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Mixed chain phospholipids containing a saturated fatty acid at sn1 and a polyunsaturated fatty acid in sn2 are common in the specialized biological membranes prevalent in neural, retinal and organ tissues. Particularly important are mixed lipids containing palmitic or stearic acid and arachidonic or docosahexaenoic acid. Gradient temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements and phase transitions. Herein we utilize GTRS for 1-18:0, 2-20:4n-6 PC; 1-18:0 2-22:6n-3 PC; and 1-18:0, 2-18:0 PC from −80 to 50 °C temperatures. 20 Mb three-dimensional data arrays with 0.2 °C increments and first/second derivatives allowed detailed vibrational mode assignment and analysis. Samples were analyzed neat and with molecular hydration. Previously reported phase transitions for hydrated 18:0−20:4PC and 18:0−22:6PC and numerous spectral differences resulting from hydration and the double bond structure were clearly observed. Molecular models showed that the addition of minimal water molecules results in significant structural differences compared to the neat molecules; 18:0−22:6PC is strikingly compact with water when viewed from the hydrophilic end. This precise Raman data cannot be observed in typically utilized fully hydrated vesicle samples, however the improved GTRS will allow for more precise analysis in fully hydrated vesicles because the underlying modes in the unavoidably broadened spectra can be identified.

Gradient Temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur at or near phase transitions. 20 Mb threedimensional data arrays with 1.0 or 0.2°C increments allow complete assignment of solid, liquid and transition state vibrational modes, including low intensity/frequency vibrations that cannot be readily analyzed with conventional Raman. We compared GTRS and DSC data for commercial fish oil supplements that are excellent sources of docosahexaenoic acid (DHA; 22:6n-3) and eicosapentaenoic acid (EPA; 20:5n-3). Krill oils and whole fish and shellfish have nearly all their PUFA contained within phospholipids (PL). Development of any fast-throughput optical identification system for seafood products will require improved PL Raman data. We also analyzed molecularly hydrated PL with DHA and other unsaturated lipids. Each fish oil and PL have a unique, distinctive response to the thermal gradient, which graphically and spectroscopically differentiates them. The entire set or any subset of the any of the contour plots, first derivatives or second derivatives can be utilized to create a graphical standard to quickly authenticate a given product or source material.

Specialized pro-resolving mediators provide promising targets for new drugs and natural products. Much work has been accomplished on the structure/ function of the lipoxygenase and cyclooxygenase enzymes but not on the substrates. A better visualization of three-dimensional lipid structures will allow increased refinement of the interactions that produce the pro-resolving mediators, and lead to improvements in synthetic pathways. We present systematic analysis of oleic (18:1n-9), linoleic (18:2n-6), alpha-linolenic (18:3n-3), arachidonic (20:4n-6), docosapentaenoic (22:5n-3), and docosahexaenoic (22:6n-3) acids. Continuous gradient temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry to Raman spectroscopy. GTRS can identify and differentiate specific carbon chain sites, finally allowing Raman analysis to explain why the long-chain polyunsaturated fatty acids (LC-PUFA) exhibit such extreme functional differences despite minimal changes in chemical structure. Detailed vibrational analysis of the important frequency ranges 1450 - 1200 cm-1 (includes CH2 bending and twisting) and 1750 - 1425 cm-1 (includes C=C stretching and C-C stretching plus H-C in-plane rocking) shows for the first time that each molecule has its own characteristic set of modes with only some redundancy/commonality. The number and frequency of modes correlates with three-dimensional molecular structure, not the degree of unsaturation. The high degree of specificity of lipoxygenase and cyclooxygenase enzymes should be reconsidered in light of the fact that individual sites on the polyunsaturated fatty acid chain are nonequivalent, and each LC-PUFA molecule has an individual, specific three dimensional structure incorporating torsion.

Since the 1950's, the broad-spectrum, organochlorine insecticide endosulfan (6,7,8, 9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) has been used on numerous crops. Due to its persistence, bioaccumulation, long-range transport, and adverse effects to human health and ecosystems, it was officially identified as a persistent organic pollutant (POP) in 2011. The last uses in the United States were phased out in 2016. Endosulfan consists of two diastereomers, α-endosulfan and β-endosulfan, and while the α-isomer exists as two asymmetrical, twist-chair enantiomers which interchange, the β-isomer is a symmetrical-chair conformation. In addition, the β-isomer was found to isomerize to the α-isomer. Gradient Temperature Raman Spectroscopy (GTRS) enables identification the molecular sites at which bending vibrational modes becomes twisting or wagging vibrational modes. Previous studies using GTRS and chemical calculations afforded evidence for specific bond movements and the irreversibility of the isomerization mechanism. However, not all of the vibrational modes observed in the spectra could be explained. Thus, new analyses of the GTRS data were conducted to examine the effects of torsional forces on the bond movement, which allowed for the identification of all the peaks. These newly-identified torsional forces provide further confirmation of the isomerization mechanism and its irreversibility. Finally, this isomerization explains why β-endosulfan is rarely detected in the atmosphere.

