Phenolics in sugar cane juice : potential degradation by hydrogen peroxide and Fenton’s reagent

The presence of colour in raw sugar plays a key role in the marketing strategy of the Australian raw sugar industry. Some sugars are relatively difficult to decolourise during refining and develop colour during storage. A new approach that might result in efficient and cost-effective colour removal during the sugar manufacturing process is the use of an advanced oxidation process (AOP), known as Fenton oxidation, that is, catalytic production of hydroxyl radicals from the decomposition of hydrogen peroxide using ferrous iron. As a first step towards developing this technology, this study determined the composition of colour precursors present in the juice of cane harvested by three different methods. The methods were harvesting cane after burning, harvesting the whole crop with half of the trash extracted and harvesting the whole crop with no trash extracted. The study also investigated the degradation at pH 3, 4 and 5 of a phenolic compound, caffeic acid (3,4–dihydroxycinnamic acid), which is present in sugar cane juice, using both hydrogen peroxide and Fenton’s reagent. The results show that juice expressed from whole crop cane has significantly higher colour than juices expressed from burnt cane. However, the concentrations of phenolic acids were lower in the juices expressed from whole crop cane. The main phenolic acids present in these juices were p-coumaric, vanillic, 2,3–dihydroxybenzoic, gallic and 3,4–dihydroxybenzoic acids. The degradation of caffeic acid significantly improved using Fenton’s reagent in comparison to hydrogen peroxide alone. The Fenton oxidation was optimum at pH 5 when up to ~86% of caffeic acid degraded within 5 min.

Vibrational spectroscopic study of multianion mineral clinotyrolite Ca2Cu9[(As,S)O4]4(OH)10•10(H2O)

The molecular structure of the mixed anion mineral Clinotyrolite Ca2Cu9[(As,S)O4]4(OH)10•10(H2O) has been determined by the combination of Raman and infrared spectroscopy. Characteristic bands associated with arsenate, sulphate and hydroxyl units are identified. Broad bands in the OH stretching region are observed and are resolved into component bands. Estimates of hydrogen bond distances were made using a Libowitzky function and both short and long hydrogen bonds are identified. Two intense Raman bands at 842 and ~796 cm-1 are assigned to the ν1 (AsO4)3- symmetric stretching and ν3 (AsO4)3- antisymmetric stretching modes. The comparatively sharp Raman band at 980 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode and a broad Raman spectral profile centred upon 1100 cm-1 is attributed to the ν3 (SO4)2- antisymmetric stretching mode.

Vibrational spectroscopic study of the copper silicate mineral ajoite (K,Na)Cu7AlSi9O24(OH)6•3H2O

Ajoite (K,Na)Cu7AlSi9O24(OH)6•3H2O is a mineral named after the Ajo district of Arizona. Raman and infrared spectroscopy were used to characterise the molecular structure of ajoite. The structure of the mineral shows disorder which is reflected in the difficulty of obtaining quality Raman spectra. The Raman spectrum is characterised by a broad spectral profile with a band at 1048 cm-1 assigned to the ν1 (A1g) symmetric stretching vibration. Strong bands at 962, 1015 and 1139 cm-1 are assigned to the ν3 SiO4 antisymmetric stretching vibrations. Multiple ν4 SiO4 vibrational modes indicate strong distortion of the SiO4 tetrahedra. Multiple AlO and CuO stretching bands are observed. Raman spectroscopy and confirmed by infrared spectroscopy clearly shows that hydroxyl units are involved in the ajoite structure. Based upon the infrared spectra, water is involved in the ajoite structure, probably as zeolitic water.

Gold coating of silica and zinc oxide nanoparticles by the surface reduction of gold(I) chloride

