Thermal Rearrangement Research Articles

Thermally rearranged OH-containing polyimide composite membranes with enhanced gas separation performance and physical aging resistance

Gas separation membranes play a pivotal role in various industrial processes, demanding continuous improvement in their efficiency and durability. This study focuses on thin-film composite (TFC) membranes based on polyimide, utilizing a hydroxyl-containing polyimide selective layer for its processability and selectivity. A complete and smooth surface for the selective layer in the composite membranes was achieved by exclusively selecting a 10% concentration of the polyimide spin-coating solution. Subsequent thermal rearrangement at 430°C induced the formation of a rigid polybenzoxazole structure, enhancing gas permeance. Optimal separation performance was achieved through a two-hour rearrangement, resulting in a more than 30-fold increase in gas permeance while preserving selectivity. The study also delved into anti-physical aging performance. The thermally treated PI-10 wt%−2 h membrane exhibited a 10% reduction in CO2 and O2 permeance over 90 days, with O2/N2 and CO2/N2 selectivities nearly maintaining their initial levels. This research provides valuable insights for the development of efficient and durable gas separation membranes.

Analysis of root volatiles and functional characterization of a root-specific germacrene A synthase in Artemisia pallens.

The study demonstrated that Artemisia pallens roots can be a source of terpene-rich essential oil and root-specific ApTPS1 forms germacrene A contributing to major root volatiles. Davana (Artemisia pallens Bess) is a valuable aromatic herb within the Asteraceae family, highly prized for its essential oil (EO) produced in the aerial parts. However, the root volatile composition, and thegenes responsible for root volatiles have remained unexplored until now. Here, we show that A. pallens roots possess distinct oil bodies and yields ~ 0.05% of EO, which is primarily composed of sesquiterpenes β-elemene, neryl isovalerate, β-selinene, and α-selinene, and trace amounts of monoterpenes β-myrcene, D-limonene. This shows that, besides aerial parts, roots of davana can also be a source of unique EO. Moreover, we functionally characterized a terpene synthase (ApTPS1) that exhibited high in silico expression in the root transcriptome. The recombinant ApTPS1 showed the formation of β-elemene and germacrene A with E,E-farnesyl diphosphate (FPP) as a substrate. Detailed analysis of assay products revealed that β-elemene was the thermal rearrangement product of germacrene A. The functional expression of ApTPS1 in Saccharomyces cerevisiae confirmed the in vivo germacrene A synthase activity of ApTPS1. At the transcript level, ApTPS1 displayed predominant expression in roots, with significantly lower level of expression in other tissues. This expression pattern of ApTPS1 positively correlated with the tissue-specific accumulation level of germacrene A. Overall, these findings provide fundamental insights into the EO profile of davana roots, and the contribution of ApTPS1 in the formation of a major root volatile.

Theoretical mechanistic insights on the thermal and acid-catalyzed rearrangements of N-methyl-N-nitroanilines.

The thermal and acid-catalyzed rearrangement mechanisms of N-methyl-N-nitroanilines were theoretically investigated via density functional theory (DFT) calculations for all possible proposed mechanisms. The results indicate that the thermal rearrangement of N-methyl-N-nitroanilines undergoes a radical pair complex mechanism through the homolysis of their N-N bond to generate a radical pair complex and the recombination of the radical pairs followed by aromatization. For the acid-catalyzed rearrangements, N-methyl-N-nitroanilines are first protonated on the nitrogen atom of their aniline moiety and then generate protonated N-methyl-O-nitroso-N-phenylhydroxylamines through a three-membered spirocyclic oxadiaziridine transition state. The N-protonated N-methyl-O-nitroso-N-phenylhydroxylamines favor homolytic dissociation to generate N-methylaniline cationic radical and nitrogen dioxide complexes, which further combine together and aromatize to afford protonated N-methyl-o-nitroanilines and N-methyl-p-nitroanilines, respectively. The radical pair complexes are more stable than the corresponding solvent-caged radical pairs. The thermal rearrangements require higher activation energy than the corresponding acid-catalyzed rearrangements.

