Reply To: Scripts 2014

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    Chemical Transformations (Figure 2a)
    Reduction and oxidation are coupled processes in natural systems and involve the transfer of electrons to and from chemical moieties. A number of NMs may be composed of or contain constituents that undergo reduction, oxidation, or both in aquatic and terrestrial environments. These include elemental metal NMs such as silver(21, 22) and iron.(23) Ceria NPs can contain both Ce(III) and Ce(IV) and subsequent sorption of macromolecules can alter the ratio of Ce(III)/Ce(IV) on the NP surface.(24) The sulfur and selenium in some metal sulfides and metal selenides, major components of quantum dots, are also susceptible to oxidation that may release soluble toxic metal ions such as Cd.(2, 25) In some cases, oxidation may result in the accumulation of a relatively insoluble oxide surface coating on the NP that passivates the surface and reduces subsequent oxidation, while also forming metal-oxide phases with a high capacity for binding ions from solution. In other cases, (e.g., Ag NPs), oxidation of Ag(0) to Ag(I) is required to dissolve and release bactericidal Ag+.(22) Natural waters and aerated soils are predominantly oxidizing environments, while carbon-rich sediments and groundwater may be depleted of oxygen and result in NM reduction. In dynamic redox environments such as tidal zones one may well encounter cycling of NMs between different redox states.—Sunlight-catalyzed redox reactions (photooxidation and photoreduction) may prove to be very important transformation processes affecting NM coatings, oxidation state, generation of reactive oxygen species (ROS), and persistence. The oxidation and mineralization of fullerenes dispersed in water by natural sunlight may attenuate carbon-based nanomaterials.(26) Sunlight exposure caused the degradation of gum arabic coatings on Ag NPs and induced aggregation and sedimentation from solution.(27) Many NMs will be innately photoactive (e.g., TiO2 and CNTs), potentially producing ROS when exposed to sunlight.(28) Others may be oxidized or reduced by sunlight, changing their redox state, charge, and therefore potential for toxicity.-Dissolution and sulfidation are important processes affecting NP surface properties, toxicity, and persistence. This is especially true for NMs made from Class B soft metal cations (e.g., Ag, Zn, and Cu) because they form partially soluble metal-oxides, and because they have a strong affinity for inorganic and organic sulfide ligands. Class B metal NMs commonly express toxicity through dissolution and release of toxic cations, such that persistence is reduced but toxicity is increased.[F4] Complete dissolution may allow prediction of their impact using existing models for metal speciation and effects. However, Class B metals’ affinities for electron-dense sulfur molecules make them highly reactive with sulfur-containing biomacromolecules and inorganic sulfur in sediments, soils, and air. Formation of a relatively insoluble metal-sulfide shell on the particle surface can alter the surface charge and induce aggregation.(10) Determining the particle properties (e.g., particle size, capping agent, etc.) and environmental conditions (redox state and availability of free sulfide) that affect their dissolution and/or sulfidation rates are important for assessing their potential to release toxic metal cations, and their ultimate toxicity(29) and persistence in the environment.(30)–Adsorption of macromolecules or organic and inorganic ligands on NM surfaces can significantly affect their surface chemistry and resulting behavior in biological and environmental systems. For example, adsorption of polymer coatings on NPs generally decreases their attachment to silica surfaces, suggesting greater mobility in the environment and potentially less effective removal in drinking water treatment.(31)[F5] Adsorption of biomacromolecules is a particularly important transformation and is treated separately below. Adsorption of organic ligands or metal cations or oxo-anions can occur on either the surface of the core NM or within the organic macromolecular coating of the particle. Organic ligands, such as those containing thiol groups may affect NM dissolution, charge, and stability against aggregation.(32, 33) Organics present in the atmosphere can also condense onto airborne NMs, altering their surface chemistry.(34) Understanding the effects of organic ligands and adsorbed cocontaminants on NM toxicity is needed to fully assess the potential for harm.
