 30% lower (i.e. ~300 µatm at a target pCO2 of 1000 µatm) than those calculated from AT and pH or CT and pH. This study presents and discusses these discrepancies as well as likely consequences for the ocean acidification community. Until this problem is solved, one has to consider that calculated parameters of the carbonate system (e.g. pCO2, calcite saturation state) may not be comparable between studies, and that this may have important implications for the interpretation of CO2 perturbation experiments.

Inactivation and structural changes of E. Cloacae and B. Subtilis Endospores during IR laser water treatment

IR radiation has been studied for micro-organism inactivation of bacterial spores on metal substrates [1] and on metal and paper substrates [2]. A near-point near infrared laser water treatment apparatus for use in dental hand-pieces was also developed [3]. To date water sterilisation research using a mid-IR laser technique is very rare. According to the World Health Organisation [4], examinations for faecal indicator bacteria remain the most sensitive and specific way of assessing the hygienic quality of water. Bacteria that fall into this group are E. coli, other coliform bacteria (including E. cloacae) and to a lesser extent, faecal streptococci [5]. Protozoan cysts from organisms which cause giardiasis are the most frequently identified cause of waterborne diseases in developed countries [6,7]. The use of aerobic bacterial endospores to monitor the efficiency of various water treatments has been shown to provide a reliable and simple indicator of overall performance of water treatment[8,9].The efficacy of IR radiation for water disinfection compared to UV treatment has been further investigated in the present study. In addition FTIR spectroscopy in conjunction with Principle Component Analysis was used to characterise structural changes within the bacterial cells and endospores following IR laser treatment. Changes in carbohydrate content of E. cloacae following IR laser treatment were observed.

Using paint to investigate fires: an ATR-IR study of the degradation of paint samples upon heating

Fire investigation is a challenging area for the forensic investigator. The aim of this work was to use spectral changes to paint samples to estimate the temperatures to which a paint has been heated. Five paint samples (one clay paint, two car paints, one metallic paint, and one matt emulsion) have been fully characterized by a combination of attenuated total reflectance Fourier transform infrared (ATR-IR), Raman, X-ray fluorescence spectroscopy and powder X-ray diffraction. The thermal decomposition of these paints has been investigated by means of ATR-IR and thermal gravimetric analysis. Clear temperature markers are observed in the ATR-IR spectra namely: loss of m(C = O) band, >300°C; appearance of water bands on cooling, >500°C; alterations to m(Si–O) bands due to dehydration of silicate clays, >700°C; diminution of m(CO3) and d(CO3) modes of CaCO3, >950°C. We suggest the possible use of portable ATR-IR for nondestructive, in situ analysis of paints.

New-on-line method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us simultaneously to measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the online water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δ D robustness. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water, resulting in an artificial water background with well-known δ D and δ18O values. The speleothem sample is placed in a copper tube, attached to the line, and after system stabilisation it is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements, a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain &delta D; and δ18O isotopic compositions of measured water aliquots. Precision is better than 1.5 ‰ for δ D and 0.4 ‰ for δ18O for water measurements for an extended range (−210 to 0 ‰ for δ D and −27 to 0 ‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to the isotope ratio mass spectrometry (IRMS) technique.

Diagnosis of inflammatory lesions by high-wavenumber FT-Raman spectroscopy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

New online method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us simultaneously to measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the online water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δ D robustness. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water, resulting in an artificial water background with well-known δ D and δ18O values. The speleothem sample is placed in a copper tube, attached to the line, and after system stabilisation it is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements, a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain &delta D; and δ18O isotopic compositions of measured water aliquots. Precision is better than 1.5 ‰ for δ D and 0.4 ‰ for δ18O for water measurements for an extended range (−210 to 0 ‰ for δ D and −27 to 0 ‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to the isotope ratio mass spectrometry (IRMS) technique.

Fabrication and optimizing of metal nano silicate as toxic metal absorbent from sea water