Docosahexaenoic acid (DHA, 22:6n-3) is exclusively utilized in fast signal processing tissues such as retinal, neural and cardiac. N-3 docosapentaenoic acid (n-3DPA, 22:5n-3), with just one less double bond, is also found in the marine food chain yet cannot substitute for DHA. Gradient temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur near and at phase transitions. Herein we apply GTRS and both conventional and modulated DSC to n-3DPA and DHA from -100 to 20°C. Three-dimensional data arrays with 0.2°C increments and first derivatives allowed complete assignment of solid, liquid and transition state vibrational modes. Melting temperatures n-3DPA (-45°C) and DHA (-46°C) are similar and show evidence for solid-state phase transitions not seen in n-6DPA (-27°C melt). The C6H2 site is an elastic marker for temperature perturbation of all three lipids, each of which has a distinct three dimensional structure. N-3 DPA shows the spectroscopic signature of saturated fatty acids from C1 to C6. DHA does not have three aliphatic carbons in sequence; n-6DPA does but they occur at the methyl end, and do not yield the characteristic signal. DHA appears to have uniform twisting from C6H2 to C12H2 to C18H2 whereas n-6DPA bends from C12 to C18, centered at C15H2. For n-3DPA, twisting is centered at C6H2 adjacent to the C2-C3-C4-C5 aliphatic moiety. These molecular sites are the most elastic in the solid phase and during premelting.

One of the great unanswered biological questions is the absolute necessity of the polyunsaturated lipid docosahexaenoic acid (DHA; 22:6n-3) in retinal and neural tissues. Everything from the simple eye spot of dinoflagellates to cephalopods to every class of vertebrates uses DHA, yet it is abundant only in cold water marine food chains. Docosapentaenoic acids (DPAs; 22:5n-6 and especially 22:5n-3) are fairly plentiful in food chains yet cannot substitute for DHA. About 600 million years ago, multi-cellular, air breathing systems evolved rapidly and 32 phyla came into existence in a short geological time span; the "Cambrian Explosion". Eukaryotic intracellular detail requires cell membranes, which are constructed of complex lipids, and proteins. Proteins and nucleic acids would have been abundant during the first 2.5-5 billion years of anaerobic life but lipids, especially unsaturated fatty acids, would not. We hypothesize lipid biology was a key driver of the Cambrian Explosion, because it alone provides for compartmentalization and specialization within cells DHA has six methylene interrupted double bonds providing controlled electron flow at precise energy levels; this is essential for visual acuity and truthful execution of the neural pathways which make up our recollections, information processing and consciousness. The last double bond is critical for the evolution and function of the photoreceptor and neuronal and synaptic signaling systems. It completes a quantum mechanical device for the regulation of current flow with absolute signal precision based on electron tunneling (ET). DHA's methylene interruption distance is6 Å, making ET transfer between the π-orbitals feasible throughout the molecule. The possibility fails if one double bond is removed and replaced by a saturated bond as in the DPAs. The molecular biophysical foundation of neural signaling can also include the discrete pattern of paired spin states that arise in the DHA double bond and methylene regions. The complexity depends upon the number of C13 and H1 molecular sites in which spin states are coupled. Electron wave harmonics with entanglement and cohesion provide a mechanism for learning and memory, and power cognition and complex human brain functions.

We analyzed the unsaturated fatty acids oleic (OA, 18:1n-9) and linoleic (LA, 18:2n-3), and a 3:1 LA:OA mixture from −100 to 50 °C with continuous gradient temperature Raman spectroscopy (GTRS). The 20 Mb three-dimensional data arrays with 0.2 °C increments and first/second derivatives allowed rapid, complete assignment of solid, liquid, and transition state vibrational modes. For OA, large spectral and line width changes occurred in the solid state γ to α transition near −4 °C, and the melt (13 °C) over a range of only 1 °C. For LA, major intensity reductions from 200 to 1750 cm−1 and some peak shifts marked one solid state phase transition at −50 °C. A second solid state transition (−33 °C) had minor spectral changes. Large spectral and line width changes occurred at the melt transition (−7 °C) over a narrow temperature range. For both molecules, melting initiates at the diene structure, then progresses towards the ends. In the 3:1 LA:OA mixture, some less intense and lower frequencies present in the individual lipids are weaker or absent. For example, modes assignable to C8 rocking, C9H–C10H wagging, C10H–C11H wagging, and CH3 rocking are present in OA but absent in LA:OA. Our data quantify the concept of lipid premelting and identify the flexible structures within OA and LA, which have characteristic vibrational modes beginning at cryogenic temperatures.

