RECENT PUBLICATIONS

Interactions of cisplatin and the copper transporter CTR1 in human colon cancer cells

Dr Liz New

Dr Liz New

Posted 20 June 2017
Mia Akerfeldt, Carmen Tran, Clara Shen, Trevor Hambley and Elizabeth New. Journal of Biological Inorganic Chemistry, 22 (5), 765-774, 2017. DOI: 10.1007/s00775-017-1467-y

Abstract
There is much interest in understanding the mechanisms by which platinum-based anticancer agents enter cells, and the copper transporter CTR1 has been the focus of many recent studies. While there is a clinical correlation between CTR1 levels and platinum efficacy, cellular studies have provided conflicting evidence relating to the relationship between cisplatin and CTR1. We report here our studies of the relationship between cisplatin and copper homeostasis in human colon cancer cells. While the accumulation of copper and platinum do not appear to compete with each other, we did observe that cisplatin perturbs CTR1 distribution within 10 min, a far shorter incubation time than commonly employed in cellular studies of cisplatin. Furthermore, on these short time-scales, cisplatin caused an increase in the cytoplasmic labile copper pool. While the predominant focus of studies to date has been on CTR1, these studies highlight the importance of investigating the interaction of cisplatin with other copper proteins.


Tunable porous coordination polymers for the capture, recovery and storage of inhalation anesthetics

Professor Cameron Kepert

Prof Cameron Kepert

Posted 20 June 2017
Cameron Kepert and Peter Southon et al. Chemistry: A European Journal, 23 (33), 7871-7875, 2017. DOI: 10.1002/chem.201700389

Abstract
The uptake of inhalation anesthetics by three topologically identical frameworks is described. The 3D network materials, which possess square channels of different dimensions, are formed from the relatively simple combination of ZnII centres and dianionic ligands that contain a phenolate and a carboxylate group at opposite ends. All three framework materials are able to adsorb N2O, Xe and isoflurane. Whereas the framework with the widest channels is able to adsorb large quantities of the various guests from the gas phase, the frameworks with the narrower channels have superior binding enthalpies and exhibit higher levels of retention. The use of ligands in which substituents are bound to the aromatic rings of the bridging ligands offers great scope for tuning the adsorption properties of the framework materials.


High cytotoxicity of vanadium(IV) complexes with 1,10-phenanthroline and related ligands is due to decomposition in cell culture medium

Professor Peter Lay

Prof Peter Lay

Posted 20 June 2017
Maria Le, Oliver Rathje, Aviva Levina and Peter Lay. Journal of Biological Inorganic Chemistry, 22 (5), 663-672, 2017. DOI: 10.1007/s00775-017-1453-4

Abstract
Cytotoxic effects of Metvan (cis-[VIVO(OSO3)(Me2phen)2], where Me2phen = 4,7-dimethyl-1,10-phenanthroline) and its analogues with 1,10-phenanthroline (phen) and 2,2'-bipyridine (bpy) ligands in cultured human lung cancer (A549) cells have been re-investigated in conjunction with reactivity of the V(IV) complexes in neutral aerated aqueous solutions and in cell culture medium. All the V(IV) complexes underwent rapid oxidation to the corresponding V(V) species (cis-[VV(O)2L2]+), followed by release of free ligands (shown by electrospray mass spectrometry). Decomposition of V(IV) complexes in cell culture medium within minutes at 310 K was confirmed by UV-Vis and EPR spectroscopies. High cytotoxicities (low muM or sub-muM IC50 range in 72 h assays) were observed for the phen and Me2phen complexes, but they were not different from that of the corresponding free ligands, which confirmed that the original V(IV) complexes played no significant role in the observed biological activities. The cytotoxicities of the ligands were most likely due to their complexation of redox-active essential metal ions, such as Cu(II) and Fe(II), in the medium, and their increased cellular uptake, leading to oxidative stress-related cell death. These results emphasize the need to assess the stability of metal-based drugs under the conditions of biological assays, particularly when biologically active ligands, such as 1,10-phenanthroline and its derivatives, are used. These ligands have high systemic toxicities in vivo and their release in the GI tract and blood makes the complexes unsuitable for use as anti-cancer drugs.