The possibility of a surface inner sphere electron transfer mechanism leading to the coating of gold via the surface reduction of gold(I) chloride on metal and semi-metal oxide nanoparticles was investigated. Silica and zinc oxide nanoparticles are known to have very different surface chemistry, potentially leading to a new class of gold coated nanoparticles. Monodisperse silica nanoparticles were synthesised by the well known Stöber protocol in conjunction with sonication. The nanoparticle size was regulated solely by varying the amount of ammonia solution added. The presence of surface hydroxyl groups was investigated by liquid proton NMR. The resultant nanoparticle size was directly measured by the use of TEM. The synthesised silica nanoparticles were dispersed in acetonitrile (MeCN) and added to a bis acetonitrile gold(I) co-ordination complex [Au(MeCN)2]+ in MeCN. The silica hydroxyl groups were deprotonated in the presence of MeCN generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]+ complex to undergo ligand exchange with the silica nanoparticles, which formed a surface co-ordination complex with reduction to gold(0), that proceeded by a surface inner sphere electron transfer mechanism. The residual [Au(MeCN)2]+ complex was allowed to react with water, disproportionating into gold(0) and gold(III) respectively, with gold(0) being added to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of gold(III) to gold(0) by ascorbic acid. This process generated a thin and uniform gold coating on the silica nanoparticles. This process was modified to include uniformly gold coated composite zinc oxide nanoparticles (Au@ZnO NPs) using surface co-ordination chemistry. AuCl dissolved in acetonitrile (MeCN) supplied chloride ions which were adsorbed onto ZnO NPs. The co-ordinated gold(I) was reduced on the ZnO surface to gold(0) by the inner sphere electron transfer mechanism. Addition of water disproportionated the remaining gold(I) to gold(0) and gold(III). Gold(0) bonded to gold(0) on the NP surface with gold(III) was reduced to gold(0) by ascorbic acid (ASC), which completed the gold coating process. This gold coating process of Au@ZnO NPs was modified to incorporate iodide instead of chloride. ZnO NPs were synthesised by the use of sodium oxide, zinc iodide and potassium iodide in refluxing basic ethanol with iodide controlling the presence of chemisorbed oxygen. These ZnO NPs were treated by the addition of gold(I) chloride dissolved in acetonitrile leaving chloride anions co-ordinated on the ZnO NP surface. This allowed acetonitrile ligands in the added [Au(MeCN)2]+ complex to surface exchange with adsorbed chloride from the dissolved AuCl on the ZnO NP surface. Gold(I) was then reduced by the surface inner sphere electron transfer mechanism. The presence of the reduced gold on the ZnO NPs allowed adsorption of iodide to generate a uniform deposition of gold onto the ZnO NP surface without the use of additional reducing agents or heat.

Vibrational spectroscopic study of the minerals cavansite and pentagonite Ca(V4+O)Si4O10.4H2O

The bright blue minerals cavansite and pentagonite, a calcium vanadium silicate Ca(V4+O)Si4O10.4H2O, have been studied by UV–Visible, Raman and infrared spectroscopy. Cavansite shows an open porous structure with very small micron sized holes. Strong UV–Visible absorption bands are observed at around 403, 614 and 789 nm for cavansite and pentagonite. The Raman spectrum of cavansite is dominated by an intense band at 981 cm -1 and pentagonite by a band at 971 cm-1 attributed to the stretching vibrations of (SiO3)n units. Cavansite is characterised by two intense bands at 574 and 672 cm-1 whereas pentagonite by a single band at 651 cm-1. The Raman spectrum of cavansite in the hydroxyl stretching region shows bands at 3504, 3546, 3577, 3604 and 3654 cm-1 whereas pentagonite is a single band at 3532 cm_1. These bands are attributed to water coordinated to calcium and vanadium. XPS studies show that bond energy of oxygen in oxides is 530 eV, and in hydroxides -531.5 eV and for water -533.5 eV. XPS studies show a strong peak at 531.5 eV for cavansite, indicating some OH units in the structure of cavansite.

Raman spectroscopic study of the mineral xonotlite Ca 6Si 6O 17(OH) 2-A component of plaster boards

The mineral xonotlite Ca 6Si 6O 17(OH) 2 is a crystalline calcium silicate hydrate which is widely used in plaster boards and in many industrial applications. The structure of xonotlite is best described as having a dreierdoppelketten silicate structure, and describes the repeating silicate trimer which forms the silicate chains, and doppel indicating that two chains combine. Raman bands at 1042 and 1070 cm -1 are assigned to the SiO stretching vibrations of linked units of Si 4O 11 units. Raman bands at 961 and 980 cm -1 serve to identify Si 3O 10 units. The broad Raman band at 862 cm -1 is attributed to hydroxyl deformation modes. Intense Raman bands at 593 and 695 cm -1 are assigned to OSiO bending vibrations. Intense Raman bands at 3578, 3611, 3627 and 3665 cm -1 are assigned to OH stretching vibrations of the OH units in xonotlite. Infrared spectra are in harmony with the Raman spectra. Raman spectroscopy with complimentary infrared spectroscopy enables the characterisation of the building material xonotlite.