Numerous health benefits of seafoods are attributed to their n−3 long-chain polyunsaturated fatty acid content, especially eicosapentaenoic acid (EPA; 20:5n−3) and docosahexaenoic acid (DHA; 22:6n−3). EPA, DHA and their precursor α-linolenic acid (ALA; 18:3n−3) differ vastly biochemically, but from a physical chemical standpoint are close structural analogs. There remains, for example, no satisfactory explanation why only DHA can be utilized in fast signal processing tissues such as neuronal, retinal and cardiac. Recently, gradient temperature Raman spectroscopy has identified key lipid structural differences that require further NMR elucidation. 1H and 13C 1D experiments were performed on neat EPA, DHA, and ALA and 4 different 2D experiments on EPA. The methine 13C spectra show six chemical shifts for ALA; 10 for an EPA, and 12 for DHA. The chemical shift of the first C closest to the C1 carbonyl site is always the most upfield; that of the last C closest to the methyl end is always the most downfield. 1H chemical shift of almost none of the methine protons match. The 13C paired molecular sites identified as conformationally redundant are not identical to the 1H molecular sites identified as conformationally paired. For EPA, long-range coupling is stronger and extends longer at the methyl-ended C18 to C10H2 section and is shorter at C5 to C7H2; also C18 and C17 coupling differ. Repeating (H C C H) CH2 moieties are planar; unequal torsion alters both curvature and twist both ends of the lipids. The methyl end is the most elastic. Asymmetry in twist between the two ends results in torque at the methylene site near the geometric center, resulting in unusually strong electron 13C and 1H shielding.

Continuous gradient temperature Raman spectroscopy (GTRS) is a simple, rapid technique for determining the unique structures of fatty acids, triacylglycerols and phospholipids. Improved lipid spectra and vibrational assignments have many applications in food safety and quality. Herein we analyze the residual lipid components in porcine and poultry meat and bone meal (MBM) collected directly from rendering operations. We are developing a rapid throughput GTRS method that requires no special extraction methods or toxic/expensive solvents, and can be adapted to field use. Crude ethanol, methanol and water extracts of pork, poultry samples and 20:80 pork:poultry MBM were investigated from -100 to 80°C. GTRS provides 20 Mb three-dimensional data arrays with 0.2°C increments and graphical first and second derivatives. Comparison of second derivative data showed good reproducibility among samples, with some vibrational modes distinct for either pork or chicken. The 20:80 pork:poultry data showed for the first time that lipid prepared from mixed MBM can be positively identified. Oil from pollack waste was also examined. GTRS and other methods can easily identify pure fishmeal or fishmeal mixed into terrestrial MBM; fishmeal is distinguished by its long-chain polyunsaturated fatty acid content. The analytical challenge is to determine economic or accidental adulteration whereby porcine, bovine or ovine MBM are mixed with each other, or mixed into poultry or fish meals.

Despite its biochemical importance, a complete Raman analysis of arachidonic acid (AA, 20:4n-6) has never been reported. Gradient temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur near and at phase transitions. Herein we utilize the GTRS technique for AA and 1 -18:0, 2 -20:4n-6 phosphatidyl choline (AAPC) from cryogenic to mammalian body temperatures. 20 Mb three-dimensional data arrays with 0.2 °C increments and first/second derivatives allowed complete assignment of solid, liquid and transition state vibrational modes. The AA DSC shows a large exothermic peak at −60 °C indicating crystallization or a similar major structural change. No exothermic peak of this magnitude was observed in six other unsaturated lipids (DHA, n-3DPA, n-6DPA, LA, ALA, OA). Melting in AA occurs over a large range: (−60 to −35 °C): very large frequency offsets and intensity changes correlate with premelting initiating circa −60 °C, followed by melting (−37 °C). Novel, unique 3D structures for both molecules reveal that AA is not symmetric as a free fatty acid, and it changes significantly when in the sn-2 phospholipid position. Further, different CH and CH 2 sites are unequally elastic and nonequivalent.