    Figure 2. (a) Representative chemical transformations of metal nanomaterials and the potential impacts on their behavior and effects in the environment. AgNPs are used to exemplify the types of transformations that may occur. The magnitude of arrows approximately correlates with potential for these processes to occur as determined from the limited data available on these processes. (b) Effects of physical transformations including aggregation and heteroaggregation on the reactivity and transport of nanomaterials. The magnitude of arrows approximately correlates with potential for these processes to occur as determined from the limited data available on these processes. (c) Biologically mediated transformations of nanomaterials and their coatings, and the subsequent impact on fate, transport, and effects. Arrows do not indicate the relative potential for these processes to occur due to the limited data currently available for that assessment. (d) Effects of nanomaterial interactions with macromolecules such as proteins and natural organic matter. Adsorbed macromolecules can affect aggregation, nanoparticle-biointeractions, biouptake, and fate, transport, and effects in the environment. Arrows do not indicate the relative potential for these processes to occur due to the limited data currently available for that assessment.
    Physical Transformations (Figure 2b)
    Aggregation of NPs reduces the surface area to volume effects on NM reactivity. This increase in aggregate size in turn affects their transport in porous media, sedimentation, reactivity, uptake by organisms, and toxicity. Over time, aggregation of NPs into clusters is inevitable without engineered or incidental coatings to decrease aggregation. Aggregation may take on two forms: homoaggregation between the same NMs, or heteroaggregation between a NM and another particle in the environment. In most cases, the greater concentration of environmental particles compared to NMs will result in heteroaggregation. Where aggregation occurs, the number concentration of NMs in the suspension decreases, with a concomitant increase in their effective (aggregate) size. For example, 30–70 nm diameter Fe(0) NPs rapidly aggregate in water to form micrometer-sized aggregates,(35) greatly decreasing their mobility in the subsurface and likely pathways of exposure to sensitive receptors. Heteroaggregation between NMs and comparatively larger particles (e.g., clay) could change NM behavior if the NM–clay heteroaggregates ultimately move more like a clay particle that the NM.(36)
    Aggregation can also decrease the “available” surface area of the materials, thereby decreasing reactivity[F6]. However, the decrease in specific surface area will depend on particle number, size distribution, and the fractal dimensions of the aggregate.(37) Aggregation can therefore decrease toxicity when the toxic response is a result of a surface area-mediated reaction such as ROS generation or dissolution. Aggregation may also serve to increase the persistence of the NM if aggregation decreases the rate of dissolution or degradation, albeit in a different location compared to the dispersed NPs. The size of a NP may also affect its bioavailability to organisms. When aggregates or heteroaggregates become too large for direct transport across the cell wall and/or membrane, uptake may be prevented. Phagocytosis and similar mechanisms may also be affected. Conversely, heteroaggregation with soft biogenic particles might increase NM bioavailability (e.g., uptake by filter feeders who preferentially remove larger particles). Delineating the effects of aggregation on uptake and any subsequent toxicity will be challenging since it is a dynamic process, uptake will be highly dependent on both the species examined and its aqueous chemical environment and metabolic state, and because instruments for tracking NMs in situ or in vivo are lacking.
    Biologically Mediated Transformations (Figure 2c)
    Biological transformations of NMs are inevitable in living tissues (both intracellular and extracellular) and environmental media (e.g., soils). [F7]Redox reactions are fundamental to growth in all biological systems. These reactions take place in the cytoplasm, cell wall, cell membrane, and extracellularly via redox-labile enzymes and cytochromes or through ancillary intracellular ROS production such as hydroxyl radicals or H2O2. The redox reactions between bacteria and naturally occurring, nanoscale iron oxide are well understood.(38) Moreover, bacteria such as Geobacter and Shewanella spp. were recently demonstrated to produce nanoscale silver particles by reduction of Ag+ from solution.(39)
    Biologically mediated transformations of both the underlying NM core and the coatings are possible, and these transformations can affect the behavior of the NMs including surface charge, aggregation state, and reactivity, which ultimately can affect transport, bioavailability, and toxicity. The oxidation and carboxylation of CNTs by OH radicals produced from the horseradish peroxidase enzyme has been demonstrated.(40) This oxidation increases the surface charge of the CNTs and stability against aggregation while decreasing hydrophobicity. Moreover, this biological oxidation and surface functionalization may affect the toxic potential of CNTs.(41)
    Biotransformation of polymer coatings used on many NMs for biomedical applications is also feasible.[F8] Covalently bound poly(ethylene glycol) (PEG) coatings on engineered NMs, for instance, were shown to be bioavailable to microorganisms isolated from an urban stream.(20) Moreover, the biotransformation of the PEG coating caused the NMs to aggregate. Biological transformations of NMs, especially carbon-based ones, and their organic coatings may ultimately act to attenuate their concentrations in the environment or to affect transport, but it remains to be seen if these processes occur at rates that are high enough to be important. Perhaps the most critical biotransformation of NMs is adsorption of biomacromolecules on their surfaces as discussed next.
