Second-order NMR spectra at high field of common organic functional groups

The proton NMR spectra of aryl n-propyl sulfides gave rise to what may appear to be first-order proton NMR spectra. Upon oxidation to the corresponding sulfone, the spectra changed appearance dramatically and were clearly second-order. A detailed analysis of these second-order spectra, in the sulfone series, provided vicinal coupling constants which indicated that these compounds had a moderate preference for the anti-conformer, reflecting the much greater size of the sulfone over the sulfide. It also emerged, from this study, that the criterion for observing large second-order effects in the proton NMR spectra of 1,2-disubstituted ethanes was that the difference in vicinal coupling constants must be large and the difference in geminal coupling constants must be small. n-Propyl triphenylphosphonium bromide and 2-trimethylsilylethanesulfonyl chloride, and derivatives thereof, also exhibited second-order spectra, again due to the bulky substituents. Since these spectra are second-order due to magnetic nonequivalence of the nuclei in question, not chemical shifts, the proton spectra are perpetually second-order and can never be rendered first-order by using higher field NMR spectrometers.

Adsorption of metal ions on nitrogen surface functional groups in activated carbons

A commercially available coconut-shell-derived active carbon was oxidized with nitric acid, and both the original and oxidized active carbons were treated with ammonia at 1073 K to incorporate nitrogen functional groups into the carbon. An active carbon with very high nitrogen content (similar to9.4 wt % daf) was also prepared from a nitrogen-rich precursor, polyacrylonitrile (PAN). These nitrogen-rich carbons had points of zero charge (pH(pzc)) similar to H-type active carbons. X-ray absorption near-edge structure (XANES) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and temperature-programmed desorption (TPD) were used to characterize the nitrogen functional groups in the carbons. The nitrogen functional groups present on the carbon surface were pyridinic, pyrrolic (or indolic), and pyridonic structures. The adsorption of transition metal cations Cd2+, Ni2+, and Cu2+ from aqueous solution on the suite of active carbons showed that adsorption was markedly higher for carbons with nitrogen functional groups present on the surface than for carbons with similar pH(pzc) values. In contrast, the adsorption characteristics of Ca2+ from aqueous solution were similar for all the carbons studied. Flow microcalorimetry (FMC) studies showed that the enthalpies of adsorption of Cd2+(aq) on the active carbons with high nitrogen contents were much higher than for nitric acid oxidized carbons studied previously, which also had enhanced adsorption characteristics for metal ion species. The enthalpies of adsorption of Cu2+ were similar to those obtained for Cd2+ for specific active carbons. The nitrogen functional groups in the carbons act as surface coordination sites for the adsorption of transition metal ions from aqueous solution. The adsorption characteristics of these carbons are compared with those of oxidized carbons.

Magnitude differences in bioactive compounds, chemical functional groups, fatty acid profiles, nutrient degradation and digestion, molecular structure and metabolic characteristics of protein in newly developed yellow-seeded and black-seeded canola lines.