The aim of this article is to draw attention to the special significance of docosahexaenoic acid (DHA) in the brain, the potential relevance of its abundance to the evolution of the brain in past history, and now the relevance of paucity in the food supply to the rise in mental ill-health. Membrane lipids of photoreceptors, synapses, and neurons over the last 600 million years contained consistent and similarly high levels of DHA despite wide genomic change. The consistency is despite the DHA precursor differing only by 2 protons. This striking conservation is an example of Darwin's “Conditions of Existence,” which he described as the higher force in evolution. A purpose of this article is to suggest that the present paradigm of food production currently based on protein requirements, should change to serve the specific lipid needs of the brain to address the rise in mental ill-health.1

The structural, cognitive and visual development of the human brain and retina strictly require long-chain polyunsaturated fatty acids (LC-PUFA). Excluding water, the mammalian brain is about 60% lipid. One of the great unanswered questions with respect to biological science in general is the absolute necessity of the LC-PUFA docosahexaenoic acid (DHA; 22:6n-3) in these fast signal processing tissues. A lipid of the same chain length with just one less diene group, docosapentaenoic acid (DPA; 22:5n-6) is fairly abundant in terrestrial food chains yet cannot substitute for DHA. Gradient Temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur near and at phase transitions. Herein we apply GTRS to DPA, and DHA from -100 to 20°C. 20 Mb three-dimensional data arrays with 1°C increments and first/second derivatives allows complete assignment of solid, liquid and transition state vibrational modes, including low intensity/frequency vibrations that cannot be readily analyzed with conventional Raman. DPA and DHA show significant spectral changes with premelting (-33 and -60°C, respectively) and melting (-27 and -44°C, respectively). The CH2-(HC=CH)-CH2 moieties are not identical in the second half of the DHA and DPA structures. The DHA molecule contains major CH2 twisting (1265 cm -1 ) with no noticeable CH 2 bending, consistent with a flat helical structure with small pitch. Further modeling of neuronal membrane phospholipids must take into account this structure for DHA, which would be configured parallel to the hydrophilic head group line.

One of the great unanswered questions with respect to biological science in general is the absolute necessity of docosahexaenoic acid (DHA, 22:6n-3) in fast signal processing tissues. N-6 docosapentaenoic acid (n-6DPA, 22:5n-6), with just one less double bond, group, is fairly abundant in terrestrial food chains yet cannot substitute for DHA. Gradient temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur near and at phase transitions. Herein we apply GTRS and DSC to n-6DPA and DHA from -100 to 20°C. 20Mb three-dimensional data arrays with 0.2°C increments and first/second derivatives allowed complete assignment of solid, liquid and transition state vibrational modes, including low intensity/frequency vibrations that cannot be readily analyzed with conventional Raman. N-6DPA and DHA show significant spectral changes with premelting (-33 and -60°C, respectively) and melting (-27 and -44°C, respectively). The CH2(HCCH)CH2 moieties are not identical in the second half of the DHA and DPA structures. DPA has bending (1450cm-1) over almost the entire temperature range. In contrast, DHA contains major CH2 twisting (1265cm-1) with no noticeable CH2 bending, consistent with a flat helical structure with a small pitch. Further modeling of neuronal membrane phospholipids must take into account torsion present in the DHA structure, which essential in determining whether the lipid chain is configured more parallel or perpendicular to the hydrophilic head group.

Life originated on this planet about 3 billion years ago. For the first 2.5 billion years of life there was ample opportunity for DNA modification. Yet there is no evidence of significant change in life forms during that time. It was not until about 600 million years ago, when the oxygen tension rose to a point where air-breathing life forms became thermodynamically possible, that a major change can be abruptly seen in the fossil record. The sudden appearance of the 32 phyla in the Cambrian fossil record was also associated with the appearance of intracellular detail not seen in previous life forms. That detail was provided by cell membranes made with lipids (membrane fats) as structural essentials. Lipids thus played a major, as yet unrecognised, role as determinants in evolution. The compartmentalisation of intracellular, specialist functions as in the nucleus, mitochondria, reticulo-endothelial system and plasma membrane led to cellular specialisation and then speciation. Thus, not only oxygen but also the marine lipids were drivers in the Cambrian explosion. Docosahexaenoic acid (DHA) (all- cis-docosa-4,7,10,13,16,19-hexaenoic acid, C22:6ω3 or C22:6, n-3, DHA) is a major feature of marine lipids. It requires six oxygen atoms to insert its six double bonds, so it would not have been abundant before oxidative metabolism became plentiful. DHA provided the membrane backbone for the emergence of new photoreceptors that converted photons into electricity, laying the foundation for the evolution of other signalling systems, the nervous system and the brain. Hence, the ω3 DHA from the marine food web must have played a critical role in human evolution. There is also clear evidence from molecular biology that DHA is a determinant of neuronal migration, neurogenesis and the expression of several genes involved in brain growth and function. That same process was essential to the ultimate cerebral expansion in human evolution. There is now incontrovertible support of this hypothesis from fossil evidence of human evolution taking advantage of the marine food web. Lipids are still modifying the present evolutionary phase of our species; their signature is evident in the changing panorama of non-communicable diseases. The most worrying change in disease pattern is the sharp rise in brain disorders, which, in the European Union, has overtaken the cost of all other burdens of ill health at €386 billion for the 25 member states at 2004 prices. In 2007, the UK cost was estimated at £77 billion and confirmed in 2010 at £105 billion – greater than heart disease and cancer combined. The rise in mental ill health is now being globalised. The solution to the rising vascular disorders in the last century and now brain disorders in this century lies in a radical reappraisal of the food system, which last century was focussed on protein and calories, with little attention paid to the requirements of the brain – the very organ that was the determinant of human evolution. With the marine fish catch having plateaued 20 years ago and its sustainability now under threat, a critical aspect of this revision is the development of marine agriculture from estuarine, coastal and oceanic resources. Such action is likely to play a key role in future health and intelligence.

