Infrared and Raman spectroscopic characterization of the arsenate mineral ceruleite Cu2Al7(AsO4)4(OH)13⋅11.5(H2O)

The molecular structure of the arsenate mineral ceruleite has been assessed using a combination of Raman and infrared spectroscopy. The most intense band observed at 903 cm-1 is assigned to the (AsO4)3- symmetric stretching vibrational mode. The infrared spectrum shows intense bands at 787, 827 and 886 cm-1, ascribed to the triply degenerate m3 antisymmetric stretching vibration. Raman bands observed at 373, 400, 417 and 430 cm-1 are attributed to the m2 vibrational mode. Three broad bands for ceruleite found at 3056, 3198 and 3384 cm-1 are assigned to water OH stretching bands. By using a Libowitzky empirical equation, hydrogen bond distances of 2.65 and 2.75 Å are calculated. Vibrational spectra enable the molecular structure of the ceruleite mineral to be determined and whilst similarities exist in the spectral patterns with the roselite mineral group, sufficient differences exist to be able to determine the identification of the minerals.

Raman, infrared and near-infrared spectroscopic characterization of the herderite-hydroxylherderite mineral series

Natural single-crystal specimens of the herderite-hydroxylherderite series from Brazil, with general formula CaBePO4(F,OH), were investigated by electron microprobe, Raman, infrared and near-infrared spectroscopies. The minerals occur as secondary products in granitic pegmatites. Herderite and hydroxylherderite minerals show extensive solid solution formation. The Raman spectra of hydroxylherderite are characterized by bands at around 985 and 998 cm-1, assigned to ν1 symmetric stretching mode of the HOPO33- and PO43- units. Raman bands at around 1085, 1128 and 1138 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The set of Raman bands observed at 563, 568, 577, 598, 616 and 633 cm-1 are assigned to the ν4 out of plane bending modes of the PO4 and H2PO4 units. The OH Raman stretching vibrations of hydroxylherderite were observed ranging from 3626 cm-1 to 3609 cm-1. The infrared stretching vibrations of hydroxylherderites were observed between 3606 cm-1 and 3599 cm-1. By using a Libowitzky type function, hydrogen bond distances based upon the OH stretching bands were calculated. Characteristic NIR bands at around 6961 and 7054 cm-1 were assigned to the first overtone of the fundamental, whilst NIR bands at 10194 and 10329 cm-1 are assigned to the second overtone of the fundamental OH stretching vibration. Insight into the structure of the herderite-hydroxylherderite series is assessed by vibrational spectroscopy.

Vibrational spectroscopic study of the natural layered double hydroxide manasseite now defined as hydrotalcite-2H – Mg6Al2(OH)16[CO3]⋅4H2O

Raman and thermo-Raman spectroscopy have been applied to study the mineral formerly known as manasseite now simply renamed as hydrotalcite-2H Mg6Al2(OH)16[CO3]⋅4H2O. The mineral is a member of the homonymous hydrotalcite supergroup. Hydrogen bond distances calculated using a Libowitzky-type empirical function varied between 2.61 and 3.00 Å. Stronger hydrogen bonds were formed by water units as compared to the hydroxyl units. Raman spectroscopy enabled the identification of bands attributed to the hydroxyl units. Two Raman bands at 1059 and 1064 cm-1 are assigned to symmetric stretching modes of the carbonate anion. Thermal treatment shifts these bands to higher wavenumbers indicating a change in the strength of the carbonate bonding.

The spectroscopic characterization of the sulphate mineral ettringite from Kuruman manganese deposits, South Africa

The mineral ettringite has been studied using a number of techniques, including XRD, SEM with EDX, thermogravimetry and vibrational spectroscopy. The mineral proved to be composed of 53% of ettringite and 47% of thaumasite in a solid solution. Thermogravimetry shows a mass loss of 46.2% up to 1000 °C. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a band at 1072 cm−1 attributed to a carbonate symmetric stretching mode, confirming the presence of thaumasite. The observation of multiple bands in the ν4 spectral region between 700 and 550 cm−1 offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3629 cm−1 is assigned to the OH unit stretching vibration and the broad feature at around 3487 cm−1 to water stretching bands. Vibrational spectroscopy enables an assessment of the molecular structure of natural ettringite to be made.

Unsteady buoyancy driven flows and heat transfer through coupled thermal boundary layers in a partitioned triangular enclosure

A numerical investigation has been carried out for the coupled thermal boundary layers on both sides of a partition placed in an isosceles triangular enclosure along its middle symmetric line. The working fluid is considered as air which is initially quiescent. A sudden temperature difference between two zones of the enclosure has been imposed to trigger the natural convection. It is anticipated from the numerical simulations that the coupled thermal boundary layers development adjacent to the partition undergoes three distinct stages; namely an initial stage, a transitional stage and a steady state stage. Time dependent features of the coupled thermal boundary layers as well as the overall natural convection flow in the partitioned enclosure have been discussed and compared with the non-partitioned enclosure. Moreover, heat transfer as a form of local and overall average Nusselt number through the coupled thermal boundary layers and the inclined walls is also examined.

