The genus Ecphora of Muricid gastropods from the mid-Miocene Calvert Cliffs, Maryland is characterised by distinct reddish-brown colouration that results from shell-binding proteins associated with pigments within the outer calcite (CaCO3) portion of the shell. The mineral composition and robustness of the shell structure make Ecphora unique among the Neogene gastropods. Acid-dissolved shells produce a polymeric sheet-like organic residue of the same colour as the initial shell. NMR analysis indicates the presence of peptide bonds, while hydrolysis of the polymeric material yields 11 different amino acid residues, including aspartate and glutamate, which are typical of shell-binding proteins. Carbon and nitrogen elemental and isotopic analyses of the organic residue reveals that total organic carbon ranges from 4 to 40 weight %, with 11 < C/Nat < 18. Isotope values for carbon (-17 < delta C < - 15%) are consistent with a shallow marine environment, while values for nitrogen (4 < delta N < 12.2%) point to Ecphora's position in the trophic structure with higher values indicating predator status. The preservation of the pigmentation and shell-binding proteinaceous material presents a unique opportunity to study the ecology of this important and iconic Chesapeake Bay organism from 8 to 18 million years ago.

The genus Ecphora of Muricid gastropods from the mid-Miocene Calvert Cliffs, Maryland is characterised by distinct reddish-brown colouration that results from shell-binding proteins associated with pigments within the outer calcite (CaCO3) portion of the shell. The mineral composition and robustness of the shell structure make Ecphora unique among the Neogene gastropods. Acid-dissolved shells produce a polymeric sheet-like organic residue of the same colour as the initial shell. NMR analysis indicates the presence of peptide bonds, while hydrolysis of the polymeric material yields 11 different amino acid residues, including aspartate and glutamate, which are typical of shell-binding proteins. Carbon and nitrogen elemental and isotopic analyses of the organic residue reveals that total organic carbon ranges from 4 to 40 weight %, with 11 < C/Nat < 18. Isotope values for carbon (-17 < delta C < - 15%) are consistent with a shallow marine environment, while values for nitrogen (4 < delta N < 12.2%) point to Ecphora's position in the trophic structure with higher values indicating predator status. The preservation of the pigmentation and shell-binding proteinaceous material presents a unique opportunity to study the ecology of this important and iconic Chesapeake Bay organism from 8 to 18 million years ago.

Aqueous organic solid formation from formaldehyde via the formose reaction and subsequent reactions is a possible candidate for the origin of complex primitive chondritic insoluble organic matter (IOM) and refractory carbon in comets. The rate of formation of organic solids from formaldehyde was studied as a function of temperature and time, with and without ammonia, in order to derive kinetic expressions for polymer yield. The evolution in molecular structure as a function of time and temperature was studied using infrared spectroscopy. Using these kinetic expressions, the yield of organic solids is estimated for extended time and temperature ranges. For example, the half-life for organic solid formation is similar to 5 days at 373 K, similar to 200 days at 323 K, and similar to 70 years at 273 K with ammonia, and similar to 25 days at 373 K, similar to 13 years at 323 K, and similar to 2 x 10(4) years at 273 K without ammonia. These results indicate that organic solids could form during the aqueous alteration in meteorite parent bodies. If liquid water existed early in the interiors of Kuiper belt objects (KBOs), formaldehyde could convert into organic solids at temperatures close to 273 K, and possibly even below 273 K in the ammonia-water system. (C) 2014 Elsevier Inc. All rights reserved.

Aqueous organic solid formation from formaldehyde via the formose reaction and subsequent reactions is a possible candidate for the origin of complex primitive chondritic insoluble organic matter (IOM) and refractory carbon in comets. The rate of formation of organic solids from formaldehyde was studied as a function of temperature and time, with and without ammonia, in order to derive kinetic expressions for polymer yield. The evolution in molecular structure as a function of time and temperature was studied using infrared spectroscopy. Using these kinetic expressions, the yield of organic solids is estimated for extended time and temperature ranges. For example, the half-life for organic solid formation is similar to 5 days at 373 K, similar to 200 days at 323 K, and similar to 70 years at 273 K with ammonia, and similar to 25 days at 373 K, similar to 13 years at 323 K, and similar to 2 x 10(4) years at 273 K without ammonia. These results indicate that organic solids could form during the aqueous alteration in meteorite parent bodies. If liquid water existed early in the interiors of Kuiper belt objects (KBOs), formaldehyde could convert into organic solids at temperatures close to 273 K, and possibly even below 273 K in the ammonia-water system. (C) 2014 Elsevier Inc. All rights reserved.