The genus Alyssum contains >50 Ni hyperaccumulator species; many can achieve >2.5% Ni in dry leaf. In soils with normal Mn levels, Alyssum trichome bases were previously observed to accumulate Ni and Mn to high levels. Here we report concentration and localization patterns in A. murale and A. corsicum grown in soils with nonphytotoxic factorial additions of Ni and Mn salts. Four leaf type subsets based on size and age accumulated Ni and Mn similarly. The greatest Mn accumulation (10 times control) was observed in A. corsicum with 40 mmol Mn kg−1 and 40 mmol Ni kg−1 added to potting soil. Whole leaf Ni concentrations decreased as Mn increased. Synchrotron X-ray fluorescence mapping of whole fresh leaves showed localized in distinct high-concentration Mn spots associated with trichomes, Ni and Mn distributions were strongly spatially correlated. Standard X-ray fluorescence point analysis/mapping of cryofractured and freeze-dried samples found that Ni and Mn were co-located and strongly concentrated only in trichome bases and in cells adjacent to trichomes. Nickel concentration was also strongly spatially correlated with sulfur. Results indicate that maximum Ni phytoextraction by Alyssum may be reduced in soils with higher phytoavailable Mn, and suggest that Ni hyperaccumulation in Alyssum species may have developed from a Mn handling system.

Chromium (Cr) picolinate (CrPic) is a widely used nutritional supplement for optimal insulin function. A relationship among Cr status, diabetes, and associated pathologies has been established. Virtually all trials using CrPic supplementation for subjects with diabetes have demonstrated beneficial effects. Thirteen of 15 clinical studies (including 11 randomized, controlled studies) involving a total of 1,690 subjects (1,505 in CrPic group) reported significant improvement in at least one outcome of glycemic control. All 15 studies showed salutary effects in at least one parameter of diabetes management, including dyslipidemia. Positive outcomes from CrPic supplementation included reduced blood glucose, insulin, cholesterol, and triglyceride levels and reduced requirements for hypoglycemic medication. The greater bioavailability of CrPic compared with other forms of Cr (e.g., niacin-bound Cr or CrCl(3)) may explain its comparatively superior efficacy in glycemic and lipidemic control. The pooled data from studies using CrPic supplementation for type 2 diabetes mellitus subjects show substantial reductions in hyperglycemia and hyperinsulinemia, which equate to a reduced risk for disease complications. Collectively, the data support the safety and therapeutic value of CrPic for the management of cholesterolemia and hyperglycemia in subjects with diabetes.

We have developed commercially viable phytoremediation/phytomining technologies employing Alyssum Ni-hyperaccumulator species to quantitatively extract Ni from soils. The majority of Ni is stored either in Alyssum leaf epidermal cell vacuoles or in the basal portions only of the numerous stellate trichomes. Here, we report simultaneous and region-specific localization of high levels of Ni, Mn, and Ca within Alyssum trichomes as determined by scanning electron microscopy/energy-dispersive X-ray analysis (SEM/EDX). Plants were grown in high Ni soil, achieving up to 48 400 microg g(-1) Ni in total leaf concentration; however, Ca and Mn were not enriched in the experimental soils. The region-specific localization of hyperaccumulated Ca, Mn, and Ni occurred in three soil types, five Alyssum species/ecotypes, and over a wide range of soil Ni concentrations. The metal concentration in the trichome basal compartment was approximately 15-20% dry weight, the highest ever reported for healthy vascular plant tissue.

