Molar Basis Research Articles

Role of phosphorous additives on nitrogen conservation and maturity during pig manure composting.

This study compared different types and addition amounts of phosphorous additives on nitrogen conservation and maturity during pig manure composting. Phosphogypsum and superphosphate were applied with the same amount of phosphorus (5% of the initial total nitrogen, molar basis) or weight (10% of initial dry matter) and compared to a control treatment without additives. Results show that phosphorous additives could effectively conserve nitrogen. Adding phosphogypsum could significantly reduce NH3 emission and total nitrogen loss, but increase N2O emission. Application of 10% superphosphate mitigated NH3 emissions and total nitrogen loss but inhibited the organic matter degradation and compost maturity. More importantly, with the addition of 5% initial total nitrogen (i.e., 2.5% dry matter), superphosphate could synchronously reduce NH3 and N2O emissions and improve compost quality by introducing additional nutrients into the compost. In comprehensive evolution of gaseous emissions, nitrogen loss, and compost maturity, superphosphate addition with 2.5% of initial dry matter was suggested to be used in practice.

Effect of nickel loading on the performance of Ni/MgAl2O4 catalysts for LPG steam reforming

Ni catalysts with different loadings (10, 15 and 20 wt%) supported on MgAl2O4 were studied for Liquefied Petroleum Gas (LPG) steam reforming. In-situ X-ray diffraction (XRD) and XANES (X-ray absorption near-edge structure), analyses showed that the initial reduction temperature was related to the percentage of Ni present in the catalyst. Extended X-ray absorption fine structure (EXAFS) data indicated similar Ni-Ni interatomic distances for all the samples and very close to the simulated value found for reference of Ni0, indicating the complete reduction of the samples. MgAl2O4 supported Ni catalysts were active for LPG steam reforming at 873 K, with some deactivation after 24 h of reaction. The samples with higher Ni loadings (20Ni/MgAl2O4 and 15Ni/MgAl2O4) showed similar LPG steam reforming products, with H2 representing around 78% of the products detected in the gas phase (dry molar basis). 10Ni/MgAl2O4 was less active, although it also presented high H2 formation. Thermogravimetric analysis showed that carbon deposition was a significant factor for catalyst deactivation.

The plasma lipidome of the Quaker parrot (Myiopsitta monachus).

Dyslipidemias and lipid-accumulation disorders are common in captive parrots, in particular in Quaker parrots. Currently available diagnostic tests only measure a fraction of blood lipids and have overall problematic cross-species applicability. Comprehensively analyzing lipids in the plasma of parrots is the first step to better understand their lipid metabolism in health and disease, as well as to explore new lipid biomarkers. The plasma lipidome of 12 Quaker parrots was investigated using UHPLC-MS/MS with both targeted and untargeted methods. Targeted methods on 6 replicates measured 432 lipids comprised of sterol, cholesterol ester, bile acid, fatty acid, acylcarnitine, glycerolipid, glycerophospholipid, and sphingolipid panels. For untargeted lipidomics, precursor ion mass-to-charge ratios were matched to corresponding lipids using the LIPIDMAPS structure database and LipidBlast at the sum composition or acyl species level of information. Sterol lipids and glycerophospholipids constituted the majority of plasma lipids on a molar basis. The most common lipids detected with the targeted methods included free cholesterol, CE(18:2), CE(20:4) for sterol lipids; PC(36:2), PC(34:2), PC(34:1) for glycerophospholipids; TG(52:3), TG(54:4), TG(54:5), TG(52:2) for glycerolipids; SM(d18:1/16:0) for sphingolipids; and palmitic acid for fatty acyls. Over a thousand different lipid species were detected by untargeted lipidomics. Sex differences in the plasma lipidome were observed using heatmaps, principal component analysis, and discriminant analysis. This report presents the first comprehensive database of plasma lipid species in psittacine birds and paves the way for further research into blood lipid diagnostics and the impact of diet, diseases, and drugs on the parrot plasma lipidome.