Preparation of fluorinated poly(benzoxazole-co-imide) with low dielectric constants based on the thermal rearrangement reaction of o-hydroxy polyimides

This paper proposes a new strategy to prepare PIs with excellent overall performance by combining various modifications such as triphenyl pyridine structure, long-chain anhydride, trifluoromethyl, and thermal rearrangement reaction.

Metal ion-driven formation of 2H-silolides and -germolides.

The synthesis of potassio-1H-silolides and -germolides substituted with an amidinate-stabilized silylene is reported. Both anions undergo a thermal rearrangement to the 2H-isomer yielding cyclic sila- and germavinyl anions. The reaction is driven by complex formation with metal ions.

Formation of (Aza)fulvenallene, Cyanocyclopentadiene, and (Aza)fluorenes in the Thermal Rearrangements of Indazoles, Azaindazoles, and Homoquinolinic Anhydride.

Flash vacuum pyrolysis (FVP) of pyrazoles and indazoles constitutes a valuable route to carbenes and nitrenes. In this study, we employed M062X and CCSD(T) calculations to provide a mechanistic rationale for the formation of fulvenallene and fluorenes from indazoles and the corresponding formation of azafulvenallene 15, cyanocyclopentadiene 19, and azafluorenes, e.g. 45, from azaindazoles, e.g. 12, and from homoquinolinic anhydride. The results reveal the importance of initial tautomerization in the pyrazole moiety of 7-azaindazole 12, which drives the mechanism toward 2-diazo-3-methylene-2,3-dihydropyridine 29 and hence 3-methylene-2,3-dihydropyridin-2-ylidene 26, followed by Wolff-type ring contraction to 1-azafulvenallene 15. This path has a calculated activation energy ∼10 kcal/mol lower than that for an alternate route involving ring opening to 3-diazomethylpyridine, dediazotization, and rearrangement of 3-pyridylcarbene to azacycloheptatetraene and phenylnitrene 24. FVP of 2,5-diphenyltetrazoles and phenyl(pyridyl)tetrazoles leads to nitrile imines, which cyclize to 3-phenylindazoles and -azaindazoles. Nitrogen elimination from these (aza) indazoles results in the formation of (aza) fluorenes, for which two alternate mechanisms are described: route A by rearrangement of (aza) indazoles to diazo(aza)cyclohexadienes and (aza)cyclohexadienylidenes and route B by rearrangement to diaryldiazomethanes and diarylcarbenes. Both paths are energetically feasible, but path A is preferred and corresponds to the azafluorenes obtained experimentally.

Isolation of (Aryl)-(Imino) Phosphide and (Aryl)-(Phosphaalkene) Amide Complexes of Alkali Metals from Carbene-Phosphinidenes under Reductive-Thermal Rearrangements.

Two-electron reduction of cyclic alkyl(amino) carbene (cAAC)-supported chloro-phosphinidene cAAC=P-Cl (1) followed by unprecedented thermal rearrangements afforded the alkali metal complexes of (aryl)-(cyclic alkyl(imino)) phosphides 3 a-3 c, 4 a-4 b through migration of the 2,6-diisopropylphenyl (dipp) group from N to the P centre, and the (aryl)-(cyclic alkyl(phosphaalkene)) amide 5 through cleavage of the CMe2 -N bond followed by energetically favoured 5-exo-tet ring-closure in the presence of the alkali metals Cs (3 a-3 c), K (4 a, 4 b), and Li (5). Compound 3 a was found to be photoluminescent (PL), emitting bright orange light under a laboratory UV lamp of wavelength 365 nm with PL quantum yield (ϕPL ) of 2.6 % (λem =600 nm), and an average lifetime (τ) of 4.8 μs. Reaction of 3 a with CuCl and AgOTf afforded (aryl)-(cyclic alkyl(imino)) phosphide-stabilized tetra-nuclear CuI (6), and octa-nuclear AgI (7) clusters, respectively. Moreover, complexes 3 a-3 c provided a direct route for the stabilization of cyclic alkyl(aminoboryl) phosphaalkenes 8 a-8 c when treated with 1-bromo-N,N,N',N'-tetraisopropylboranediamine.