Pure Water, is a crucial demand of creature life. Following industrial development, extra amount of toxic metals such as chromium enters the environmental cycle through the sewage, which is considered as a serious threat for organisms. One of the modern methods of filtration and removal of contaminants in water, is applying Nano-technology. According to specific property of silicate materials, in this article we try to survey increased power in composites and various absorption in several morphologies and also synthesis of Nano-metal silicates with different morphologies as absorbent of metal toxic ions. At first, we synthesize nano zink silicate with three morphologies considering context and the purpose of this survey. 1) Nano synthesis of zink silicate hollow cavity by hydrothermal method in mixed solvent system of ethanol/glycol polyethylene. 2) Zink nano wires silicate in a water-based system by controlling the amount of sodium silicate. 3) Synthesis of nano zink silicate membrane. After synthesizing, we measured the cadmium ion absorbance by synthesized nano zink silicates. Controlling PH, is the applied absorption method. Next step, we synthesized nano zink-magnesium silicate composite in two various morphologies of nanowires and membrane by different precent of zink and magnesium, in order to optimize synthesized nano metal silicate. We used zink nitrate and magnesium nitrate and also measured cadmium absorption by synthesized nano metal silicates in the same way of PH control absorption. In the 3rd step, in order to determine the impact of the type of metal in nano metal silicate, we synthesized nano magnesium silicate and compared its absorption with nano zink silicate. Furthermore, we calculated the optimal concentration in one of synthesizes. Optimal concentration is the process which has the maximum absorption. While applying two methods of absorption in the test, finally we compared the effect of absorption method on the absorption level. Below you find further steps of synthesis: 1) Using IR, RAMAN, XRD spectroscopy to check the accuracy of synthesis. 2) Checking the dispersion of nano particles in ethanol solution by light microscope. 3) Measuring and observing particles with scanning electron microscope (SEM). 4) Using atomic absorption device for measuring the cadmium concentration in water-based solutions. The nano metal silicates were synthesized successfully. All of synthesized nano absorbents have the cadmium ion absorbency. The cadmium absorption via nano absorbents depend on various factors such as kind of metal in nano silicate and percent of metal in nano metal silicate composite. Meanwhile the absorption and PH control of medium containing the absorbent and solution would affect the cadmium absorption.

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.

Characterisation of red mud and seawater neutralised red mud using vibrational spectroscopic techniques

Bauxite refinery residues are derived from the Bayer process by the digestion of crushed bauxite in concentrated caustic at elevated temperatures. Chemically, it comprises, in varying amounts (depending upon the composition of the starting bauxite), oxides of iron and titanium, residual alumina, sodalite, silica, and minor quantities of other metal oxides. Bauxite residues are being neutralised by seawater in recent years to reduce the alkalinity in bauxite residue, through the precipitation of hydrotalcite-like compounds and some other Mg, Ca, and Al hydroxide and carbonate minerals. A combination of X-ray diffraction (XRD) and vibrational spectroscopy techniques, including mid-infrared (IR), Raman, near-infrared (NIR), and UV-Visible, have been used to characterise bauxite residue and seawater neutralised bauxite residue. Both the ferrous (Fe2+) and ferric (Fe3+) ions within bauxite residue can be identified by their characteristic NIR bands, where ferrous ions produce a strong absorption band at around 9000 cm-1, while ferric ions produce two strong bands at 25000 and 14300 cm-1. The presence of adsorbed carbonate and hydroxide anions can be identified at around 5200 and 7000 cm-1, respectively, attributed to the 2nd overtone of the 1st fundamental overtones observed in the mid-IR spectra. The complex bands in the Raman and mid-IR spectra around 3500 cm-1 are assigned to the OH stretching vibrations of the various oxides present in bauxite residue, and water. The combination of carbonate and hydroxyl units and their fundamental overtones give rise to many of the features of the NIR spectra.

Raman spectroscopy of pyrite in marble from Chillagoe, Queensland

Samples of marble from Chillagoe, North Queensland have been analysed using scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) and Raman spectroscopy. Different types of marble were studied including soft white marble, hard white marble and a black marble. In this work, we try to ascertain why the black marble has this colour. Chemical analyses provide evidence for the presence of minerals other calcite in the marble, including the pyrite mineral. Some of these chemical analyses correspond to pyrite minerals in the black marble. The Raman spectra of these crystals were obtained and the Raman spectrum corresponds to that of pyrite from the RRUFF data base. The combination of SEM with EDS and Raman spectroscopy enables the characterisation of the mineral pyrite in Chillagoe black marble.