    Statins and Mitochondrial Side Effects
    From the viewpoint of side effect causation there are two primary effects of statins. The first is what this class of drugs was designed for – inhibition of cholesterol synthesis through inhibition of the mevalonate pathway. –
    The second has to do with the other consequences of mevalonate blockade – cellular dysfunction brought on primarily by reduction of CoQ10 and dolichols. –There are many, many other consequences of mevalonate blockade, but the two effects alluded to above designate those having the most important and disastrous clinical consequences. –Most clinicians should now be well aware that to lower cholesterol is to cause cognitive dysfunction. Over 7,000 reports of transient global amnesia (TGA) have been reported to FDA via Medwatch just for the single statin, Lipitor, and TGA is just the tip of the iceberg of true clinical effects from cholesterol lowering. –My focus on this article is that other main group of side effects, those due to the other consequences of mevalonate pathway inhibition – CoQ10 and dolichols. These effects strike at the very heart of cellular function our mitochondria that create the energy for the cells in our bodies.-A report by a research group in France – F. Galtier and others – titled Effects of high dose statins on muscular mitochondrial metabolism (Toxicology and Applied Pharmacology. 28 June 2012) highlighted the effects of statins on mitochndria. -Nearly a decade ago I postulated a mitochondrial DNA origin to statin damage. This French study appeals because it is current and clear-cut. Twenty-four healthy male subjects were used. Half received simvastatin (Zocor) 80 mg daily for 8 weeks. The remaining half took placebo. Blood, urine and a stress test were done at baseline and at follow-up 8 weeks later and studies of mitochondrial oxidative function were done on muscle biopsies taken 4 days before the second stress test. –The results were analyzed and compared documenting that the statin induced muscle toxicity was directly related to mitochondrial oxidation. The reduction of CoQ10 and dolichols by the use of the statin had led to excess mitochondrial oxidation. –Most of us have no awareness of just how critical CoQ10 is to our function. After the age of 50 we become increasingly unable to synthesize it and must depend almost entirely on what we take in by mouth. Since dietary CoQ10 is usually completely inadequate, supplements become the mainstay of CoQ10 function as we age (the richest dietary sources are foods not widely eaten like hearts from cows, lambs, pigs and chickens). –Even on our best days, mitochondrial mutations occur by the tens of thousands. They are an inevitable consequence of normal metabolic activity. The “reactive oxygen species” (ROS) such as peroxidases and hydroxyl radicals, are produced as a byproduct of metabolism, and desperately seek electrons to balance their electrical state. — It is this “stealing” of electrons from adjacent tissue, including DNA strands, that causes the damage. We have evolved a very efficient anti-oxidative system for the purpose of minimizing this electron theft. Included in this system are such enzymes as superoxide dismutase and glutathione, and such non-enzymatic substances as coenzyme Q10 and vitamins C and E. [F9]
    Although CoQ10 has plenty of help in its anti-oxidant role, I stress CoQ10’s special importance because of its location within the mitochondria as a vital component of both complex one and complex two of the mitochondria’s electron transfer sequence. What better location for the job at hand than being physically there, where the action is occurring. –CoQ10 is not only a vital component in this process of energy formation, it is also superbly placed for its powerful anti-oxidant function. In concert with the other members of this protective system, CoQ10 suffices to keep oxidative damage to a minimum. –The DNA lesions that finally occur after the neutralizing effects of our legions of anti-oxidant warriors are then identified and corrected by another protective system of amazing efficiency. Tens of thousands of DNA lesions occur daily despite all our anti-oxidant system can do. This is a sobering reality of the constant skirmish for change, seeking the best solution for meeting environmental differences. –Fortunately most of these errors never make it beyond the next cell division, at which point they are replaced naturally by normal configurations. But the gradual buildup of these DNA errors can result in progressive loss of functional DNA, the usual cause of chronic disease and aging. –Most of the serious damage is to our bases, those four amino acids: adenine, cytosine, thymine and