Thermo-mechanical behaviour of microbial induced carbonate precipita-tion (MICP) sand for geothermal pavements

Introduction
 Ground source heat pump (GSHP) or shallow geothermal energy systems are gaining attention for helping combat global warming and the negative effects of urbanisation caused by human activities. In recent decades, energy geo-structure techniques have developed by using subsurface infrastructures to exchange heat with the ground. These techniques can provide space heating and cooling while still preserving the primary structural function. As a result, they have become a valuable part of geothermal energy systems. Researchers have developed an understanding of incorporating ground heat exchangers into foundation piles, retaining walls, and tunnel linings with modest additional cost [1-4]. Pavements are also structures in contact with the ground that have the potential to be used as energy geo-structures (i.e., geothermal pavements), yet, their use has not been extensively studied [5-8].
 Soil thermal conductivity is an important factor influencing the efficiency of geothermal pavements since heat transfer in soils occurs primarily by conduction [9]. Microbially induced calcium carbonate (CaCO3) precipitation (MICP) is an innovative technique for strengthening sandy soils by coating and binding soil grains with calcium carbonate crystals. The distribution and arrangement of the CaCO3 within the pore spaces play a crucial role in determining the resulting strength of the treated sand. In addition, these crystals can act as thermal bridges to enhance the soil's thermal conductivity [10]. Combining geothermal pavements with MICP sand is still nascent, and the limited number of studies that exist mainly focus on the associated thermal property changes [11]. However, since the principal function of pavements is transmitting (dynamic) loads to the subbase and the underlying soil, the thermal conductivity of the MICP-treated pavement may vary as a result of the applied mechanical loads (e.g., due to the partial or total loss of thermal bridges and/or particle rearrangement). This research thus investigates the changes in the thermal conductivity of MICP-treated sands as they are subjected to quasi-static triaxial compression. The experimental results collected can deepen our understanding of the thermo-mechanical behaviour of MICP-treated sands and provide practical insights for using MICP to reinforce the subbase or underlying soil of geothermal pavements.
 Methodology
 This research performed a series of quasi-static triaxial tests on MICP-treated Houston sand, fine-grained, high-purity silica sand. Sporosarcina pasteurii (strain designation DSM 33) was used for the MICP treatment of the soil specimen. To study the effect of CaCO3 content on the thermo-mechanical performance of MICP-treated sand, three cementation solution treatment cycles were applied, yielding theoretical CaCO3 contents of 0.6%, 1.6% and 2.7% by weight, respectively. Details on the MICP treatment of the samples can be found in [12]. Samples for triaxial testing were treated in cylindrical tubes of 50mm inner diameter and 100mm height. To investigate the influence of the CaCO3 content on the soil thermal conductivity, MICP-treated specimens were air-dried prior to triaxial testing Triaxial tests were subsequently conducted in dry conditions to isolate the effect of the MICP and avoid the influence of water content on soil thermal conductivity (λ). Furthermore, a new miniaturised transient sensor was embedded in the triaxial samples to monitor the λ changes during the sharing phase [12].
 Results
 An example of the evolution of the deviatoric stress with axial strain under 50kPa confining stress (σ3) in the triaxial cell is shown in Figure 1a. Compared to the untreated sand, MICP-treated samples lead to higher peak strength and stiffness. Importantly, λ changes during triaxial testing for different CaCO3 contents are summarised in Figure 1b. Results indicate that the increase in CaCO3 content can significantly improve λ, and that λ rapidly decreases post-peak strength due to dilation and CaCO3 bond breakage. Once the samples reach its ultimate state, λ remains unchanged.