Time-resolved and temperature tuneable measurements of fluorescent intensity using a smartphone fluorimeter

Professor John Canning

Prof John Canning

Posted 20 June 2017
Md Arafat Hossain, John Canning*, Zhikang Yu, Peter Rutledge, Joseph Wong, Abbass Jamalipour and Max Crossley. Analyst, 142 (11), 1953-1961, 2017. DOI: 10.1039/c7an00535k

Abstract
A smartphone fluorimeter capable of time-based fluorescence intensity measurements at various temperatures is reported. Excitation is provided by an integrated UV LED (λex = 370 nm) and detection obtained using the in-built CMOS camera. A Peltier is integrated to allow measurements of the intensity over T = 10 to 40 °C. All components are controlled using a smartphone battery powered Arduino microcontroller and a customised Android application that allows sequential fluorescence imaging and quantification every δt = 4 seconds. The temperature dependence of fluorescence intensity for four emitters (rhodamine B, rhodamine 6G, 5,10,15,20-tetraphenylporphyrin and 6-(1,4,8,11-tetraazacyclotetradecane)2-ethyl-naphthalimide) are characterised. The normalised fluorescence intensity over time of the latter chemosensor dye complex in the presence of Zn2+ is observed to accelerate with an increasing rate constant, k = 1.94 min-1 at T = 15 °C and k = 3.64 min-1 at T = 30 °C, approaching a factor of -2 with only a change in temperature of ΔT = 15 °C. Thermally tuning these twist and bend associated rates to optimise sensor approaches and device applications is proposed.


Experimental and computational study of the magnetic properties of ZrMn(2-x)Co(x)Ge(4)O(12)

Associate Professor Chris Ling

A/Prof Chris Ling

Posted 20 June 2017
Matthew Sale, Maxim Avdeev and Chris Ling et al. Dalton Transactions, 46 (21), 6921-6933, 2017. DOI: 10.1039/c7dt00975e

Abstract
Polycrystalline samples in the solid solution ZrMn2-xCoxGe4O12 (x = 0.0, 0.5, 1.0, 1.5 and 2.0) have been prepared using the ceramic method and characterised by a combination of magnetometry, X-ray diffraction and neutron diffraction. They all adopt the space group P4/nbm with a - 9.60, c - 4.82 Å and show long-range magnetic order with transition temperatures, TC, in the range 2 < TC/K < 10. The underlying magnetic structure is the same in each case but the ordered spins lie along [001] when x = 0.0 and in the (001) plane for all other compositions. In all cases the magnetically-ordered phase is a weak ferromagnet although the magnitude of the spontaneous magnetisation and the strength of the coercive field are composition-dependent. The magnetic structure can be rationalized by considering the strengths of the interactions along the distinct M-O-Ge-O-M superexchange pathways in the crystal and the observed magnetic structure is entirely consistent with the predictions of ab initio calculations.


Acute and residual effects in adolescent rats resulting from exposure to the novel synthetic cannabinoids AB-PINACA and AB-FUBINACA

Professor Michael Kassiou

Prof Michael Kassiou

Posted 13 June 2017
Michael Moir, Samuel Banister and Michael Kassiou et al. Journal of Psychopharmacology, 31 (6), 757-769, 2017. DOI: 10.1177/0269881116684336

Abstract
Synthetic cannabinoids (SCs) have rapidly proliferated as recreational drugs, and may present a substantial health risk to vulnerable populations. However, information on possible effects of long-term use is sparse. This study compared acute and residual effects of the popular indazole carboxamide SC compounds AB-PINACA and AB-FUBINACA in adolescent rats with delta9-tetrahydrocannabinol (THC) and control treatments. Albino Wistar rats were injected (i.p.) with AB-PINACA or AB-FUBINACA every second day (beginning post-natal day (PND) 31), first at a low dose (0.2 mg/kg on 6 days) followed by a higher dose (1 mg/kg on a further 6 days). THC-treated rats received equivalent doses of 6 × 1 mg/kg and 6 x 5 mg/kg. During drug treatment, THC, AB-PINACA, and AB-FUBINACA decreased locomotor activity at high and low doses, increased anxiety-like behaviours and audible vocalisations, and reduced weight gain. Two weeks after dosing was completed, all cannabinoid pre-treated rats exhibited object recognition memory deficits. These were notably more severe in rats pre-treated with AB-FUBINACA. However, social interaction was reduced in the THC pre-treated group only. Six weeks post-dosing, plasma levels of cytokines interleukin (IL)-1alpha and IL-12 were reduced by AB-FUBINACA pre-treatment, while cerebellar endocannabinoids were reduced by THC and AB-PINACA pre-treatment. The acute effects of AB-PINACA and AB-FUBINACA were broadly similar to those of THC, suggesting that acute SC toxicity in humans may be modulated by dose factors, including inadvertent overdose and product contamination. However, some lasting residual effects of these different cannabinoid receptor agonists were subtly different, hinting at recruitment of different mechanisms of neuroadaptation.