guanine, comprising our DNA strands. Some of the oxidative damage can be reversed simply by direct chemical means. –Far more important to us is the base excision repair process, in which faulty bases must be excised and replaced by correct ones. This is one of the major repair requirements, occurring tens of thousands of times daily and each one requiring a specific glycohydrolase. –Since glycohydrolase is one of our ubiquitous glycoproteins, requiring dolichols for synthesis, one must consider the possibility of altered glycohydrolase availability with statin use because of the well-known tendency of statins to inhibit dolichols along with CoQ10. –Please understand that the effect I am writing about is not some rare, remotely possible event. Mevalonate blockade of varying degrees is inevitable when statins are used. Although every cell in our bodies is affected by reductase inhibition those cells having greater need of energy such as muscle and heart cells, kidney and liver will be affected more. –The only escape from the consequences of this inhibition is the presence of pathway alternatives to the usual mevalonate one for synthesis of CoQ10, dolichols or even cholesterol. Serum cholesterol occasionally does not respond to statin use, suggesting the presence of alternative pathways for synthesis. If this is true for cholesterol, it is true for all other biochemicals equally dependent upon the mevalonate pathway. –Other than for these considerations, mevalonate blockade is inevitable with statin use and is the cause of the overwhelming majority of adverse reactions. The consequence of CoQ10 and dolichol inhibition is mitochondrial damage. It is inescapable and every MD using or recommending these drugs needs to understand this.
    Onion extract structural changes during in vitro digestion and its potential antioxidant effect on brain lipids obtained from low- and high-fat-fed mice.
    Free Radic Res. 2013 Dec;47(12):1009-15
    Authors: Hur SJ, Lee SJ, Kim DH, Chun SC, Lee SK
    This study investigated the effects of onion (Allium cepa, L.) extract on the antioxidant activity of lipids in low-and high-fat-fed mouse brain lipids and its structural change during in vitro human digestion. The onion extracts were passed through an in vitro human digestion model that simulated the composition of the mouth, stomach, and small intestine juice. The brain lipids were collected from low- and high-fat-fed mouse brain and then incubated with the in vitro-digested onion extracts to determine the lipid oxidation. The results confirmed that the main phenolics of onion extract were kaempferol, myricetin, quercetin, and quercitrin. The quercetin content increased with digestion of the onion extract. Antioxidant activity was strongly influenced by in vitro human digestion of both onion extract and quercetin standard. After digestion by the small intestine, the antioxidant activity values were dramatically increased, whereas the antioxidant activity was less influenced by digestion in the stomach for both onion extract and quercetin standard. The inhibitory effect of lipid oxidation of onion extract in mouse brain lipids increased after digestion in the stomach. The inhibitory effect of lipid oxidation of onion extract was higher in the high-fat-fed mouse brain lipids than that in the low-fat-fed mouse brain lipids. The major study finding is that the antioxidative effect of onion extract may be higher in high-fat-fed mouse brain lipids than that in low-fat-fed mouse brain lipids. Thus, dietary onion may have important applications as a natural antioxidant agent in a high-fat diet.–PMID: 24074442 [PubMed – indexed for MEDLINE]
    Hot bath for the treatment of chronic renal failure.
    Ren Fail. 2014 Feb;36(1):126-30
    Authors: Ye T, Tu W, Xu G
    BACKGROUND: Dialysis and its complications were debated recently. There was lack of an adjuvant renal replacement method to reduce the complications of patients with chronic renal failure and dialysis itself.
    MATERIALS AND METHODS: In this article, we reviewed the role of thermal sweating in treating of the patients with chronic renal failure, and the role of traditional Chinese medicine in the therapy of chronic kidney diseases.
    RESULTS: Thermal sweating can reduce interdialytic weight gain and improve the patients’ blood pressure; Chinese herbal medicine can promote the excretion of uremic toxicities and relieve the skin disorders of these patients.-CONCLUSIONS: Traditional Chinese medicine-mediated hot bath could be one of the adjuvant renal replacement methods.–PMID: 24060101 [PubMed – indexed for MEDLINE]
    Antioxidant and anti-cancer cell proliferation activity of propolis extracts from two extraction methods.