Fabrication of high-performance poly(benzoxazole-co-imide) membrane by utilizing synergistic effect of thermal rearrangement and Zn2+ modification

Developing membranes that combine excellent gas separation performance with robust resistance to plasticization is highly demanded for membrane separation but remains a challenge. Herein, a series of Zn2+ functionalized poly(benzoxazole-co-imide) membrane was constructed via co-polymerizing (4,4′-hexafluoroisopropylidene) diphthalic anhydride (6FDA) with o-hydroxyl diamine 2,2′-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (BisAPAF) and 1,3,5-tris(4-aminophenyl)benzene (TAPB) followed by thermal rearrangement (TR) and Zn2+ modification processes. The TR conversion opened the polymer chains with larger d-spacing and higher BET surface area, thus, greatly increased the gas permeability. Meanwhile, the post Zn2+ modification resulted in a huge improved selectivity because of the π-complexation reactions between Zn2+ and CO2 and the formation of a Zn2+ coordination crosslinking network. As a result, due to the synergistic effect of TR and Zn2+ modification, the overall gas transport properties of these newly developed membranes were greatly improved. Furthermore, the dual network structures that arise from the remaining network PI and the Zn2+ coordination crosslinking contribute to the resultant membrane with excellent anti-plasticization capability. A represent membrane termed as PBOI-Zn2+-14h membrane exhibits great CO2/CH4 separation performance, delivering a CO2 permeability of 1048.1 Barrer and a CO2/CH4 selectivity of 46.1 that is exceeded the 2008 Roberson limitation. Furthermore, this membrane possesses remarkable resistance to CO2-induced plasticization, withstanding pressures above 35 Bar. Overall, this study presents an effective way for constructing polymer membranes with both high gas separation performance and strong resistance to plasticization issue.

Computational Exploration of the Thermal Rearrangement of Basketene: One Forbidden versus Two Allowed Pericyclic Reactions.

The thermal rearrangement of basketene to Nenitzescu's hydrocarbon has been explored using density functional theory (M06-2X and ωB97X-D) and DLPNO-CCSD(T) quantum mechanics. Both the sequential thermally allowed retro Diels-Alder followed by Cope rearrangement and the thermally forbidden retro-[2 + 2] cycloaddition were studied. The controlling role of orbital symmetry rather than reaction thermodynamics is demonstrated.

Benzimidazole-diamide (bida) Pincer Chromium Complexes: Structures and Reactivity.

Serendipitous discovery of bida (i.e., N1-Ar-N2-((1-Ar-1-benzo[d]imidazol-2-yl)methyl)benzene-1,2-diamide; Ar = 2,6-iPr-C6H3), a potentially redox noninnocent, hemilabile pincer ligand with a methylene group that may facilitate proton/H atom reactivity, prompted its investigation. Chromium was chosen for study due to its multiple stable oxidation states. Disodium salt (bida)Na2(THF)n was prepared by thermal rearrangement of (dadi)Na2(THF)4 (i.e., (N,N'-di-2-(2,6-diisopropylphenylamine)phenylglyoxaldiimine)-Na2(THF)4). Salt metathesis of (bida)Na2(THF)n (generated in situ) with CrCl3(THF)3 or Cl3V═NAr (Ar = 2,6-iPr2C6H3) afforded (bida)CrCl(THF) (1-THF) and (bida)ClV═NAr, respectively. Substitutions provided (bida)CrCl(PMe2Ph) (1-PMe2Ph) and (bida)CrR(THF) (2-R, where R = Me, CH2CMe2Ph (Nph)). Oxidation of 1-THF with ArN3 (Ar = 2,6-iPr2C6H3) or AdN3 (Ad = 1-adamantyl) generated (bida)ClCr═NAr (3═NAr) and (bida)ClCr═NAd (3═NAd) and subsequent alkylation converted these to (bida)R'Cr═NR (R' = Me, R = Ad, Ar, 5═NR; R' = CH2CMe2Ph (Nph), R = Ad, Ar, 6═NR). In contrast, the addition of AdN3 to 2-Nph gave the insertion product (bida)Cr(κ2-N,N-ArN3Nph) (7). Addition of N-chlorosuccinimide to 1-THF produced (bia)CrCl2(THF) (8), where bia is the pincer derived via hydrogen atom loss from bida methylene. A similar HAT afforded (bia)ClCr(CNAr')2 (9, Ar' = 2,6-Me2C6H3) when 3═NAd was exposed to Ar'NC. An empirical equation of charge was applied to each bida species, whose metric parameters are unchanging despite formal oxidation state conversions from Cr(III) to Cr(V). Calculations and Mulliken spin density assessments reveal several situations in which antiferromagnetic (AF) coupling and admixtures of integer ground states (GSs) describe a complicated electronic structure.