Functional coordination polymers based on redox-active tetrathiafulvalence and its derivatives

Associate Professor Deanna D

A/Prof Deanna D'Alessandro

Posted 13 June 2017
Chanel Leong and Deanna D'Alessandro et al. Coordination Chemistry Reviews, 345, 342-361, 2017. DOI: 10.1016/j.ccr.2016.10.011

Abstract
This review article focuses on the development of coordination polymers based on tetrathiafulvalene and its derivatives. We aim to demonstrate novel opportunities for these coordination polymers in terms of their architectures and potential applications. The review is presented in five general sections according to the type of coordinating functional group in the organic linkers. Synthetic approaches, structural analyses, as well as physical and chemical properties are presented for each example. Valuable potential applications and perspectives for these novel materials are also discussed.


Tailoring phase transition temperatures in perovskites via A-site vacancy generation

Associate Professor Siegbert Schmid

A/Prof Siggi Schmid

Posted 13 June 2017
Thomas Whittle, William Brant and Siegbert Schmid et al. Dalton Transactions, 46 (22), 7253-7260, 2017. DOI: 10.1039/c7dt00352h

Abstract
The structures across the Sr0.8Ti0.6-xZrxNb0.4O3, 0 < x < 0.6, defect perovskite series were investigated using complementary synchrotron X-ray and neutron powder diffraction data. The locations of second order compositional and temperature dependent phase transitions between the high symmetry cubic Pm[3 with combining macron]m phase and the lower symmetry tetragonal I4/mcm phase were determined. Deviation of the oxygen x coordinate from the high symmetry value and the B-O-B bond angle from 180° as well as the tetragonal strain squared were each found to be suitable order parameters to monitor the transitions. Tolerance factor calculations confirmed that these A-site deficient perovskites retain a higher symmetry to a lower value than their fully occupied counterparts. Therefore, adjusting vacancy concentrations can be employed as a general strategy to design compounds with specifically tailored phase transition temperatures.


The energy dependence of CO(v,J) produced from H2CO via the transition state, roaming, and triple fragmentation channels

Associate Professor Meredith Jordan

A/Prof Meredith Jordan

Posted 13 June 2017
Duncan Andrews, Meredith Jordan and Scott Kable et al. The Journal of Chemical Physics, 147 (1), 013935, 2017. DOI: 10.1063/1.4983138

Abstract
The dynamics of CO production from photolysis of H2CO have been explored over a 8000 cm-1 energy range (345 nm-266 nm). Two-dimensional ion imaging, which simultaneously measures the speed and angular momentum distribution of a photofragment, was used to characterise the distribution of rotational and translational energy and to quantify the branching fraction of roaming, transition state (TS), and triple fragmentation (3F) pathways. The rotational distribution for the TS channel broadens significantly with increasing energy, while the distribution is relatively constant for the roaming channel. The branching fraction from roaming is also relatively constant at 20% of the observed CO. Above the 3F threshold, roaming decreases in favour of triple fragmentation. Combining the present data with our previous study on the H-atom branching fractions and published quantum yields for radical and molecular channels, absolute quantum yields were determined for all five dissociation channels for the entire S1<–S0 absorption band, covering almost 8000 cm-1 of excitation energy. The S0 radical and TS molecular channels are the most important over this energy range. The absolute quantum yield of roaming is fairly constant -5% at all energies. The T1 radical channel is important (20%-40%) between 1500 and 4000 cm-1 above the H + HCO threshold, but becomes unimportant at higher energy. Triple fragmentation increases rapidly above its threshold reaching a maximum of 5% of the total product yield at the highest energy.