Analysis of nonlinear sequences and streamciphers

Streamciphers are common cryptographic algorithms used to protect the confidentiality of frame-based communications like mobile phone conversations and Internet traffic. Streamciphers are ideal cryptographic algorithms to encrypt these types of traffic as they have the potential to encrypt them quickly and securely, and have low error propagation. The main objective of this thesis is to determine whether structural features of keystream generators affect the security provided by stream ciphers.These structural features pertain to the state-update and output functions used in keystream generators. Using linear sequences as keystream to encrypt messages is known to be insecure. Modern keystream generators use nonlinear sequences as keystream.The nonlinearity can be introduced through a keystream generator's state-update function, output function, or both. The first contribution of this thesis relates to nonlinear sequences produced by the well-known Trivium stream cipher. Trivium is one of the stream ciphers selected in a final portfolio resulting from a multi-year project in Europe called the ecrypt project. Trivium's structural simplicity makes it a popular cipher to cryptanalyse, but to date, there are no attacks in the public literature which are faster than exhaustive keysearch. Algebraic analyses are performed on the Trivium stream cipher, which uses a nonlinear state-update and linear output function to produce keystream. Two algebraic investigations are performed: an examination of the sliding property in the initialisation process and algebraic analyses of Trivium-like streamciphers using a combination of the algebraic techniques previously applied separately by Berbain et al. and Raddum. For certain iterations of Trivium's state-update function, we examine the sets of slid pairs, looking particularly to form chains of slid pairs. No chains exist for a small number of iterations.This has implications for the period of keystreams produced by Trivium. Secondly, using our combination of the methods of Berbain et al. and Raddum, we analysed Trivium-like ciphers and improved on previous on previous analysis with regards to forming systems of equations on these ciphers. Using these new systems of equations, we were able to successfully recover the initial state of Bivium-A.The attack complexity for Bivium-B and Trivium were, however, worse than exhaustive keysearch. We also show that the selection of stages which are used as input to the output function and the size of registers which are used in the construction of the system of equations affect the success of the attack. The second contribution of this thesis is the examination of state convergence. State convergence is an undesirable characteristic in keystream generators for stream ciphers, as it implies that the effective session key size of the stream cipher is smaller than the designers intended. We identify methods which can be used to detect state convergence. As a case study, theMixer streamcipher, which uses nonlinear state-update and output functions to produce keystream, is analysed. Mixer is found to suffer from state convergence as the state-update function used in its initialisation process is not one-to-one. A discussion of several other streamciphers which are known to suffer from state convergence is given. From our analysis of these stream ciphers, three mechanisms which can cause state convergence are identified.The effect state convergence can have on stream cipher cryptanalysis is examined. We show that state convergence can have a positive effect if the goal of the attacker is to recover the initial state of the keystream generator. The third contribution of this thesis is the examination of the distributions of bit patterns in the sequences produced by nonlinear filter generators (NLFGs) and linearly filtered nonlinear feedback shift registers. We show that the selection of stages used as input to a keystream generator's output function can affect the distribution of bit patterns in sequences produced by these keystreamgenerators, and that the effect differs for nonlinear filter generators and linearly filtered nonlinear feedback shift registers. In the case of NLFGs, the keystream sequences produced when the output functions take inputs from consecutive register stages are less uniform than sequences produced by NLFGs whose output functions take inputs from unevenly spaced register stages. The opposite is true for keystream sequences produced by linearly filtered nonlinear feedback shift registers.

A Raman spectroscopic comparison of calcite and dolomite

Raman spectroscopy was used to characterize and differentiate the two minerals calcite and dolomite and the bands related to the mineral structure. The (CO3)2− group is characterized by four prominent Raman vibrational modes: (a) the symmetric stretching, (b) the asymmetric deformation, (c) asymmetric stretching and (d) symmetric deformation. These vibrational modes of the calcite and dolomite were observed at 1440, 1088, 715 and 278 cm−1. The significant differences between the minerals calcite and dolomite are observed by Raman spectroscopy. Calcite shows the typical bands observed at 1361, 1047, 715 and 157 cm−1, and the special bands at 1393, 1098, 1069, 1019, 299, 258 and 176 cm−1 for dolomite are observed. The difference is explained on the basis of the structure variation of the two minerals. Calcite has a trigonal structure with two molecules per unit cell, and dolomite has a hexagonal structure. This is more likely to cause the splitting and distorting of the carbonate groups. Another cause for the difference is the cation substituting for Mg in the dolomite mineral.