Recently, new lines of yellow-seeded (CS-Y) and black-seeded canola (CS-B) have been developed with chemical and structural alteration through modern breeding technology. However, no systematic study was found on the bioactive compounds, chemical functional groups, fatty acid profiles, inherent structure, nutrient degradation and absorption, or metabolic characteristics between the newly developed yellow- and black-seeded canola lines. This study aimed to systematically characterize chemical, structural, and nutritional features in these canola lines. The parameters accessed include bioactive compounds and antinutrition factors, chemical functional groups, detailed chemical and nutrient profiles, energy value, nutrient fractions, protein structure, degradation kinetics, intestinal digestion, true intestinal protein supply, and feed milk value. The results showed that the CS-Y line was lower (P ≤ 0.05) in neutral detergent fiber (122 vs 154 g/kg DM), acid detergent fiber (61 vs 99 g/kg DM), lignin (58 vs 77 g/kg DM), nonprotein nitrogen (56 vs 68 g/kg DM), and acid detergent insoluble protein (11 vs 35 g/kg DM) than the CS-B line. There was no difference in fatty acid profiles except C20:1 eicosenoic acid content (omega-9) which was in lower in the CS-Y line (P < 0.05) compared to the CS-B line. The glucosinolate compounds differed (P < 0.05) in terms of 4-pentenyl, phenylethyl, 3-CH3-indolyl, and 3-butenyl glucosinolates (2.9 vs 1.0 μmol/g) between the CS-Y and CS-B lines. For bioactive compounds, total polyphenols tended to be different (6.3 vs 7.2 g/kg DM), but there were no differences in erucic acid and condensed tannins with averages of 0.3 and 3.1 g/kg DM, respectively. When protein was portioned into five subfractions, significant differences were found in PA, PB1 (65 vs 79 g/kg CP), PB2, and PC fractions (10 vs 33 g/kg CP), indicating protein degradation and supply to small intestine differed between two new lines. In terms of protein structure spectral profile, there were no significant differences in functional groups of amides I and II, α helix, and β-sheet structure as well as their ratio between the two new lines, indicating no difference in protein structure makeup and conformation between the two lines. In terms of energy values, there were significant differences in total digestible nutrient (TDN; 149 vs 133 g/kg DM), metabolizable energy (ME; 58 vs 52 MJ/kg DM), and net energy for lactation (NEL; 42 vs 37 MJ/kg DM) between CS-Y and CS-B lines. For in situ rumen degradation kinetics, the two lines differed in soluble fraction (S; 284 vs 341 g/kg CP), potential degradation fraction (D; 672 vs 590 g/kg CP), and effective degraded organic matter (EDOM; 710 vs 684 g/kg OM), but no difference in degradation rate. CS-Y had higher digestibility of rumen bypass protein in the intestine than CS-B (566 vs 446 g/kg of RUP, P < 0.05). Modeling nutrient supply results showed that microbial protein synthesis (MCP; 148 vs 171 g/kg DM) and rumen protein degraded balance (DPB; 108 vs 127 g/kg DM) were lower in the CS-Y line, but there were no differences in total truly digested protein in small intestine (DVE) and feed milk value (FMV) between the two lines. In conclusion, the new yellow line had different nutritional, chemical, and structural features compared to the black line. CS-Y provided better nutrient utilization and availability.

Reactions of nitrogen and oxygen surface groups in nanoporous carbons under inert and reducing atmospheres

The reactions of surface functional groups have an important role in controlling conversion of char nitrogen to NOx during coal combustion. This study involved an investigation of the thermal stability and reactions of nitrogen surface functional groups in nanoporous carbons. Four suites of carbons, which were used as models for coal chars, were prepared with a wide range of nitrogen and oxygen contents and types of functional groups. The porous structures of the carbons were characterized by gas adsorption methods while chemical analysis, X-ray photoelectron spectroscopy, and X-ray near edge structure spectroscopy were used to characterize the surface functional groups. Temperature programmed desorption and temperature programmed reduction methods were used to study the reactivity of the surface functional groups during heat treatment under inert and reducing conditions. Heat treatment studies show that the order of stability of the functional groups is quaternary nitrogen > pyridinic > pyrrolic > pyridine N-oxide. Pyridine N-oxide surface groups desorb NO and form N-2 via surface reactions at low temperature. Pyrrolic and pyridinic functional groups decompose and react with surface species to give NH3, HCN, and N-2 as desorption products, but most pyrrolic groups are preferentially converted to pyridinic and quaternary nitrogen. The main desorption product is N-2. Approximately 15-40 wt % of the original nitrogen was retained in the carbons mainly as quaternary nitrogen after heat treatment to 1673 K. The results are discussed in terms of decomposition ranges for surface functional groups and reaction mechanisms of surface species.

Functional role of microarthropods in soil aggregation

Soil aggregation has received a lot of attention in the last years; however, the focus was mostly on soil microorganismsor larger soil fauna, especially earthworms. The impact of the large group of microarthropods, e.g. Collembola and Acari, is nearly unknown and hence underrepresented in the literature. Here we propose and discuss potential direct and indirect mechanisms of how microarthropods could influence this process with the focus on collembolans, which are in general a relatively well studied taxon.Indirect mechanisms are likely to have larger impacts on soil aggregation than direct effects. The variety of indirect mechanisms based on the provision of organic material like faecal pellets, molts and necromass as food source for microorganisms is high and given available evidence we propose that these mechanismsare the most influential. We highlight the need for overcoming the challenges of culturing and handling of these animals in order to be able to design small scale experiments and field studies which would enable us to understand the role of the different
functional groups, their interaction with other soil faunaand the impact of land use practices on soil aggregation.