The structure anion order, and Ce3+ luminescence of Y4A12O9-Y4Si2O7N2 solid solutions

Dr Chun-Hai Wang

Dr Chun-Hai Wang

Posted 13 June 2017
Chun-Hai Wang et al. Journal of Materials Chemistry C, 5 (19), 4654-4660, 2017. DOI: 10.1039/c7tc00965h

Abstract
Oxonitridoalumosilicates Y4Al2-2xSi2xO9-2xN2x (0.00 < x < 1.00) were prepared and the substitution effect of [Al3+O2-] pairs by [Si4+N3-] pairs in Y4Al2O9-Y4Si2O7N2 solid solutions on the structure and its corresponding influence on the Ce3+ activated luminescence properties are investigated. Y4Al2-2xSi2xO9-2xN2x (0.00 < x < 1.00) shows two solid solution regions, x = 0.00-0.40 for solid solution I, x = 0.50-1.00 for solid solution II from X-ray and neutron diffraction analysis. In the solid solution I, the Ce3+ emission is mainly in the UV range with the maximum wavelength at 350 nm, and the intensity decreases rapidly with the increase of the N content. In the solid solution II, the Ce3+ doped samples show blue-green luminescence with the maximum wavelength at -450 nm and the wide excitation bands extend from UV to 450 nm. The phosphors in the solid solution II are promising candidates for white-LED applications.


Conformational dynamics in an organic ionic plastic crystal

Associate Professor Chris Ling

A/Prof Chris Ling

Posted 7 June 2017
Chris Ling and Adriano Pavan et al. The Journal of Physical Chemistry B, 121 (21), 5439-5446, 2017. DOI: 10.1021/acs.jpcb.7b02780

Abstract
Understanding the short-range molecular motions of organic ionic plastic crystals is critical for the application of these materials as solid-state electrolytes in electrochemical devices such as lithium batteries. However, the theory of short-range-motions was originally developed for simple molecular plastic crystals and does not take account of strong interionic interactions that are present in organic ionic plastic crystals. Here we report a fundamental investigation of the dynamic behavior of an archetypal example triethyl(methyl)phosphonium bis(fluorosulfonyl)amide ([P1222][FSI]) through calorimetry, impedance spectroscopy, synchrotron X-ray diffraction, and solid-state NMR and Raman spectroscopies. For the first time, we show the presence of conformational dynamics in the solid state for the FSI anion. We relate the dynamics to a unique second-order displacive phase transition of [P1222][FSI]. This detailed analysis suggests a new disorder mechanism involving cooperative motion between the cation and FSI anion in the plastic crystal due to strong interionic interactions.


Structural and magnetic properties of the osmium double perovskites Ba2-xSrxYOsO6

Professor Brendan Kennedy

Prof Brendan Kennedy

Posted 7 June 2017
Paula Kayser, Sean Injac and Brendan Kennedy*. Inorganic Chemistry, 56 (11), 6565-6575, 2017. DOI: 10.1021/acs.inorgchem.7b00691

Abstract
The impact of chemical doping on the structures and magnetic properties of the ordered double perovskites Ba2-xSrxYOsO6 was investigated using neutron and X-ray diffraction, X-ray spectroscopy, and bulk magnetic susceptibilities. The structure to evolve from cubic to monoclinic as the Sr content is increased. The oxides all have an AFM1-type magnetic structure and analysis of the Os L3/L2 branching ratio, as determined by X-ray absorption, shows that spin-orbit coupling is constant across the series.