Development of a Continuous Flow Baldwin Rearrangement Process and Its Comparison to Traditional Batch Mode.

A new and highly efficient continuous flow process is presented for the synthesis of aziridines via the thermal Baldwin rearrangement. The process was initially explored using traditional batch synthesis techniques but suffered from moderate yields, long reaction times, and moderate diastereoselectivities. Here we demonstrate that the process can be greatly improved upon its transfer to continuous flow, which afforded the aziridine targets in high yields, short reaction times, and consistently high diastereoselectivities, with the high-throughput process rendering multigram quantities of product in short periods of time. In addition, flow processing extended the substrate scope including several examples that had failed in batch mode, thus demonstrating the value of this overlooked entry into valuable aziridine species.

Effect of pendant ester groups on gas transport property of 6FDA-BAPP/6FAP copolyimide membrane

Despite the various methods that have been developed, controlling the microstructure of polyimide membranes to achieve excellent separation performance based on target gases remains a challenge. One such method involves rearranging polyimides containing ortho-hydroxyl groups into polybenzoxazoles at temperatures above 400 °C, which can effectively distort the backbones and improve gas diffusion. However, this approach is limited by the extremely high conversion temperatures required and low conversion degrees achieved. The esterification process of the polyimide, which contains ortho-hydroxyl groups to the imide ring, represents a simple and effective approach to enhance the membrane's competitiveness in gas separation without undergoing thermal rearrangement at high temperatures. The polyimide was prepared by the polycondensation of 4,4'-(Hexafluoro isopropylidene) diphthalic anhydride (6FDA), 2,2-double (4,4-amino phenoxy) propane (BAPP), and 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (6FAP). Microstructures and gas transport coefficients were analyzed when the esterification of 6FDA-BAPP/6FAP was conducted using acetic anhydride and caproic anhydride. In CO2/N2 separation, a-6FDA-BAPP/6FAP exhibits CO2 permeability of 1279.41 ± 66.93 Barrer and perm-selectivity of 40.80 ± 2.27, owing to the significantly improved affinity to CO2. The membrane of c-6FDA-BAPP/6FAP exhibit the further improved CO2 permeability and deteriorated perm-selectivity, due to a leveling effect on the diffusion of CO2 and N2 caused by the pendant caproates with longer alkyl chains. The results confirmed that the gas separation performance of polyimide membrane containing ortho-hydroxyl groups is sensitive to the pendant group.

Gas adsorption isotherm, pore size distribution, and free volume fraction of polymer-polymer mixed matrix membranes before and after thermal rearrangement

In this work, CO2 adsorption at 273.15 K and N2 adsorption at 77 K of mixed matrix membranes has been studied, as a method to directly determine their fractional free volume (FFV). These membranes consist of a continuous phase of copoly(o-hydroxyamide)s (HPA) or copoly(o-hydroxyamide-amide)s (PAA) and a relatively highly porous polymer network filler (PPN1). Both the pure copolymers and the mixed matrix membranes (MMMs) have been analyzed before and after a thermal rearrangement (TR) process.The CO2 adsorption results have allowed characterizing the pore size distribution of the studied membranes in the 3–15 Å range, by using the Non-Local Density Functional Theory (NLDFT). Whereas the N2 adsorption has allowed determining the pore size distributions in the range between 20 and 250 Å.The experimental determination of the pore volume and the density allows the direct calculation of the membranes’ free volume fractions, which were in good agreement with the most usual FFV evaluation methods. In addition, part of the pore volume detected by N2 adsorption was associated with defects and poor integration of the membrane components. This correction has allowed us to make a new evaluation of the density of these materials.