Phytoplankton quantity as an indicator of eutrophication in Finnish coastal waters : Applications within the Water Framework Directive

The tackling of coastal eutrophication requires water protection measures based on status assessments of water quality. The main purpose of this thesis was to evaluate whether it is possible both scientifically and within the terms of the European Union Water Framework Directive (WFD) to assess the status of coastal marine waters reliably by using phytoplankton biomass (ww) and chlorophyll a (Chl) as indicators of eutrophication in Finnish coastal waters. Empirical approaches were used to study whether the criteria, established for determining an indicator, are fulfilled. The first criterion (i) was that an indicator should respond to anthropogenic stresses in a predictable manner and has low variability in its response. Summertime Chl could be predicted accurately by nutrient concentrations, but not from the external annual loads alone, because of the rapid affect of primary production and sedimentation close to the loading sources in summer. The most accurate predictions were achieved in the Archipelago Sea, where total phosphorus (TP) and total nitrogen (TN) alone accounted for 87% and 78% of the variation in Chl, respectively. In river estuaries, the TP mass-balance regression model predicted Chl most accurately when nutrients originated from point-sources, whereas land-use regression models were most accurate in cases when nutrients originated mainly from diffuse sources. The inclusion of morphometry (e.g. mean depth) into nutrient models improved accuracy of the predictions. The second criterion (ii) was associated with the WFD. It requires that an indicator should have type-specific reference conditions, which are defined as "conditions where the values of the biological quality elements are at high ecological status". In establishing reference conditions, the empirical approach could only be used in the outer coastal water types, where historical observations of Secchi depth of the early 1900s are available. The most accurate prediction was achieved in the Quark. In the inner coastal water types, reference Chl, estimated from present monitoring data, are imprecise - not only because of the less accurate estimation method but also because the intrinsic characteristics, described for instance by morphometry, vary considerably inside these extensive inner coastal types. As for phytoplankton biomass, the reference values were less accurate than in the case of Chl, because it was possible to estimate reference conditions for biomass only by using the reconstructed Chl values, not the historical Secchi observations. An paleoecological approach was also applied to estimate annual average reference conditions for Chl. In Laajalahti, an urban embayment off Helsinki, strongly loaded by municipal waste waters in the 1960s and 1970s, reference conditions prevailed in the mid- and late 1800s. The recovery of the bay from pollution has been delayed as a consequence of benthic release of nutrients. Laajalahti will probably not achieve the good quality objectives of the WFD on time.    The third criterion (iii) was associated with coastal management including the resources it has available. Analyses of Chl are cheap and fast to carry out compared to the analyses of phytoplankton biomass and species composition; the fact which has an effect on number of samples to be taken and thereby on the reliability of assessments. However, analyses on phytoplankton biomass and species composition provide more metrics for ecological classification, the metrics which reveal various aspects of eutrophication contrary to what Chl alone does.

Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods and Na0.33V2O5 center dot 1.5H(2)O/RGO composite fabricated by a facile one pot synthesis and its lithium storage behavior

In this work, Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods and Na0.33V2O5 center dot 1.5H(2)O/reduced graphene oxide (RGO) composites have been prepared through a facile hydrothermal route in acidic medium at 200 degrees C for 2 days. The hydrothermally derived products have been characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, UV-Visible spectroscopy, Thermogravimetric analysis (TGA), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM) and electrochemical discharge-charge cycling in lithium ion battery. XRD pattern exhibits the layered structure of Na0.33V2O5 center dot 1.5H(2)O and the composite shows the presence of RGO at 2 theta = 25.8 degrees. FTIR spectrum shows that the band at 760 cm(-1) could be assigned to a V-OH2 stretching mode due to coordinated water. Raman spectrum shows that the band at 264 cm(-1) is due to the presence of water molecules between the layers. FESEM/TEM micrographs reveal that the products consist of nanorings of inner diameter 5 mu m and thickness of the ring is found to be 200-300 nm. Addition of exfoliated graphene oxide (EGO) destroys the formation of rings. The reduction of EGO sheets into RGO is also evidenced by the red shift of the absorbance peak from 228 nm to 264 nm. In this composite Na0.33V2O5 center dot 1.5H(2)O nanorods may adhere to the surface of RGO and/or embedded in the RGO nanosheets. As a result, an effective three-dimensional conducting network was formed by bridging RGO nanosheets, which can facilitate electron transport effectively and thus improve the kinetics and rate performance of Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods. The Na0.33V2O5 center dot 1.5H(2)O/RGO composites exhibited a discharge capacity of 340 mAh g(-1) at a current density of 0.1 mA g(-1) and also an improved cyclic stability. RGO plays a `flexible confinement' function to enwrap Na0.33V2O5 center dot 1.5H(2)O nanorods, which can compensate for the volume change and prevent the detachment and agglomeration of pulverized Na0.33V2O5 center dot 1.5H(2)O, thus extending the cycling life of the electrode. A probable reaction mechanism for the formation of Na0.33V2O5 center dot 1.5H(2)O nanorings is also discussed. (C) 2012 Elsevier B.V. All rights reserved.