Structural investigation of cobalt oxide clusters derived from molecular cobalt cubane, trimer, and dimer oligomers in a phosphate electrolyte

Professor Thomas Maschmeyer

Prof Thomas Maschmeyer

Posted 7 June 2017
Xiaobo Li, Edwin Clatworthy, Stuart Bartlett, Tony Masters and Thomas Maschmeyer*. The Journal of Physical Chemistry C, 121 (21), 11021-11026, 2017. DOI: 10.1021/acs.jpcc.6b11607

Abstract
Cobalt oxide clusters were formed from three molecular cobalt oligomers, the Co-cubane, [Co4(μ3-O)4(μ-OAc)4(py)4], Co-trimer, [Co3(μ3-O)(μ-OAc)6(py)3][PF6], and Co-dimer, [Co2(μ-OH)2(μ-OAc)(OAc)2(py)4][PF6], in phosphate buffer electrolyte after aging. Phosphate is essential for the formation of these cobalt oxide clusters. XAS characterization shows the cobalt oxide clusters are CoII/IIIOx clusters with CoII(O)4 and CoIII(O)6 subunits. The cobalt oxide clusters formed have a structure similar to that of aged “CoPi” oxygen evolution catalysts prepared by electrodeposition.


The impact of anion ordering on octahedra distortion and phase transitions in SrTaO2N and BaTaO2N

Professor Brendan Kennedy

Prof Brendan Kennedy

Posted 7 June 2017
Chun-Hai Wang, Brendan Kennedy*, Andre de Oliveira and Julia Polt et al. Acta Cryst., B73 (Part 3), 389-398, 2017. DOI: 10.1107/S2052520617001123

Abstract
In this work we synthesized BaTaO2N and SrTaO2N using a two-step high-temperature solid-state reaction method and analysed the structural distortions, relative to the ideal cubic perovskite structure, according to group theory. From a complete distortion analysis/refinement using high-resolution neutron diffraction data in the temperature range 8 to 613 K, we identified tetragonal structures for BaTa02N [P4/mmm (No. 123)] and SrTaO2N [I4/mcm (No. 140)]. In contrast to an anion-disordered cubic perovskite (Pm \overline{3}m No. 221) with Ta at the cell center, both systems show a site preference for oxygen anions in the two opposite corners (along the c axis) of the Ta-O/N octahedra rather than the four square corners in the ab plane (Γ3+ occupancy distortion), which induces a tetragonal elongation of the unit cell with the c axis being longer than the a axis. A further Ta-O/N octahedra displacement [R5-(a,0,0), rotation about the c axis] distortion was observed in SrTaO2N. This distortion mode is accompanied by an increased unit-cell distortion that decreases as the temperature increases. Ultimately a second-order phase transition caused by the loss of the R5-(a,0,0) mode was observed at 400-450 K.


Production of high quality syncrude from lignocellulosic biomass

Professor Thomas Maschmeyer

Prof Thomas Maschmeyer

Posted 7 June 2017
Thomas Maschmeyer et al. ChemCatChem, 9 (9), 1574-1578, 2017. DOI: 10.1002/cctc.201601677

Abstract
Wood chips were hydrothermally treated in near critical point water in the presence of a catalyst to yield a raw biocrude, containing a wide range of organic components. This product was subsequently distilled to remove its heaviest fraction, which tends to yield chary products if heated above 350 8C. The biocrude obtained has an oxygen content of 12 wt% and was subsequently hydrotreated to obtain a hydrocarbon stream. Varying the hydrotreatment operating conditions and catalyst yielded a deoxygenated syncrude which quality improved with operation severity. The hydroprocessed stream produced under very mild conditions can be further upgraded in conventional refinery operations while the stream produced after more severe hydrotreatment can be mixed with conventional diesel. This proof of concept was demonstrated with commercial hydrotreating catalysts, operating between 350 and 380 8C, 40 to 120 bar pressure and 0.5 to 1 h-1 contact


Electron spin dynamics of two-dimensional layered materials

Dr Mohammad Choucair

Dr Mohammad Choucair

Posted 7 June 2017
Mohammad Choucair et al. Advanced Functional Materials, 27 (19), 1604040, 2017. DOI: 10.1002/adfm.201604040

Abstract
The growing library of two-dimensional layered materials is providing researchers with a wealth of opportunity to explore and tune physical phenomena at the nanoscale. Here, we review the experimental and theoretical state-of-art concerning the electron spin dynamics in graphene, silicene, phosphorene, transition metal dichalcogenides, covalent heterostructures of organic molecules and topological materials. The spin transport, chemical and defect induced magnetic moments, and the effect of spin-orbit coupling and spin relaxation, are also discussed in relation to the field of spintronics.