In the 13C NMR spectra of natural, unenriched docosahexaenoic acid-rich sardine oil and cod muscle glycerophosphocholine significant signal intensity differences across the 1D spectrum between undiluted and diluted samples were observed. In undiluted samples 13C−13C 2D nuclear Overhauser enhancement spectroscopy (NOESY) interchain cross-peaks for CH, CH2, CH3, and CC structures were observed. Results indicate that in undiluted natural lipids, NMR signal intensity is influenced by polarization transfer from the extended lipid structure. The NOE enhancement of specific molecular sites especially in unsaturated lipids is evidence that some natural lipids remain oriented relative to each other and in an orderly arrangement at the molecular level long enough for the effect to be detected by the NMR experiment. The presence of polyunsaturated fatty acids in mixtures of natural lipids could stabilize specific local molecular conformations within the remaining less saturated lipids. Keywords: 13C−13C 2D NOESY; 13...

The causes and control of type 2 diabetes mellitus are not clear, but there is strong evidence that dietary factors are involved in its regulation and prevention. We have shown that extracts from cinnamon enhance the activity of insulin. The objective of this study was to isolate and characterize insulin-enhancing complexes from cinnamon that may be involved in the alleviation or possible prevention and control of glucose intolerance and diabetes. Water-soluble polyphenol polymers from cinnamon that increase insulin-dependent in vitro glucose metabolism roughly 20-fold and display antioxidant activity were isolated and characterized by nuclear magnetic resonance and mass spectroscopy. The polymers were composed of monomeric units with a molecular mass of 288. Two trimers with a molecular mass of 864 and a tetramer with a mass of 1152 were isolated. Their protonated molecular masses indicated that they are A type doubly linked procyanidin oligomers of the catechins and/or epicatechins. These polyphenolic polymers found in cinnamon may function as antioxidants, potentiate insulin action, and may be beneficial in the control of glucose intolerance and diabetes.

Hyperspectral Raman imaging has the potential for rapid screening of solid-phase samples for potential adulterants. We can improve mixture analysis algorithms by defining a temperature range in which the contaminant spectrum changes dramatically and uniquely compared with unadulterated material. Raman spectra were acquired for urea, biuret, cyanuric acid, and melamine (pure and at 1% in dried milk powder) from 50 to 310 °C with a gradient of 1 °C min−1. Adulterants were clearly indentified in the milk powder. Specific frequencies that were mainly associated with ring breathing, stretching, and in-plane deformation shifted with respect to temperature up to 12 cm−1 in all four molecules. Specific frequencies significantly increased/decreased in intensity within narrow temperature ranges independent of whether the amine was mixed in milk. Correlation of Raman and differential scanning calorimetry data identified structural components and vibrational modes, which concur with or trigger phase transitions.

Past applications of biosolids to soils at some locations added higher Cd levels than presently permitted. Cadmium phytoextraction would alleviate current land use constraints. Unamended farm soil, and biosolids amended farm and mine soils were obtained from a Fulton Co., IL biosolids management facility. Soils contained 0.16, 22.8, 45.3 mg Cd kg–1 and 43.1, 482, 812 mg Zn kg–1 respectively with initial pH 6.0, 6.1, 6.4. In greenhouse studies, Swiss chard (Beta vulgaris var. cicla), a Cd-accumulator maize (inbred B37 Zea mays) and a southern France Cd-hyperaccumulator genotype of Noccaea caerulescens were tested for Cd accumulation and phytoextraction. Soil pH was adjusted from ∼5.5–7.0. Additionally 100 rice (Oryza sativa) genotypes and the Ni-hyperaccumulator Alyssum murale were screened for potential phytoextraction use.Chard suffered phytotoxicity at low pH and accumulated up to 90 mg Cd kg–1 on the biosolids amended mine soil. The maize inbred accumulated up to 45 mg Cd kg–1 with only mild phytotoxicity symptoms during early growth at pH > 6.0. N. caerulescens did not exhibit phytotoxicity symptoms at any pH, and accumulated up to 235 mg Cd kg–1 in 3 months. Reharvested N. caerulescens accumulated up to 900 mg Cd kg–1 after 10 months. Neither Alyssum nor 90% of rice genotypes survived acceptably.Both N. caerulescens and B37 maize show promise for Cd phytoextraction in IL and require field evaluation; both plants could be utilized for nearly continuous Cd removal. Other maize inbreds may offer higher Cd phytoextraction at lower pH, and mono-cross hybrids higher shoot biomass yields. Further, maize grown only for biomass Cd maximum removal could be double-cropped.