Exploring inverse vulcanisation mechanisms from the perspective of dark sulfur

The build-up of elemental sulfur waste poses problems such that only the advancement of process and product design might act as a solution. Inverse vulcanisation, a process for the generation of high sulfur content polymeric materials may be one such resolution. However, a complete understanding of how these materials form is yet to be fully agreed in this emerging field. Herein is an investigation into the understanding of ‘dark sulfur’ – amorphous, unreacted sulfur, not incorporated into the polymer backbone – in an attempt to understand further the formation mechanisms behind inverse vulcanisation. This research posits theories regarding polymer formation, thermal rearrangement, and the actions of OH to control the degree of product crosslinking, in relation to the quantity of sulfur unreacted into the polymer structure. The detriments and benefits of this dark sulfur in relation to application and general usage are also investigated, showing that a high content of dark sulfur may encourage planktonic bactericidal activity, while also promoting safety considerations from generated species such as hydrogen sulfide and carbon disulfide, concluded as components of this dark sulfur.

Do Phenyl Substituents Affect the Properties of Azobenzocrown Derivatives?

New products of photo- and thermal rearrangements of 19-membered azoxybenzocrown with phenyl substituents in benzene rings in the para positions to oligooxyethylene fragments are characterized. The yields of photochemical transformations depend on the solvent. Para-hydroxyazocrown is formed with yields over 50% in propan-2-ol. Ortho-hydroxyazobenzocrown is obtained with yields up to 70% in toluene/acetic acid mixture. Macrocyclic Ph-20-ester is obtained in yield 90% under thermochemical rearrangement conditions. Structure of new hydroxyazobenzocrowns and also atypical product of rearrangements, 20-membered ester, was confirmed by X-ray diffraction analysis. Azophenol⇄quinone-hydrazone tautomeric equilibrium of new hydroxyazobenzocrowns and the influence of metal cations on tautomeric equilibrium was investigated using 1H NMR and UV-Vis spectroscopy in acetonitrile. The highest value of stability constant (logK 7.25) was obtained for strontium complex of p-hydroxyazobenzocrown. For the first time p-hydroxyazobenzocrown was used as a chromoionophore in the receptor layer of an optical sensor. Comparative analysis with data obtained previously for series 19-membered analogs have shown the influence of the presence of substituents in benzene rings for the course and products distribution of photo- and thermal rearrangement. The effect of substituents was also discussed against the tautomeric equilibrium and metal cation complexation properties.

Synthesis of 2-Pyrones from Renewable Resources

AbstractAn atom-economic reaction sequence on a multigram scale for synthesizing 2-pyrone was developed starting from furfuryl alcohol, a renewable resource made from bran or bagasse, utilizing a large-scale thermal rearrangement of cyclopentadienone epoxide as the key step. Additionally, 6-substituted 2-pyrone natural product derivatives are readily accessible by this approach.

Structural evolution and gas separation properties of thermally rearranged polybenzoxazole (TR-PBO), polymer-carbon transition (PCT) and early-stage carbon (ESC) membranes derived from a 6FDA-hydroxyl-functionalized Tröger's base polyimide

The changes in physical, chemical, and gas permeation properties of a heat-treated hydroxyl-functionalized Tröger's base-derived intrinsically microporous polyimide, 6FDA-HTB, were systematically studied. Polyimide samples were heat-treated for 30 min at a fixed temperature to form (i) polybenzoxazole (PBO) by thermal rearrangement (TR) from ∼420 to ∼440 °C, (ii) polymer-carbon transition (PCT) from ∼460 to ∼500 °C, and (iii) early-stage carbon (ESC) membranes from >500 to 600 °C. As frequently observed in previous studies, TR-derived PBO membranes showed an increase in gas permeability with a concomitant decrease in gas-pair selectivity. The intermediate PCT region represents a transition state from a PBO to a partially carbonized polymer with superior properties by showing a simultaneous boost in gas permeability and gas-pair selectivity. The ESC membranes formed between 550 and 600 °C possessed further enhanced selectivity due to tightening of the amorphous CMS structure. A 135-day aged 6FDA-HTB-600 membrane showed very high hydrogen permeability of 3544 barrer coupled with an outstanding H2/CH4 selectivity of 939. The mixed-gas separation properties of selected aged samples, pristine 6FDA-HTB, PBO (6FDA-HTB-420), intermediate PCT (6FDA-HTB-480), and early stage CMS analogs (6FDA-HTB-550 and 600), were investigated using a 1:1 CO2/CH4 feed up to 30 bar. In this series, early-stage CMS membranes displayed the best mixed-gas CO2/CH4 separation properties with performance significantly surpassing the 2018 polymer mixed-gas upper bound.