Opportunities in upgrading biomass crudes

Professor Thomas Maschmeyer

Prof Thomas Maschmeyer

Posted 1 June 2017
Thomas Maschmeyer et al. Faraday Discussions, 197, 389-401, 2017. DOI: 10.1039/c6fd00208k

Abstract
An unconventional crude from biomass (biocrude) has been processed to yield a hydrocarbon stream that is not only fully processable in conventional refineries but is already close to the specification of commercial fuels such as transportation diesel. The upgrading of biocrude was carried out with a combination of hydrotreatment and catalytic cracking, yielding middle distillate as the main product.


Methyl zealactonoate, a novel germination stimulant for root parasitic weeds produced by maize

Associate Professor Chris McErlean

A/Prof Chris McErlean

Posted 1 June 2017
Chris McErlean et al. Journal of Pesticide Science, 42 (2), 58-61, 2017. DOI: 10.1584/jpestics.D16-103

Abstract
One of the germination stimulants for root parasitic weeds produced by maize (Zea mays) was isolated and named methyl zealactonoate (1). Its structure was determined to be methyl (2E,3E)-4-((RS)-3,3-dimethyl-2-(3-methylbut-2-en-2-yl)-5-oxotetrahydrofuran-2-yl)-2-((((R)-4-methyl-5-oxo-2,5-dihydrofran-2-yl)oxy)methylene)but-3-enoate using by 1D and 2D NMR spectroscopy and ESI and EI–MS spectrometry. Feeding experiments with 13C-carlactone (CL), a biosynthetic intermediate for strigolactones, confirmed that 1 is produced from CL in maize. Methyl zealactonoate strongly elicits Striga hermonthica and Phelipanche ramosa seed germination, while Orobanche minor seeds are 100-fold less sensitive to this stimulant.


Molecular assemblies of metal complexes via base-pairing of nucleic acids in the crystalline state

Emertius Professor Len Lindoy

E/Prof Len Lindoy

Posted 1 June 2017
Len Lindoy et al. Chemistry: A European Journal, 23 (30), 7232-7237, 2017. DOI: 10.1002/chem.201700593

Abstract:
The nature of the molecular assemblies formed in the crystalline state by cobalt(II) terpyridine (terpy) complexes incorporating appended adenine (A) or thymine (T) bases was found to be controlled by which bases are present. Single-crystals of the cobalt(II) complexes [Co(A-C6-terpy)2](BF4)2 (1) and [Co(T-C6-terpy)2](BF4)2 (2) have needle and block habits, respectively. Subsequent mixing of 1 and 2 in MeOH resulted in isolation of [Co(A-C6-terpy)1.5(T-C6-terpy)0.5](BF4)2 (3) as plate-like crystals. A 3D network structure is present in 1 that incorporates 1D chains, whereas 2 adopts a 2D stacked structure constructed from ladder-type assemblies. For 3, “dimer-rings” consisting of [Co(A-C6-terpy)2]2+ and [Co(A-C6-terpy)(T-C6-terpy)]2+ units are generated by means of base-pairing between A and T. Notably, 3 displays the first crystal structure of a heteroleptic cobalt(II) complex of [Co(A-C6-terpy)(T-C6-terpy)](BF4)2. These assembly differences involving the terpyridine cobalt(II) complex units in 1-3 affect the cooperativities influencing their spin crossover (SCO) behavior. The influence of the terminal nucleobases on the resulting assembly has been probed by investigating the co-crystallization of [Co(terpy)2](BF4)2 (4) with [Co(C6-terpy)2](BF4)2 (5) and 1 with 5.