Chromium picolinate (CrPic) and chromium nicotinate preparations (CrNicl, CrNic2, CrNic3) were investigated with tH and 13C NMR, FTIR, and molecular modeling. CrPic is crystalline and bidentately coordinated. Cr-PicA bonding broadens the NMR signal or shifts it so far downfieid that it is not detectable. All CrNic preparations are noncrystalline, and results provide no evidence that nicotinic acid (NicA) is O-coordinated to Cr. The complex colors may be due to O-coordination with 1-120 and~or OH, not NicA. I H NMR spectra of CrNic l have two sets of peaks. One set has a significant 8 with respect to NicA, indicating that NicA is more strongly associated with Cr. CrNicl 13C data show small, uniform 8 with respect to NicA, indicating that strong localized Cr-COOH bonding is unlikely. The magnitude of 8, :3C, and 1H exchange data suggests that limited Cr-N bonding may occur in CrNicl. CrNic2 and CrNic3 show little difference from NicA spectra. FTIR spectra of all CrNic complexes, but not CrPic, PicA, or NicA, show bound OH and~ or HzO. CrNic complexes are probably olates, with Cr and NicA OHpolymerized. CrPic exchanges with CrNicl in DMSO. This exchange may provide a mechanism for the absorption and active transport of Cr in biological systems. []ournal of Inorganic Biochemistry 66, 119-130 (1997) @ 1997 Elsevier Science Inc.

Six hundred million years ago, the fossil record displays the sudden appearance of intracellular detail and the 32 phyla. The ‘‘Cambrian Explosion’’ marks the onset of dominant aerobic life. Fossil intracellular structures are so similar to extant organisms that they were likely made with similar membrane lipids and proteins, which together provided for organisation and specialisation. While amino acids could be synthesised over 4 billion years ago, only oxidative metabolism allows for the synthesis of highly unsaturated fatty acids, thus producing novel lipid molecular species for specialised cell membranes. Docosahexaenoic acid (DHA) provided the core for the development of the photoreceptor, and conversion of photons into electricity stimulated the evolution of the nervous system and brain. Since then, DHA has been conserved as the principle acyl component of photoreceptor synaptic and neuronal signalling membranes in the cephalopods, fish, amphibian, reptiles, birds, mammals and humans. This extreme conservation in electrical signalling membranes despite great genomic change suggests it was DHA dictating to DNA rather than the generally accepted other way around. We offer a theoretical explanation based on the quantum mechanical properties of DHA for such extreme conservation. The unique molecular structure of DHA allows for quantum transfer and communication of p-electrons, which explains the precise depolarisation of retinal membranes and the cohesive, organised neural signalling which characterises higher intelligence.

The ability to exploit and thrive on a wide variety of foodstuffs from diverse environments is a hallmark of Homo sapiens. Humans are particularly well adapted to exploit waterside environments, where they can forage in areas offering protection from both terrestrial and aquatic predators. Humans are able to walk, run, climb, wade, swim and dive, and our research indicates that the most parsimonious explanation for this combination of locomotor traits, and for Man's current anatomy, physiology, nutritional requirements and unique intellect is evolution in a littoral environment. This model is consistent with the location and presumed palaeoecologies of all early Homo fossils and artifacts, and could help explain the rapid dispersal of Homo in the early Pleistocene (2.56-0.78 million years ago (Ma)), the colonization of Australia and Indonesia in the middle Pleistocene (0.78-0.13 Ma), and the rapid dispersal of Homo sapiens in the late Pleistocene (0.13-0.012 Ma). Reliance on the aquatic food chain is also a facile method for providing consistently abundant brain-specific nutrition for all members of a group or society, thus facilitating the development of the technology and culture that is uniquely human.

Th is paper reviews progress in phytoextraction of soil elements and illustrates the key role of hyperaccumulator plant species in useful phytoextraction technologies. Much research has focused on elements which are not practically phytoextracted (Pb); on addition of chelating agents which cause unacceptable contaminant leaching and are cost prohibitive; and on plant species which off er no useful phytoextraction capability (e.g., Brassica juncea Czern). Nickel phytoextraction by Alyssum hyperaccumulator species, which have been developed into a commercial phytomining technology, is discussed in more detail. Nickel is ultimately accumulated in vacuoles of leaf epidermal cells which prevents metal toxicity and provides defense against some insect predators and plant diseases. Constitutive up-regulation of trans-membrane element transporters appears to be the key process that allows these plants to achieve hyperaccumulation. Cadmium phytoextraction is needed for rice soils contaminated by mine wastes and smelter emissions with 100-fold more soil Zn than Cd. Although many plant species can accumulate high levels of Cd in the absence of Zn, when Cd/Zn > 100, only Th laspi caerulescens from southern France has demonstrated the ability to phytoextract useful amounts of Cd. Production of element-enriched biomass with value as ore or fertilizer or improved food (Se) or feed supplement may off set costs of phytoextraction crop production. Transgenic phytoextraction plants have been achieved for Hg, but not for other elements. Although several researchers have been attempting to clone all genes required for eff ective hyperaccumulation of several elements, success appears years away; such demonstrations will be needed to prove we have identifi ed all necessary processes in hyperaccumulation.