DFT studies of long-chain FAMEs: theoretical justification for determining chain length and unsaturation from experimental Raman spectra

Density functional calculations, using B3LPY/6-31G(d) methods, have been used to investigate the conformations and vibrational (Raman) spectra of a series of long-chain, saturated fatty acid methyl esters (FAMEs) with the formula CH2nO2 (n = 5-21) and two series of unsaturated FAMEs. The calculations showed that the lowest energy conformer within the saturated FAMEs is the simple (all-trans) structure and, in general, it was possible to reproduce experimental data using calculations on only the all-trans conformer. The only exception was C6H12O2, where a second low-lying conformer had to be included in order to correctly simulate the experimental Raman spectrum. The objective of the work was to provide theoretical justification for the methods that are commonly used to determine the properties of the fats and oils, such as chain length and degree of unsaturation, from experimental Raman data. Here it is shown that the calculations reproduce the trends and calibration curves that are found experimentally and also allow the reasons for the failure of what would appear to be rational measurements to be understood. This work shows that although the assumption that each FAME can simply be treated as a collection of functional groups can be justified in some cases, many of the vibrational modes are complex motions of large sections of the molecules and thus would not be expected to show simple linear trends with changes in structure, such as increasing chain length and/or unsaturation. Simple linear trends obtained from experimental data may thus arise from cancellation of opposing effects, rather than reflecting an underlying simplicity.

Structure-activity studies on position 14 of human alpha-calcitonin gene-related peptide

A structure-activity study was performed to examine the role of position 14 of human alpha-calcitonin gene-related peptide (h-alpha-CGRP) in activating the CGRP receptor. Interestingly, position 14 of h-alpha-CGRP contains a glycyl residue and is part of an alpha-helix spanning residues 8-18. Analogues [Ala(14)]-h-alpha-CGRP, [Aib(14)]-h-alpha-CGRP, [Asp(14)]-h-alpha-CGRP, [Asn(14)]-h-alpha-CGRP, and [Pro(14)]-h-alpha-CGRP were synthesized by solid phase peptide methodology and purified by RP-HPLC. Secondary structure was measured by circular dichroism spectroscopy. Agonist activities were determined as the analogues' ability to stimulate amylase secretion from guinea pig pancreatic acini and to relax precontracted porcine coronary arteries. Analogues [Ala(1)4]-h-alpha-CGRP, [Aib(14)]-h-alpha-CGRP, [Asp(14)]-h-alpha-CGRP, and [Asn(14)]-h-alpha-CGRP, all containing residues with a high helical propensity in position 14, were potent full agonists compared to h-alpha-CGRP in both tissues. Interestingly, replacement of Gly(14) of h-alpha-CGRP with these residues did not substantially increase the helical content of these analogues. [Pro(14)]-h-alpha-CGRP, predictably, has significantly lower helical content and is a 20-fold less potent agonist on coronary artery, known to contain CGRP-1 receptor subtypes, and an antagonist on pancreatic acini, known to contain CGRP-2 receptor subtypes. In conclusion, the residue in position 14 plays a structural role in stabilizing the alpha-helix spanning residues 8-18. The alpha-helix is crucial for maintaining highly potent agonist effects of h-alpha-CGRP at CGRP receptors. The wide variety of functional groups that can be tolerated in position 14 with no substantial modification of agonist effects suggests the residue in this position is not in contact with the CGRP receptor. [Pro(14)]-h-alpha-CGRP may be a useful pharmacological tool to distinguish between CGRP-1 and CGRP-2 receptor subtypes.