Porcelain shards from Portuguese wrecks: Raman spectroscopic analysis of marine archaeological ceramics

Dr Liz Carter

Dr Liz Carter

Posted 1 June 2017
Elizabeth Carter and Michelle Wood et al. Heritage Science, 5 (1), article 17, 2017. DOI: 10.1186/s40494-017-0130-9

Abstract:
Raman spectroscopic analysis of shards recovered from two Portuguese shipwrecks, the Santo Espirito (1608) and the Santa Maria Madre de Deus (1643), believed to be carrying porcelains of the Ming period have revealed some interesting and novel results that inform historical ideas of porcelain production. The porcelain body of two of the four shards from the Santa Maria Madre de Deus were found to contain anatase, a low temperature polymorph of titanium dioxide, and β-wollastonite a mineral characteristic of soft-paste porcelains that are made at medium-temperature firing conditions. Previously, β-wollastonite has been found in a range of sixteenth to nineteenth century European porcelains but this is the first report of its detection in porcelain believed to be from the Ming period. These same shards exhibited unusual spectral features that were attributed to the resonance enhancement of rare earth elements that resulted from excitation using a near-infrared source.


Unravelling some of the key transformations in the hydrothermal liquefaction of lignin

Professor Thomas Maschmeyer

Prof Thomas Maschmeyer

Posted 24 May 2017
Matthew Lui, Alexander Yuen, Anthony Masters and Thomas Maschmeyer* et al. ChemSusChem, 10 (10), 2140-2144, 2017. DOI: 10.1002/cssc.201700528

Abstract:
Using both experimental and computational methods, focusing on intermediates and model compounds, some of the main features of the reaction mechanisms that operate during the hydrothermal processing of lignin were elucidated. Key reaction pathways and their connection to different structural features of lignin were proposed. Under neutral conditions, subcritical water was demonstrated to act as a bifunctional acid/base catalyst for the dissection of lignin structures. In a complex web of mutually dependent interactions, guaiacyl units within lignin were shown to significantly affect overall lignin reactivity.


Synthesis of a GlcNAcylated arginine building block for the solid phase synthesis of death domain glycopeptide fragments

Professor Richard Payne

Prof Rich Payne

Posted 23 May 2017
Siyao Wang, Leo Corcilius and Richard Payne* et al. Bioorganic and Medicinal Chemistry, 25 (11), 2895-2900, 2017. DOI: 10.1016/j.bmc.2017.03.012

Abstract:
Herein we describe the synthesis of glycopeptide fragments from the death domains of TRADD and FADD bearing the recently discovered Nω-GlcNAc-β-arginine post-translational modification. TRADD and FADD glycopeptides were accessed through the use of a suitably protected synthetic glycosylamino acid ‘cassette’ that could be directly incorporated into conventional solid phase peptide synthesis (SPPS) protocols.


Infrared spectra of gas-phase 1- and 2-propenol isomers

Associate Professor Meredith Jordan

A/Prof Meredith Jordan

Posted 23 May 2017
Miranda Shaw and Meredith Jordan et al. The Journal of Physical Chemistry A, 121 (19), 3679-3688, 2017. DOI: 10.1021/acs.jpca.7b02323

Abstract:
Fourier transform infrared spectra of isolated 1-propenol and 2-propenol in the gas-phase have been collected in the range of 900–3800 cm–1, and the absolute infrared absorption cross sections reported for the first time. Both cis and trans isomers of 1-propenol were observed with the trans isomer in greater abundance. Syn and anti conformers of both 1- and 2-propenol were also observed, with abundance consistent with thermal population. The FTIR spectrum of the smaller ethenol (vinyl alcohol) was used as a benchmark for our computational results. As a consequence, its spectrum has been partially reassigned resulting in the first report of the anti-ethenol conformer. Electronic structure calculations were used to support our experimental results and assign vibrational modes for the most abundant isomers, syn-trans-1-propenol and syn-2-propenol.


Supramolecular architectures self-assembled using long chain alkylated spin crossover cobalt(II) compounds

Emertius Professor Len Lindoy

E/Prof Len Lindoy

Posted 23 May 2017
Len Lindoy et al. Chemical Communications, 53 (34), 4685-4687, 2017. DOI: 10.1039/c7cc01501a

Abstract:
Self-assembled hybrid supramolecular architectures formed between amphiphilic anions and long alkylated cationic cobalt(II) complexes of type [Co(Cn-terpy)2](C12-Glu)2 (n = 15-20) have been synthesized and characterized by TEM, PXRD and magnetic susceptibility measurements. The hybrids display wire or rolled sheet supramolecular arrangements with odd and even alkyl chain dependence, with the cobalt(II) centres exhibiting gradual spin-crossover behaviours.