Aqueous abiotic methane concentrations in a range of geologic settings are below levels expected for equilibrium with coexisting CO2 and H-2, indicating that kinetics can control the speciation of reduced carbon-bearing fluids. Previous studies have suggested that mineral catalysts or gas-phase reactions may increase the rate of methanogenesis. Here, we report on experiments that indicate pressure can also accelerate aqueous reduction of CO2 to CH4. Four series of cold-seal hydrothermal experiments were performed from 1 to 3.5 kbar at 300 degrees C for two weeks and analyzed using gas chromatography/mass spectrometry. The starting fluids were 10-20-mu L solutions of 70-mmolal C-13-labeled formic acid ((HCOOH)-C-13) contained in welded gold capsules. Increasing pressure (P) resulted in a systematic, reproducible log-linear increase in (CH4)-C-13 yields. The pressure effect could be quantified the log-linear slope, Delta log[(CH4)-C-13]/Delta P (log mmolal per kbar). The mean slope was 0.66 +/- 0.05 (+/- 1s.e.), indicating that (CH4)-C-13 yields increased by an average factor of 40-50 over a P range of 2.5 kbar. Pressure-independent variations in [(CH4)-C-13] were observed as scatter about the log-linear regressions and as variations in the y-intercepts of the regressions. These variations were attributed to trace amounts of catalytic Fe along the inner capsule wall that remained despite cleaning the Au capsules in nitric acid prior to each experimental series. The mechanism for the pressure-dependent effect was interpreted to result from one or more of the following three processes: reduction of a metastable reaction intermediate such as methanol, formation of Fe-carbonyl complexes in the fluid, and/or heterogeneous catalysis by Fe. The results suggest that pressure may influence aqueous abiotic CH4 yields in certain geological environments, particularly when the relative effects of other kinetic factors such as temperature are diminished, e. g., in cool forearcs or other settings with a steep geothermal gradient. Because the experiments were performed over a limited pressure range, even modest isothermal increases in pressure may substantially enhance CH4 yields. A kinetic pressure effect may be especially important on the deep ocean floors of planetary bodies where pressure may compensate for the otherwise sluggish reaction kinetics expected at low T. (C) 2014 Elsevier Ltd. All rights reserved.

Aqueous abiotic methane concentrations in a range of geologic settings are below levels expected for equilibrium with coexisting CO2 and H-2, indicating that kinetics can control the speciation of reduced carbon-bearing fluids. Previous studies have suggested that mineral catalysts or gas-phase reactions may increase the rate of methanogenesis. Here, we report on experiments that indicate pressure can also accelerate aqueous reduction of CO2 to CH4. Four series of cold-seal hydrothermal experiments were performed from 1 to 3.5 kbar at 300 degrees C for two weeks and analyzed using gas chromatography/mass spectrometry. The starting fluids were 10-20-mu L solutions of 70-mmolal C-13-labeled formic acid ((HCOOH)-C-13) contained in welded gold capsules. Increasing pressure (P) resulted in a systematic, reproducible log-linear increase in (CH4)-C-13 yields. The pressure effect could be quantified the log-linear slope, Delta log[(CH4)-C-13]/Delta P (log mmolal per kbar). The mean slope was 0.66 +/- 0.05 (+/- 1s.e.), indicating that (CH4)-C-13 yields increased by an average factor of 40-50 over a P range of 2.5 kbar. Pressure-independent variations in [(CH4)-C-13] were observed as scatter about the log-linear regressions and as variations in the y-intercepts of the regressions. These variations were attributed to trace amounts of catalytic Fe along the inner capsule wall that remained despite cleaning the Au capsules in nitric acid prior to each experimental series. The mechanism for the pressure-dependent effect was interpreted to result from one or more of the following three processes: reduction of a metastable reaction intermediate such as methanol, formation of Fe-carbonyl complexes in the fluid, and/or heterogeneous catalysis by Fe. The results suggest that pressure may influence aqueous abiotic CH4 yields in certain geological environments, particularly when the relative effects of other kinetic factors such as temperature are diminished, e. g., in cool forearcs or other settings with a steep geothermal gradient. Because the experiments were performed over a limited pressure range, even modest isothermal increases in pressure may substantially enhance CH4 yields. A kinetic pressure effect may be especially important on the deep ocean floors of planetary bodies where pressure may compensate for the otherwise sluggish reaction kinetics expected at low T. (C) 2014 Elsevier Ltd. All rights reserved.