Indirect message injection for MAC generation

This paper presents a model for the generation of a MAC tag using a stream cipher. The input message is used indirectly to control segments of the keystream that form the MAC tag. Several recent proposals can be considered as instances of this general model, as they all perform message accumulation in this way. However, they use slightly different processes in the message preparation and finalisation phases. We examine the security of this model for different options and against different types of attack, and conclude that the indirect injection model can be used to generate MAC tags securely for certain combinations of options. Careful consideration is required at the design stage to avoid combinations of options that result in susceptibility to forgery attacks. Additionally, some implementations may be vulnerable to side-channel attacks if used in Authenticated Encryption (AE) algorithms. We give design recommendations to provide resistance to these attacks for proposals following this model.

Security analysis of linearly filtered NLFSRs

Non-linear feedback shift register (NLFSR) ciphers are cryptographic tools of choice of the industry especially for mobile communication. Their attractive feature is a high efficiency when implemented in hardware or software. However, the main problem of NLFSR ciphers is that their security is still not well investigated. The paper makes a progress in the study of the security of NLFSR ciphers. In particular, we show a distinguishing attack on linearly filtered NLFSR (or LF-NLFSR) ciphers. We extend the attack to a linear combination of LF-NLFSRs. We investigate the security of a modified version of the Grain stream cipher and show its vulnerability to both key recovery and distinguishing attacks.

Algebraic analysis of Trivium-like ciphers

Trivium is a bit-based stream cipher in the final portfolio of the eSTREAM project. In this paper, we apply the algebraic attack approach of Berbain et al. to Trivium-like ciphers and perform new analyses on them. We demonstrate a new algebraic attack on Bivium-A. This attack requires less time and memory than previous techniques to recover Bivium-A's initial state. Though our attacks on Bivium-B, Trivium and Trivium-N are worse than exhaustive keysearch, the systems of equations which are constructed are smaller and less complex compared to previous algebraic analyses. We also answer an open question posed by Berbain et al. on the feasibility of applying their technique on Trivium-like ciphers. Factors which can affect the complexity of our attack on Trivium-like ciphers are discussed in detail. Analysis of Bivium-B and Trivium-N are omitted from this manuscript. The full paper is available on the IACR ePrint Archive.

Vibrational spectroscopic characterization of the phosphate mineral althausite Mg2(PO4)(OH,F,O) – implications for the molecular structure

Natural single-crystal specimens of althausite from Brazil, with general formula Mg2(PO4)(OH,F,O) were investigated by Raman and infrared spectroscopy. The mineral occurs as a secondary product in granitic pegmatites. The Raman spectrum of althausite is characterized by bands at 1020, 1033 and 1044 cm-1, assigned to ν1 symmetric stretching modes of the HOPO33- and PO43- units. Raman bands at around 1067, 1083 and 1138 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The set of Raman bands observed at 575, 589 and 606 cm-1 are assigned to the ν4 out of plane bending modes of the PO4 and H2PO4 units. Raman bands at 439, 461, 475 and 503 cm-1 are attributed to the ν2 PO4 and H2PO4 bending modes. Strong Raman bands observed at 312, 346 cm-1 with shoulder bands at 361, 381 and 398 cm-1 are assigned to MgO stretching vibrations. No bands which are attributable to water were found. Vibrational spectroscopy enables aspects of the molecular structure of althausite to be assessed.

A vibrational spectroscopic study of the silicate mineral ardennite-(As)

We have used a combination of scanning electron microscopy with EDX and vibrational spectroscopy to study the mineral ardennite-(As). The mineral ardennite-(As) of accepted formula Mn2þ 4 (Al,Mg)6(Si3O10)(SiO4)2(AsO4,VO4)(OH)6 is a silicate mineral which may contain arsenate and/or vanadates anions. Because of the oxyanions present, the mineral lends itself to analysis by Raman and infrared spectroscopy. Qualitative chemical analysis shows a homogeneous phase, composed by Si, Mn, Al and As. Ca and V were also observed in partial substitution for Mn and As. Raman bands at 1197, 1225, 1287 and 1394 cm-1 are assigned to SiO stretching vibrations. The strong Raman bands at 779 and 877 cm-1 are assigned to the AsO3- 4 antisymmetric and symmetric stretching vibrations. The Raman band at 352 cm-1 is assigned to the m2 symmetric bending vibration. The series of Raman bands between 414 and 471 cm-1 are assigned to the m4 out of plane bending modes of the AsO3-4 units. Intense Raman bands observed at 301 and 314 cm-1 are attributed to the MnO stretching and bending vibrations. Raman bands at 3041, 3149, 3211 and 3298 cm-1 are attributed to the stretching vibrations of OH units. There is vibrational spectroscopic evidence for the presence of water adsorbed on the ardennite-(As) surfaces.