Algal epiphytes of Zostera marina: Variation in assemblage structure from individual leaves to regional scale

Data from a hierarchical study of four Zostera marina beds in Wales were used to identify the spatial scales of variation in epiphyte assemblages. There were significant within and among bed differences in assemblage structure. The differences in assemblage structure with spatial scale generally persisted when species identifications were aggregated into functional groups. There was also significant within and among bed variability in Zostera density and average length. Local variations in Zostera canopy variables at the quadrat scale (total leaf length, average leaf length and leaf density per quadrat) were not related to epiphyte species richness nor to the structure of the assemblage. In contrast, individual leaf length was significantly related to species richness in two of the beds and the structure of epiphyte assemblages was always related to individual leaf lengths. The absence of links between quadrat scale measurements of canopy variables and assemblage structure may reflect the high turnover of individual Zostera leaves. Experimental work is required to discriminate further between the potential causes of epiphyte assemblage variation within and between beds. No bed represented a refuge where a rare species was abundant. If a species was uncommon at the bed scale, it was also uncommon in beds where it occurred. The heterogeneous assemblages found in this study suggest that a precautionary approach to conservation is advisable.

Adsorption characteristics of Cu and Ni on Irish peat moss

Peat has been widely used as a low cost adsorbent to remove a variety of materials including organic compounds and heavy metals from water. Various functional groups in lignin allow such compounds to bind on active sites of peat. The adsorption of Cu²⁺ and Ni²⁺ from aqueous solutions on Irish peat moss was studied both as a pure ion and from their binary mixtures under both equilibrium and dynamic conditions in the concentration range of 5–100 mg/L. The pH of the solutions containing either Cu²⁺ or Ni²⁺ was varied over a range of 2–8. The adsorption of Cu²⁺ and Ni⁺² on peat was found to be pH dependent. The adsorption data could be fitted to a two-site Langmuir adsorption isotherm and the maximum adsorption capacity of peat was determined to be 17.6 mg/g for Cu²⁺ and 14.5 mg/g for Ni²⁺ at 298 K when the initial concentration for both Cu²⁺ and Ni²⁺ was 100 mg/L, and the pH of the solution was 4.0 and 4.5, respectively. Column studies were conducted to generate breakthrough data for both pure component and binary mixtures of copper and nickel. Desorption experiments showed that 2 mM EDTA solution could be used to remove all of the adsorbed copper and nickel from the bed.

Ionic liquid characteristics of 1-alkyl-n-cyanopyridinium and 1-alkyl-n-(trifluoromethyl) pyridinium salts

1-Alkyl-n-cyanopyridinium and 1-alkyl-n-(trifluoromethyl) pyridinium salts have been synthesised and characterised in order to compare the effects of different electron-withdrawing functional groups on their ability to form ionic liquids. The presence of the electron-withdrawing nitrile or trifluoromethyl substituent on the pyridinium ring leads to salts with higher melting points than with the corresponding 1-alkylpyridinium or 1-alkylpicolinium cations. Solid-state structures were determined by single crystal X-ray crystallography for seven salts; 1-methyl-4-cyanopyridinium methylsulfate, and 1-methyl-3-cyanopyridinium, 1-methyl-4-cyanopyridinium, 1-ethyl-2-cyanopyridinium, 1-ethyl-3-cyanopyridinium, 1-ethyl-4-cyanopyridinium and 1-ethyl-4-(trifluormethyl) pyridinium bis{(trifluoromethyl) sulfonyl} imide, and show the effects of ring-substitution position on hydrogen-bonding in the solid-state and on melting points.

Adsorption mechanisms of removing heavy metals and dyes from aqueous solution using date pits solid adsorbent