Proteins are responsible multiple biological functions, such as ligand binding, catalysis, and ion channeling. This functionality is enabled by proteins' three-dimensional structures that require long polypeptides. Since plausibly prebiotic synthesis of functional polypeptides has proven challenging in the laboratory, we propose that these functions may have been initially performed by alternative macromolecular constructs, namely hyperbranched polymers (HBPs), during early stages of chemical evolution. HBPs can be straightforwardly synthesized in one-pot processes, possess globular structures determined by their architecture as opposed to folding in proteins, and have documented ligand binding and catalytic properties. Our initial study focuses on glycerol-citric acid HBPs synthesized via moderate heating in the dry state. The polymerization products consisted of a mixture of isomeric structures of varying molar mass as evidenced by NMR, mass spectrometry and size-exclusion chromatography. Addition of divalent cations during polymerization resulted in increased incorporation of citric acid into the HBPs and the possible formation of cation-oligomer complexes. The chelating properties of citric acid govern the makeup of the resulting polymer, turning the polymerization system into a rudimentary smart material.

Proteins are responsible multiple biological functions, such as ligand binding, catalysis, and ion channeling. This functionality is enabled by proteins' three-dimensional structures that require long polypeptides. Since plausibly prebiotic synthesis of functional polypeptides has proven challenging in the laboratory, we propose that these functions may have been initially performed by alternative macromolecular constructs, namely hyperbranched polymers (HBPs), during early stages of chemical evolution. HBPs can be straightforwardly synthesized in one-pot processes, possess globular structures determined by their architecture as opposed to folding in proteins, and have documented ligand binding and catalytic properties. Our initial study focuses on glycerol-citric acid HBPs synthesized via moderate heating in the dry state. The polymerization products consisted of a mixture of isomeric structures of varying molar mass as evidenced by NMR, mass spectrometry and size-exclusion chromatography. Addition of divalent cations during polymerization resulted in increased incorporation of citric acid into the HBPs and the possible formation of cation-oligomer complexes. The chelating properties of citric acid govern the makeup of the resulting polymer, turning the polymerization system into a rudimentary smart material.

Low-dimensional carbon nanomaterials such as fullerenes, nanotubes, graphene and diamondoids have extraordinary physical and chemical properties(1,2). Compression-induced polymerization of aromatic molecules could provide a viable synthetic route to ordered carbon nanomaterials(3,4), but despite almost a century of study(5-9) this approach has produced only amorphous products(10-14). Here we report recovery to ambient pressure of macroscopic quantities of a crystalline one-dimensional sp(3) carbon nanomaterial formed by high-pressure solid-state reaction of benzene. X-ray and neutron diffraction, Raman spectroscopy, solid-state NMR, transmission electron microscopy and first-principles calculations reveal close-packed bundles of subnanometre-diameter sp(3)-bonded carbon threads capped with hydrogen, crystalline in two dimensions and short-range ordered in the third. These nanothreads promise extraordinary properties such as strength and stiffness higher than that of sp(2) carbon nanotubes or conventional high-strength polymers(15). They may be the first member of a new class of ordered sp(3) nanomaterials synthesized by kinetic control of high-pressure solid-state reactions.

Low-dimensional carbon nanomaterials such as fullerenes, nanotubes, graphene and diamondoids have extraordinary physical and chemical properties(1,2). Compression-induced polymerization of aromatic molecules could provide a viable synthetic route to ordered carbon nanomaterials(3,4), but despite almost a century of study(5-9) this approach has produced only amorphous products(10-14). Here we report recovery to ambient pressure of macroscopic quantities of a crystalline one-dimensional sp(3) carbon nanomaterial formed by high-pressure solid-state reaction of benzene. X-ray and neutron diffraction, Raman spectroscopy, solid-state NMR, transmission electron microscopy and first-principles calculations reveal close-packed bundles of subnanometre-diameter sp(3)-bonded carbon threads capped with hydrogen, crystalline in two dimensions and short-range ordered in the third. These nanothreads promise extraordinary properties such as strength and stiffness higher than that of sp(2) carbon nanotubes or conventional high-strength polymers(15). They may be the first member of a new class of ordered sp(3) nanomaterials synthesized by kinetic control of high-pressure solid-state reactions.