Celebrating the 50th Anniversary of Professor Hermann Sleumer's Classic Treatment of the Ericaceae for Flora Malesiana

The major taxonomic changes that have been made within the Ericaceae since the publication of Professor Sleumer’s classic Flora Malesiana account are presented, as well as how these affect the Malesian region. Examples of Professor Sleumer’s acuity in taxonomic research are cited

Waiting for the Flowers

Since the Royal Botanic Garden Edinburgh (RBGE) was established in 1670 as a collection of medicinal plants, taxonomy has been at its heart. Even before the publication of Linnaeus’s Species Plantarum it was important to establish the correct identity of medicinal plants for use by the doctors of the day. Over the years the location and focus of the Garden have evolved to serve many and varied functions. Taxonomy, however, has continued to play a key role in preserving the special nature of RBGE as a ‘botanic garden’. From the earliest years exotic plants were introduced to the Garden, giving it an international flavour, and this has continued with staff today collaborating with many different gardens and botanical institutions around the world. For over 300 years living plants have been brought to the Garden, grown to maturity and described. Many of the early novelties came from North America and China, especially gymnosperms and rhododendrons. Today, much of our effort is focused on plants from areas that are botanically rich but poorly known, such as the Malesian region, and on families Begoniaceae, Gesneriaceae, Ericaceae and Zingiberaceae. The expertise and ingenuity of the horticultural staff have been essential in cultivating unknown species and bringing them into flower so that they can be scientifically described. This has been aided by an enlightened policy of including horticulturists on collecting expeditions so that their knowledge can be used to bring plants back in good health but also to better understand the natural conditions in which they grow so that the plants can be grown to perfection in Edinburgh

Nitrate Removal Performance of Denitrifying Woodchip Bioreactors in Tropical Climates

In Australia, declining water quality in the Great Barrier Reef (GBR) is a threat to its marine ecosystems and nitrate (NO3−) from sugar cane-dominated agricultural areas in the coastal catchments of North Queensland is a key pollutant of concern. Woodchip bioreactors have been identified as a potential low-cost remediation technology to reduce the NO3− runoff from sugar cane farms. This study aimed to trial different designs of bioreactors (denitrification walls and beds) to quantify their NO3− removal performance in the distinct tropical climates and hydrological regimes that characterize sugarcane farms in North Queensland. One denitrification wall and two denitrification beds were installed to treat groundwater and subsurface tile-drainage water in wet tropics catchments, where sugar cane farming relies only on rainfall for crop growth. Two denitrification beds were installed in the dry tropics to assess their performance in treating irrigation tailwater from sugarcane. All trialled bioreactors were effective at removing NO3−, with the beds exhibiting a higher NO3− removal rate (NRR, from 2.5 to 7.1 g N m−3 d−1) compared to the wall (0.15 g N m−3 d−1). The NRR depended on the influent NO3− concentration, as low influent concentrations triggered NO3− limitation. The highest NRR was observed in a bed installed in the dry tropics, with relatively high and consistent NO3− influent concentrations due to the use of groundwater, with elevated NO3−, for irrigation. This study demonstrates that bioreactors can be a useful edge-of-field technology for reducing NO3− in runoff to the GBR, when sited and designed to maximise NO3− removal performance

Sustainable sorbitol-derived compounds for gelation of the full range of ethanol–water mixtures

During the development of soft material systems inspired by green chemistry, we show that naturally occurring starting materials can be used to prepare mono- and di-benzylidene sorbitol derivatives. These compounds gelate a range of organic, aqueous (including with mono and divalent metal salt solutions) and ethanolic (ethanol–water) solutions, with the equimolar mixture of two of the gelators gelling all compositions from 100% ethanol to 100% water (something neither of the individual components do). We explored the influence of modifications to the acetal substituents on the formation of the compounds as well as the impact of steric bulk on self-assembly properties of the gelators. The effect of solvent on the self-assembly, morphology, and rheology of the 1,3:2,4-di(4-isopropylbenzylidene)-D-sorbitol (DBS-iPr), 2,4(4-isopropylbenzylidene)-D-sorbitol (MBS-iPr) and the equimolar multicomponent (DBS–MBS-iPr) gels have been investigated. DBS-iPr gelates polar solvents to form smooth flat fibres, whereas in non-polar solvents such as cyclohexane helical fibres grow where the chirality is determined by the stereochemistry of the sugar. Oscillatory rheology revealed that MBS-iPr gels have appreciable strength and elasticity, in comparison to DBS-iPr gels, regardless of the solvent medium employed. Powder X-ray diffraction was used to probe the arrangement of the gelators in the xerogels they form, and two single crystal X-ray structures of related MBS derivatives give the first precise structural information concerning layering and hydrogen bonding in the monobenzylidene compounds. This kind of layering could explain the apparent self-sorting behaviour of the DBS–MBS-iPr multicomponent gels. The combination of sorbitol-derived gelators reported in this work could find potential applications as multicomponent systems, for example, in soft materials for personal care products, polymer nucleation/clarification, and energy technology

Photophysics and electrochemistry of a platinum-acetylide disubstituted perylenediimide