Raman spectroscopic study of the minerals apophyllite-(KF) KCa4Si8O20F.8H2O and apophyllite-(KOH) KCa4Si8O20(F,OH).8H2O

Raman spectroscopy complimented with infrared spectroscopy has been used to study the variation in molecular structure of two minerals of the apophyllite mineral group, namely apophyllite-(KF)KCa4Si8O20F.8H2O and apophyllite-(KOH) KCa4Si8O20(F,OH).8H2O. apophyllite-(KF) and apophyllite-(KOH) are different minerals only because of the difference in the percentage of fluorine to hydroxyl ions. The Raman spectra are dominated by a very intense sharp peak at 1059 cm -1. A band at around 846 cm -1 is assigned to the water librational mode. It is proposed that the difference between apophyllite-(KF) and apophyllite-(KOH) is the observation of two Raman bands in the OH stretching region at around 3563 and 3625 cm -1. Multiple water stretching and bending modes are observed showing that there is much variation in hydrogen bonding between water and the silicate surfaces.

Quinolinium 8-hydroxy-7-iodoquinoline-5-sulfonate 0.8-hydrate

In the structure of the hydrated quinolinium salt of ferron (8-hydroxy-7-iodoquinoline-5-sulfonic acid), C9H7N+ C9H5INO4S- . 0.8H2O, the quinolinium cation is fully disordered over two sites (occupancy factors 0.63 and 0.37) lying essentially within a common plane and with the ferron anions form pi-pi-associated stacks down the b axis (minimum ring centroid separation = 3.462(6)Ang.]. The cations and anions are linked into chains extending along c through hydroxyl O-H...O and quinolinium N-H...O hydrogen bonds to sulfonate O-atom acceptors which are also involved in water O-H...O hydrogen-bonding interactions down b giving a two-dimensional network structure.

Chemistry, Raman and infrared spectroscopic characterization of the phosphate mineral reddingite: (MnFe)3(PO4)2(H2O,OH)3, a mineral found in lithium-bearing pegmatite

Detailed investigation of an intermediate member of the reddingite–phosphoferrite series, using infrared and Raman spectroscopy, scanning electron microcopy and electron microprobe analysis, has been carried out on a homogeneous sample from a lithium-bearing pegmatite named Cigana mine, near Conselheiro Pena, Minas Gerais, Brazil. The determined formula is (Mn1.60Fe1.21Ca0.01Mg0.01)∑2.83(PO4)2.12⋅(H2O2.85F0.01)∑2.86 indicating predominance in the reddingite member. Raman spectroscopy coupled with infrared spectroscopy supports the concept of phosphate, hydrogen phosphate and dihydrogen phosphate units in the structure of reddingite-phosphoferrite. Infrared and Raman bands attributed to water and hydroxyl stretching modes are identified. Vibrational spectroscopy adds useful information to the molecular structure of reddingite–phosphoferrite.

Thermogravimetric analysis, PXRD, EDX and XPS study of chrysocolla (Cu,Al)2H2Si2O5(OH)4·nH2O : structural implications

Selected chrysocolla mineral samples from different origins have been studied by using PXRD, SEM, EDX and XPS. The XRD patterns show that the chrysocolla mineral samples are non-diffracting and no other phases are present in the minerals, thus showing the chrysocolla samples are pure. SEM analyses show the chrysocolla surfaces are featureless. EDX analyses enable the formulae of the chrysocolla samples to be calculated. The thermal decomposition of the mineral chrysocolla has been studied using a combination of thermogravimetric analysis and derivative thermogravimetric analysis. Five thermal decomposition mass loss steps are observed for the chrysocolla from Arizona (a) at 125 ◦C with the loss of water, (b) at 340 ◦C with the loss of hydroxyl units, (c) at 468.5 ◦C with a further loss of hydroxyls, (d) at 821 ◦C with oxygen loss and (e) at 895 ◦C with a further loss of oxygen. The thermal analysis of the chrysocolla from Congo shows mass losses at 125, 275.3, 805.6 and 877.4 ◦C and for the Nevada chrysocolla, mass loss steps at 268, 333, 463, 786.0 and 817.7 ◦C are observed. The thermal analysis of spertiniite is very different from that of chrysocolla and thermally decomposes at around 160 ◦C. XPS shows that there are two different copper species present, one which is bonded to oxygen and one to a hydroxyl unit. The O 1s is broad and very symmetrical suggesting two O species of equal number. The bond energy of 102.9 eV for the Si 2p suggests that it is in the form of a silicate. The bond energy is much higher for silicas around ∼103.5 eV. The reported value for silica gel has Si 2p at 103.4 eV. The combination of TG, PXRD, EDX and XPS adds to our fundamental knowledge of the structure of chrysocolla.