The organic geochemistry of Permian high latitude sediments in two boreholes in the southern Sydney Basin, New South Wales, Australia

Twenty six samples of Permian high latitude sedimentary rocks from the southern Sydney Basin were analysed using organic geochemical methods for their thermal maturity, organic matter inputs, and depositional environment. Fourteen samples are from the Elecom Clyde River (ECR) DDH01 borehole (inland; Southern Highlands), and 12 are from the ECR-DDH07 borehole (coastal; near Nowra). The analysed formations are the Berry Siltstone, the Nowra Sandstone, the Wandrawandian Siltstone, the Snapper Point Formation and the Pebbley Beach Formation. This study is the first organic geochemical study of samples from the Berry Siltstone and Nowra Sandstone. The formations mostly have total organic carbon varying from 1 to 2 wt%, but the Snapper Point Formation is leaner in TOC (0.2–0.7 wt%). The samples vary from low to very high thermal maturity. The samples from the ECR-DDH01 borehole are in the early to middle of the oil window (vitrinite reflectance equivalent = 0.60–0.80%), based on hopane, sterane, alkylnaphthalene, alkylphenanthrene, alkylbiphenyl, and alkyldibenzothiophene thermal maturity parameters. The samples from the ECR-DDH07 borehole are much more thermally mature, in the late part of the oil window to the early gas window (vitrinite reflectance equivalent = 1.2–1.7%). This high thermal maturity has led to the loss of nearly all polycyclic biomarkers, and the thermal rearrangement of many groups of compounds, including monomethylalkanes. The ECR-DDH01 borehole location and time-equivalent outcrop samples south-west of Ulladulla have similar thermal maturities and are close to the margins of the Sydney Basin, and it is estimated to have previously been covered by about 3 km of overburden. In contrast, the samples in the ECR-DDH07 borehole were buried much deeper, with about 4–5 km of overburden, which means that only limited information about their source inputs and depositional environment could be recovered. Aliphatic biomarker, n-alkane and aromatic data are consistent with an overall strong terrigenous organic matter input for the samples from the ECR-DDH01 borehole. Sterane/hopane ratios are mostly low, but only a few compounds diagnostic of specific source inputs were identified. There is a microbially-dominated sample near the base of the Snapper Point Formation (high C29 αβ hopane/C30 αβ hopane ratio and 2α-methylhopanes), and high amounts of parent polycyclic aromatic hydrocarbons in some samples from the Berry Siltstone, likely reflecting an occasional pyrogenic signature from palaeo-forest fires. Several parameters, including sterane carbon number distributions, terpane ratios and the relative abundance of dibenzofuran compared to phenanthrene show that the samples from the ECR-DDH01 borehole have a more strongly terrigenous signal than the previously analysed outcrop samples. This is inferred to be because the ECR-DDH01 location was closer to the palaeo-shoreline than the likely more distal outcrop samples. Based on the pristane/phytane ratio and hopane distributions, deposition of the sediments was under varying oxicity conditions, from highly oxic to suboxic. The inferred environments are marine shale/lacustrine and fluvial/deltaic, so the organic geochemical data agrees with the Permian depositional history of the southmost part of the Sydney Basin previously inferred from sedimentological and palaeogeographic studies.

Unexpected permeability enhancement of thermally rearranged (TR) copolybenzoxazole membranes

Gas transport properties of novel thermally rearranged copolybenzoxazole (TR-coPBO) membranes with various copolymerization ratios were investigated. The TR-coPBO membranes were obtained by thermal rearrangement of corresponding copoly(o-hydroxy imide)s with fluorene ring moiety via several rearranged temperatures. The TR-coPBO membranes had larger d-spacing values than corresponding neat TR-PBO membranes without copolymerization and larger specific volumes than those expected from an additive rule, suggesting excessively increased fractional free volumes. Permeability coefficients of the TR-coPBO membranes possessed positive deviations from the values expected by a semilogarithmic additive rule against the copolymerization ratio. The enhanced permeability might be brought by steric repulsion and suppressed molecular chain packing due to the partial introduction of fluorene ring moiety.