The synthesis and photophysical study of a perylene diimide (PDI) functionalised with platinum acetylide units of the type, trans{–C[triple bond, length as m-dash]C–Pt(PBu3)2–C[triple bond, length as m-dash]C–Ph} and comparison with a phenylacetylide substituted model compound are reported. The model compound demonstrates typical perylene absorption and photoluminescence spectra characteristic of singlet excited state formation and decay. The Pt-substitution, however, appears to induce spin–orbit coupling into the chromophore and giving rise to a triplet excited state which was confirmed by transient absorption measurements. This excited state is quenched by oxygen, leading to the formation of singlet oxygen in dichloromethane, recorded by time-resolved near-infrared luminescence measurements

Selective photoinduced charge separation in perylenediimide-pillar[5]arene rotaxanes

The ability to control photoinduced charge transfer within molecules represents a major challenge requiring precise control of the relative positioning and orientation of donor and acceptor groups. Here we show that such photoinduced charge transfer processes within homo- and hetero-rotaxanes can be controlled through organisation of the components of the mechanically interlocked molecules, introducing alternative pathways for electron donation. Specifically, studies of two rotaxanes are described: a homo[3]rotaxane, built from a perylenediimide diimidazolium rod that threads two pillar[5]arene macrocycles, and a hetero[4]rotaxane in which an additional bis(1,5-naphtho)-38-crown-10 (BN38C10) macrocycle encircles the central perylenediimide. The two rotaxanes are characterised by a combination of techniques including electron diffraction crystallography in the case of the hetero[4]rotaxane. Cyclic voltammetry, spectroelectrochemistry, and EPR spectroscopy areemployed to establish the behaviour of the redox states of both rotaxanes and these data are used to inform photophysical studies using time-resolved infra-red (TRIR) and transient absorption (TA) spectroscopies. The latter studies illustrate the formation of a symmetrybreaking charge-separated state in the case of the homo[3]rotaxane in which charge transfer between the pillar[5]arene and perylenediimide is observed involving only one of the twomacrocyclic components. In the case of the hetero[4]rotaxane charge separation is observed involving only the BN38C10 macrocycle and the perylenediimide leaving the pillar[5]arene components unperturbed

Nickel(II) and iron(II) triple helicates assembled from expanded quaterpyridines incorporating flexible linkages

In the present study the interaction of Fe(II) and Ni(II) with the related expanded quaterpyridines, 1,2-, 1,3- and 1,4-bis-(5'-methyl-[2,2']bipyridinyl-5-ylmethoxy)benzene ligands (4–6 respectively), incorporating flexible, bis-aryl/methylene ether linkages in the bridges between the dipyridyl domains, was shown to predominantly result in the assembly of [M2L3]4+ complexes; although with 4 and 6 there was also evidence for the (minor) formation of the corresponding [M4L6]8+ species. Overall, this result contrasts with the behaviour of the essentially rigid 'parent' quaterpyridine 1 for which only tetrahedral [M4L6]8+ cage species were observed when reacted with various Fe(II) salts. It also contrasts with that observed for 2 and 3 incorporating essentially rigid substituted phenylene and biphenylene bridges between the dipyridyl domains where reaction with Fe(II) and Ni(II) yielded both [M2L3]4+ and [M4L6]8+ complex types, but in this case it was the latter species that was assigned as the thermodynamically favoured product type. The X-ray structures of the triple helicate complexes [H2O⊂Ni2(4)3](PF6)4·THF·.2H2O, [Ni2(6)3](PF6)4·195MeCN·1.THF·1.82O, and the very unusual triple helicate PF6− inclusion complex, [(PF6)⊂Ni2(5)3](PF6)3·1.75eCN·5.25TF·0.25H2O are reported

Host–guest selectivity in a series of isoreticular metal–organic frameworks: observation of acetylene-to-alkyne and carbon dioxide-to-amide interactions

In order to develop new porous materials for applications in gas separations such as natural gas upgrading, landfill gas processing and acetylene purification it is vital to gain understanding of host-substrate interactions at a molecular level. Herein we report a series of six isoreticular metal-organic frameworks (MOFs) for selective gas adsorption. These materials do not incorporate open metal sites and thus provide an excellent platform to investigate the effect of the incorporation of ligand functionality via amide and alkyne groups on substrate binding. By reducing the linker length of our previously reported MFM-136, we report much improved CO2/CH4 (50:50) and CO2/N2 (15:85) selectivity values of 20.2 and 65.4, respectively (1 bar and 273 K), in the new amide-decorated MOF, MFM-126. The CO2 separation performance of MFM-126 has been confirmed by dynamic breakthrough experiments. In situ inelastic neutron scattering and synchrotron FT-IR microspectroscopy were employed to elucidate dynamic interactions of adsorbed CO2 molecules within MFM-126. Upon changing the functionality to an alkyne group in MFM-127, the CO2 uptake decreases but the C2H2 uptake increases by 68%, leading to excellent C2H2/CO2 and C2H2/CH4 selectivities of 3.7 and 21.2, respectively. Neutron powder diffraction enabled the direct observation of the preferred binding domains in MFM-126 and MFM-127, and, to the best of our knowledge, we report the first example of acetylene binding to an alkyne moiety in a porous material, with over 50% of the acetylene observed within MFM-127 displaying interactions (less than 4 Å) with the alkyne functionality of the framework