Kinetic study of goethite dehydration and the effect of aluminium substitution on the dehydrate

Goethite and Al-substituted goethite were synthesized and were characterized using XRD and XRF. The kinetic study of goethite dehydrate was investigated by TG and DTG at different heating rates (2, 5, 10, 15, 20 ◦C/min) and the effect of Al substitution for Fe on dehydrate was studied. The results showed that two types of absorbed water with the same Ed values of 3.4, 6.2 kJ/mol were confirmed on goethite and Alsubstituted goethite. Three types of hydroxyl units were proved, one being on the surface and the other two being in the structure of goethite. The substitution of Al for Fe in the structure of goethite decreases the desorption rate of hydroxyl, increases the dehydroxylation temperature, broadens the desorption peaks in DTG curves, and improves the Ed values from 19.4, 20.4, 26.1 kJ/mol to 21.6, 30, 33.6 kJ/mol when Al substitution comes to 9.1%.

An infrared spectroscopic comparison of four Chinese palygorskites

Infrared spectroscopy has been used to characterize and compare four palygorskite mineral samples from China. The position of the main bands identified by infrared spectra is similar, but there are some differences in intensity, which are significant. In addition, several additional bands are observed in the spectra of palygorskite and their impurities. This variability is attributed to differences in the geological environment, such as the degree of weathering and the extent of transportation of the minerals during formation or deposition, and the impurity content in these palygorskites. The bands of water and hydroxyl groups in these spectra of palygorskite samples have been studied. The characteristic band of palygorskite is observed at 1195 cm�1. Another four bands observed at 3480, 3380, 3266 and 3190 cm�1 are attributed to the water molecules in the palygorskite structure. These results suggest that the infrared spectra of palygorskites mineral from different regions are decided not only by the main physicochemical properties of palygorskite, but also by the amount and kind of impurities.

Aluminosilicates of zeolite N structure

A process for making aluminosilicates of zeolite N structure comprising the steps of: (i) combining a water soluble monovalent cation, a solution of hydroxyl anions and an aluminosilicate to form a resultant mixture having a pH greater than 10 and a H.sub.2O/Al.sub.2O.sub.3 ratio in the range 30 to 220; (ii) heating the resultant mixture to a temperature of between 50.degree. C. and boiling point of the mixture for a time between 1 minute and 100 hours until a crystalline product of zeolite N structure is formed as determined by X-ray diffraction or other suitable characteristic; and (iii) separating the zeolite N product as a solid from the mixture.

Vibrational spectroscopy of the borate mineral kotoite Mg3(BO3)2

Vibrational spectroscopy has been used to assess the structure of kotoite a borate mineral of magnesium which is isostructural with jimboite. The mineral is orthorhombic with point group: 2/m 2/m 2/m. The mineral has the potential as a new memory insulator material. The mineral has been characterised by a combination of Raman and infrared spectroscopy. The Raman spectrum is dominated by a very intense band at 835 cm−1, assigned to the symmetric stretching mode of tetrahedral boron. Raman bands at 919, 985 and 1015 cm−1 are attributed to the antisymmetric stretching modes of tetrahedral boron. Kotoite is strictly an hydrous borate mineral. An intense Raman band observed at 3559 cm−1 is attributed to the stretching vibration of hydroxyl units, more likely to be associated with the borate mineral hydroxyborate. The lack of observation of water bending modes proves the absence of water in the kotoite structure.

Vibrational spectroscopic study of the mineral penkvilksite Na2TiSi4O11·2H2O – a mineral used for the uptake of radionuclides

We have used vibrational spectroscopy to study the formula and molecular structure of the mineral penkvilksite Na 2TiSi 4O 11·2H 2O. Penkvilksite is a mineral which may be used in the uptake of radioactive elements. Both Raman and infrared spectroscopies identify a band at 3638 cm−1 attributed to an OH-stretching vibration of hydroxyl units. The inference is that OH units are involved in the structure of penkvilksite. The formula may be well written as Na 2TiSi 4O 10(OH)2·H 2O. The mineral is characterised by a very intense Raman band at 1085 cm−1 and a broad infrared band at 1080 cm−1 assigned to SiO-stretching vibrations. Raman bands at 620, 667 and 711 cm−1 are attributed to SiO and TiO chain bonds. Water-stretching vibrations are observed as Raman bands at 3197, 3265, 3425 and 3565 cm−1. Vibrational spectroscopy enables aspects of the molecular structure of the mineral penkvilksite to be ascertained. Penkvilksite is a mineral which can incorporate actinides and lanthanides from radioactive waste.