    Asian Pac J Cancer Prev. 2013;14(11):6991-5
    Authors: Khacha-ananda S, Tragoolpua K, Chantawannakul P, Tragoolpua Y
    Antioxidant activity, total phenolic, total flavonoid compounds and cytotoxicity to cancer cell lines of propolis extracts from two extraction methods were investigated in this study. Propolis was collected from Phayao province and extracted with 70% ethanol using maceration and sonication techniques. The antioxidant activity was evaluated by DPPH assay. Total phenolic and flavonoid compounds were also determined. Moreover, the cytotoxicity of propolis was evaluated using MTT assay. The percentage propolis yield after extraction using maceration (18.1%) was higher than using sonication (15.7%). Nevertheless, antioxidant and flavonoid compounds of the sonication propolis extract were significant greater than using maceration. Propolis extract from sonication showed antioxidant activity by 3.30 ± 0.15 mg gallic acid equivalents/g extract. Total phenolic compound was 18.3 ± 3.30 mg gallic acid equivalents/g extract and flavonoid compound was 20.49 ± 0.62 mg quercetin/g extract. Additionally, propolis extracts from two extraction methods demonstrated the inhibitory effect on proliferation of A549 and HeLa cancer cell lines at 24, 48 and 72 hours in a dose-dependent manner. These results are of interest for the selection of the most appropriate method for preparation of propolis extracts as potential antioxidant and anticancer agents.
    PMID: 24377638 [PubMed – indexed for MEDLINE]
    Environmental Transformations of Silver Nanoparticles- Impact on Stability and Toxicity
    Environ. Sci. Technol., 2012, 46 (13), pp 6900–6914
    DOI: 10.1021/es2037405
    Publication Date (Web): February 16, 2012
    Copyright © 2012 American Chemical Society
    *Phone: 650-723-7513. E-mail: [email protected].
    This article is part of the Transformations of Nanoparticles in the Environment special issue.
    Silver nanoparticles (Ag-NPs) readily transform in the environment, which modifies their properties and alters their transport, fate, and toxicity. It is essential to consider such transformations when assessing the potential environmental impact of Ag-NPs. This review discusses the major transformation processes of Ag-NPs in various aqueous environments, particularly transformations of the metallic Ag cores caused by reactions with (in)organic ligands, and the effects of such transformations on physical and chemical stability and toxicity. Thermodynamic arguments are used to predict what forms of oxidized silver will predominate in various environmental scenarios. Silver binds strongly to sulfur (both organic and inorganic) in natural systems (fresh and sea waters) as well as in wastewater treatment plants, where most Ag-NPs are expected to be concentrated and then released[F10]. Sulfidation of Ag-NPs results in a significant decrease in their toxicity due to the lower solubility of silver sulfide, potentially limiting their short-term environmental impact. This review also discusses some of the major unanswered questions about Ag-NPs, which, when answered, will improve predictions about their potential environmental impacts. Research needed to address these questions includes fundamental molecular-level studies of Ag-NPs and their transformation products, particularly Ag2S-NPs, in simplified model systems containing common (in)organic ligands, as well as under more realistic environmental conditions using microcosm/mesocosm-type experiments. Toxicology studies of Ag-NP transformation products, including different states of aggregation and sulfidation, are also required. In addition, there is the need to characterize the surface structures, compositions, and morphologies of Ag-NPs and Ag2S-NPs to the extent possible because they control properties such as solubility and reactivity.
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    TOP D
    [F1]So the concept that it all can come out is not entirely active and is in severe error and in the bioacumaltion is where you wind up with compromises on the bodily functions as well as environmental issues
    [F2]Morphology of the components
    [F3]Interesting –this would be contingent on what polymer they used—what type of protein or ligand was used as well
    [F4]SO the toxic effect of silver –zinc and copper in there nano format would be in there being dissolved –and as they are being dissolved they release there toxicity
    [F5]Water may need to be double or tripled filtered
    [F6]In other words shutting down normal biology or bioactivity
    [F7]Living tissues—would be anything that is living
    [F8]Coatings—polymers may in fact increase the spreading of infestation in life forms
    [F9]So these should be utilized in order to offset the breaking down on the muscles and organs
    [F10]The Removal Of NanoSilver would require Sulphur—STS-MSM-NAC-METHIONINE-TAURINE-ALPHA LIPOIC ACID—GARLIC-ONION—LEEK—CHIVES-DMSO or any supplements that has sulpur in them will bind with this and remove them