A vibrational spectroscopic study of the arsenate mineral bayldonite (Cu,Zn)3Pb(AsO3OH)2(OH)2 : a comparison with other basic arsenates

We have studied the vibrational spectra of the mineral bayldonite, a hydroxy arsenate of copper and lead of formula Cu3Pb(AsO3OH)2(OH)2 from the type locality, the Penberthy Croft Mine, St Hilary, Mount's Bay District, Cornwall, England.and relate the spectra to the mineral structure. Raman bands at 896 and 838 cm-1are assigned to the (AsO4)3- ν1 symmetric stretching mode and the second to the (AsO4)3- ν3 antisymmetric stretching mode. It is noted that the position of the symmetric stretching mode is at a higher position than the antisymmetric stretching mode. It is proposed that the Raman bands at 889 and 845 cm-1 are symmetric and antisymmetric stretching modes of the (HOAsO3)2- units. Raman bands of bayldonite at 490 and 500 cm-1 are assigned to the (AsO4)3- ν4 bending modes. Raman bands for bayldonite are noted at 396, 408 and 429 cm-1 and are assigned to the (AsO4)3- ν2 bending modes. A comparison is made with spectra of the other basic copper arsenate minerals, namely cornubite, olivenite, cornwallite.

A study of the phosphate mineral kapundaite NaCa(Fe3+)4(PO4)4(OH)3⋅5(H2O) using SEM/EDX and vibrational spectroscopic methods

Vibrational spectroscopy enables subtle details of the molecular structure of kapundaite to be determined. Single crystals of a pure phase from a Brazilian pegmatite were used. Kapundaite is the Fe3+ member of the wardite group. The infrared and Raman spectroscopy were applied to compare the structure of kapundaite with wardite. The Raman spectrum of kapundaite in the 800–1400 cm−1 spectral range shows two intense bands at 1089 and 1114 cm−1 assigned to the ν1PO43- symmetric stretching vibrations. The observation of two bands provides evidence for the non-equivalence of the phosphate units in the kapundaite structure. The infrared spectrum of kapundaite in the 500–1300 cm−1 shows much greater complexity than the Raman spectrum. Strong infrared bands are found at 966, 1003 and 1036 cm−1 and are attributed to the ν1PO43- symmetric stretching mode and ν3PO43- antisymmetric stretching mode. Raman bands in the ν4 out of plane bending modes of the PO43- unit support the concept of non-equivalent phosphate units in the kapundaite structure. In the 2600–3800 cm−1 spectral range, Raman bands for kapundaite are found at 2905, 3151, 3311, 3449 and 3530 cm−1. These bands are broad and are assigned to OH stretching vibrations. Broad infrared bands are also found at 2904, 3105, 3307, 3453 and 3523 cm−1 and are attributed to water. Raman spectroscopy complimented with infrared spectroscopy has enabled aspects of the structure of kapundaite to be ascertained and compared with that of other phosphate minerals.

A 22-nt artificial microRNA mediates widespread RNA silencing in Arabidopsis

It is known that 22-nucleotide (nt) microRNAs (miRNAs) derived from asymmetric duplexes trigger phased small-interfering RNA (phasiRNA) production from complementary targets. Here we investigate the efficacy of 22-nt artificial miRNA (amiRNA)-mediated RNA silencing relative to conventional hairpin RNA (hpRNA) and 21-nt amiRNA-mediated RNA silencing. CHALCONE SYNTHASE (CHS) was selected as a target in Arabidopsis thaliana due to the obvious and non-lethal loss of anthocyanin accumulation upon widespread RNA silencing. Over-expression of CHS in the pap1-D background facilitated visual detection of both local and systemic RNA silencing. RNA silencing was initiated in leaf tissues from hpRNA and amiRNA plant expression vectors under the control of an Arabidopsis RuBisCo small subunit 1A promoter (SSU). In this system, hpRNA expression triggered CHS silencing in most leaf tissues but not in roots or seed coats. Similarly, 21-nt amiRNA expression from symmetric miRNA/miRNA* duplexes triggered CHS silencing in all leaf tissues but not in roots or seed coats. However, 22-nt amiRNA expression from an asymmetric duplex triggered CHS silencing in all tissues, including roots and seed coats, in the majority of plant lines. This widespread CHS silencing required RNA-DEPENDENT RNA POLYMERASE6-mediated accumulation of phasiRNAs from the endogenous CHS transcript. These results demonstrate the efficacy of asymmetric 22-nt amiRNA-directed RNA silencing and associated phasiRNA production and activity, in mediating widespread RNA silencing of an endogenous target gene. Asymmetric 22-nt amiRNA-directed RNA silencing requires little modification of existing amiRNA technology and is expected to be effective in suppressing other genes and/or members of gene families.