A potential usefulness of raw date pits as an inexpensive solid adsorbent for methylene blue (MB), copper ion (Cu2+), and cadmium ion (Cd2+) has been demonstrated in this work. This work was conducted to provide fundamental information from the study of equilibrium adsorption isotherms and to investigate the adsorption mechanisms in the adsorption of MB, Cu2+, and Cd2+ onto raw date pits. The fit of two models, namely Langmuir and Freundlich models, to experimental data obtained from the adsorption isotherms was checked. The adsorption capacities of the raw date pits towards MB and both Cu2+ and Cd2+ ions obtained from Langmuir and Freundlich models were found to be 277.8, 35.9, and 39.5 mg g(-1), respectively. Surface functional groups on the raw date pits surface substantially influence the adsorption characteristics of MB, Cu2+, and Cd2+ onto the raw date pits. The Fourier transform infrared spectroscopy (FTIR) studies show clear differences in both absorbances and shapes of the bands and in their locations before and after solute adsorption. Two mechanisms were observed for MB adsorption, hydrogen bonding and electrostatic attraction, while other mechanisms were observed for Cu2+ and Cd2+. For Cu2+, binding two cellulose/lignin units together is the predominant mechanism. For Cd2+. the predominant mechanism is by binding itself using two hydroxyl groups in the cellulose/lignin unit. (C) 2009 Elsevier B.V. All rights reserved.

PtCl2/XPhos: A highly efficient and readily available catalyst for the hydrosilylation of propargylic alcohols

A highly regioselective hydrosilylation of propargylic alcohols has been developed using an in situ prepared PtCl2/XPhos catalyst system. The reaction is tolerant of many functional groups and exhibits excellent regio and geometric selectivity.

The potential of electron beam radiation for simultaneous surface modification and bioresorption control of PLLA

Bioresorbable polymers have been widely investigated as materials exhibiting significant potential for successful application in the fields of tissue engineering and drug delivery. Further to the ability to control degradation, surface engineering of polymers has been highlighted as a key method central to their development. Previous work has demonstrated the ability of electron beam (e-beam) technology to control the degradation profiles and bioresorption of a number of commercially relevant bioresorbable polymers (poly-l-lactic acid (PLLA), Llactide/DL-lactide co-polymer (PLDL) and poly(lactic-co-glycolic acid (PLGA)). This work investigates the further potential of ebeam technology to impart added biofunctionality through the manipulation of polymer (PLLA) surface properties. PLLA samples were subjected to e-beam treatments in air, with varying beam energies and doses. Surface characterization was then performed using contact angle analysis, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and atomic force microscopy. Results demonstrated a significant increase in surface wettability post e-beam treatment. In correlation with this, XPS data showed the introduction of oxygen-containing functional groups to the surface of PLLA. Raman spectroscopy indicated chain scission in the near surface region of PLLA (as predicted). However, e-beam effects on surface properties were not shown to be dependent on beam energy or dose. E-beam irradiation did not seem to affect the surface roughness of PLLA as a direct consequence of the treatment.

Impacts of sewage outfalls on rocky shores: incorporating scale, biotic assemblage structure and variability into monitoring tools.

Coastal systems, such as rocky shores, are among the most heavily anthropogenically-impacted marine ecosystems and are also among the most productive in terms of ecosystem functioning. One of the greatest impacts on coastal ecosystems is nutrient enrichment from human activities such as agricultural run-off and discharge of sewage. The aim of this study was to identify and characterise potential effects of sewage discharges on the biotic diversity of rocky shores and to test current tools for assessing the ecological status of rocky shores in line with the EU Water Framework Directive (WFD). A sampling strategy was designed to test for effects of sewage outfalls on rocky shore assemblages on the east coast of Ireland and to identify the scale of the putative impact. In addition, a separate sampling programme based on the Reduced algal Species List (RSL), the current WFD monitoring tool for rocky shores in Ireland and the UK, was also completed by identifying algae and measuring percent cover in replicate samples on rocky shores during Summer. There was no detectable effect of sewage outfalls on benthic taxon diversity or assemblage structure. However, spatial variability of assemblages was greater at sites proximal or adjacent to sewage outfalls compared to shores without sewage outfalls present. Results based on the RSL, show that algal assemblages were not affected by the presence of sewage outfalls, except when classed into functional groups when variability was greater at the sites with sewage outfalls. A key finding of both surveys, was the prevalence of spatial and temporal variation of assemblages. It is recommended that future metrics of ecological status are based on quantified sampling designs, incorporate changes in variability of assemblages (indicative of community stability), consider shifts in assemblage structure and include both benthic fauna and flora to assess the status of rocky shores.