Two strategies of phytoextraction have been shown to have promise for practical soil remediation: domestication of natural hyperaccumulators and bioengineering plants with the genes that allow natural hyperaccumulators to achieve useful phytoextraction. Because different elements have different value, some can be phytomined for profit and others can be phytoremediated at lower cost than soil removal and replacement. Ni phytoextraction from contaminated or mineralized soils offers economic return greater than producing most crops, especially when considering the low fertility or phytotoxicity of Ni rich soils. Only soils that require remediation based on risk assessment will comprise the market for phytoremediation. Improved risk assessment has indicated that most Zn + Cd contaminated soils will not require Cd phytoextraction because the Zn limits practical risk from soil Cd. But rice and tobacco, and foods grown on soils with Cd contamination without corresponding 100-fold greater Zn contamination, allow Cd to readily enter food plants and diets. Clear evidence of human renal tubular dysfunction from soil Cd has only been obtained for subsistence rice farm families in Asia. Because of historic metal mining and smelting, Zn + Cd contaminated rice soils have been found in Japan, China, Korea, Vietnam and Thailand. Phytoextraction using southern France populations of Thlaspi caerulescens appears to be the only practical method to alleviate Cd risk without soil removal and replacement. The southern France plants accumulate 10-20-fold higher Cd in shoots than most T. caerulescens populations such as those from Belgium and the UK. Addition of fertilizers to maximize yield does not reduce Cd concentration in shoots; and soil management promotes annual Cd removal. The value of Cd in the plants is low, so the remediation service must pay the costs of Cd phytoextraction plus profits to the parties who conduct phytoextraction. Some other plants have been studied for Cd phytoextraction, but annual removals are much lower than the best T. caerulescens. Improved cultivars with higher yields and retaining this remarkable Cd phytoextraction potential are being bred using normal plant breeding techniques.

The polyunsaturated fatty acid (PUFA) composition of the mammalian central nervous system is almost wholly composed of two long-chain polyunsaturated fatty acids (LC-PUFA), docosahexaenoic acid (DHA) and arachidonic acid (AA). PUFA are dietarily essential, thus normal infant/neonatal brain, intellectual growth and development cannot be accomplished if they are deficient during pregnancy and lactation. Uniquely in the human species, the fetal brain consumes 70% of the energy delivered to it by mother. DHA and AA are needed to construct placental and fetal tissues for cell membrane growth, structure and function. Contemporary evidence shows that the maternal circulation is depleted of AA and DHA during fetal growth. Sustaining normal adult human brain function also requires LC-PUFA.Homo sapiens is unlikely to have evolved a large, complex, metabolically expensive brain in an environment which did not provide abundant dietary LC-PUFA. Conversion of 18-carbon PUFA from vegetation to AA and DHA is considered quantitatively insufficient due to a combination of high rates of PUFA oxidation for energy, inefficient and rate limited enzymatic conversion and substrate recycling. The littoral marine and lacustrine food chains provide consistently greater amounts of pre-formed LC-PUFA than the terrestrial food chain. Dietary levels of DHA are 2.5-100 fold higher for equivalent weights of marine fish or shellfish vs. lean or fat terrestrial meats. Mammalian brain tissue and bird egg yolks, especially from marine birds, are the richest terrestrial sources of LC-PUFA. However, land animal adipose fats have been linked to vascular disease and mental ill-health, whereas marine lipids have been demonstrated to be protective. At South African Capesites, large shell middens and fish remains are associated with evidence for some of the earliest modern humans. Cape sites dating from 100 to 18 kya cluster within 200 km of the present coast. Evidence of early H. sapiens is also found around the Rift Valley lakes and up the Nile Corridor into the Middle East; in some cases there is an association with the use of littoral resources. Exploitation of river, estuarine, stranded and spawning fish, shellfish and sea bird nestlings and eggs by Homo could have provided essential dietary LC-PUFA for men, women, and children without requiring organized hunting/fishing, or sophisticated social behavior. It is however, predictable from the present evidence that exploitation of this food resource would have provided the advantage in multi-generational brain development which would have made possible the advent of H. sapiens. Restriction to land based foods as postulated by the savannah and other hypotheses would have led to degeneration of the brain and vascular system as happened without exception in all other land based apes and mammals as they evolved larger bodies.

a Imperial College, Department of Cancer and Surgery, Division of Reproductive Physiology, Obstetrics and Gynaecology, Room 334, Chelsea and Westminster Hospital Campus, 369 Fulham Road, London SW109NH, UK b United States Department of Agriculture Agricultural Research Service, Beltsville, MD, USA c Department of Mathematics and Computer Science, Liverpool Hope University, UK d London Metropolitan University, Holloway Campus, London, UK