Proline is a quencher of singlet oxygen and superoxide both in in vitro systems and isolated thylakoids.

Proline is a versatile plant metabolite, which is produced in large amounts in plants exposed to osmotic and oxidative stress. Proline has been shown to provide protection against various reactive oxygen species (ROS), such as hydrogen peroxide and hydroxyl radicals. On the other hand, its protective effect against singlet oxygen has been debated, and it is considered ineffective against superoxide. Here we used various methods for the detection of singlet oxygen (electron paramagnetic resonance, EPR, spin trapping by 2,2,6,6-tetramethyl-4-piperidone, fluorescence probing by singlet oxygen sensor green, SOSG, and oxygen uptake due to chemical trapping) and superoxide (oxygen uptake due to oxygen reduction) in vitro and in isolated thylakoids. We demonstrated that proline does quench both singlet oxygen and superoxide in vitro. By comparing the effects of chemical scavengers and physical quenchers, we concluded that proline eliminates singlet oxygen via a physical mechanism, with a bimolecular quenching rate of ca. 1.5-4 106 M-1 s-1 . Our data also show that proline can eliminate superoxide in vitro in a process that is likely to proceed via an electron transfer reaction. We could also show that proline does quench both singlet oxygen and superoxide produced in isolated thylakoids. The scavenging efficiency of proline is relatively small on a molar basis, but considering its presence in high amounts in plant cells under stress conditions it may provide a physiologically relevant contribution to ROS scavenging, supplementing other nonenzymatic ROS scavengers of plant cells.

Environmental Sustainability of Mixed Cation Perovskite Materials in Photovoltaics Manufacturing

Efficiencies of lead halide perovskite photovoltaics have increased to 25%, putting them on track for commercialization within the next 1–3 years. Devices exhibiting the best combination of high efficiency and long operational lifetimes have used mixed cation perovskite absorber layers such as cesium/methylammonium/formamidinium lead iodide (CsxMAyFA1-x-yPbI3). However, the associated environmental burdens of the supply chains of perovskite precursors should also be considered when selecting compositions for commercialization. Prior literature based on laboratory-scale data reported a particularly high environmental burden for FA and warned against using these highest-performing film compositions. Here, we report a comprehensive study of the environmental impacts of common precursor salts used to form mixed cation perovskite films, using a life cycle assessment approach. We have used updated data sources, process scale-up concepts, and sensitivity analysis to build commercial-scale life cycle inventory models for perovskite precursors that can inform industrial manufacturing choices with more transparent and robust environmental analysis. Our results indicate that the process-based climate change, cumulative energy demand, and human toxicity impacts of CsI, MAI, and FAI are similar to each other and lead to iodide (PbI2) salts on a molar basis. The current cesium supply appears sufficient for near-future perovskite deployment. Additionally, the impacts of the perovskite precursors are ∼1000-fold smaller than those of glass when considering amounts needed per module area. Therefore, selection of perovskite composition can be based on PV efficiency and operational stability, without additional constraints of environmental impact.

Pilot-scale production of poly-3-hydroxybutyrate-co-3-hydroxyvalerate from fermented dairy manure: Process performance, polymer characterization, and scale-up implications

Polyhydroxyalkanoate (PHA) production from waste feedstocks using mixed microbial consortia (MMCs) is a promising alternative to conventional commercial production from refined feedstocks with axenic cultures. Prior work has reinforced this potential with nutrient-limited waste feedstocks and stringently controlled operation. The process would be more competitive, however, without these restrictions. To that end, a pilot-scale three-stage feast-famine MMC PHA system using dairy manure was operated with relaxed control for 87 days. All three stages absorbed operational fluctuations and exhibited stable performance comparable to tightly controlled analogs. PHA mass fractions (0.29 to 0.40 g/g; volatile solids basis) approached commercial viability and the purified PHA (21 ± 3% 3-hydroxyvalerate; mole basis) exhibited similarly stable material properties. Finally, characterization of the MMC's PHA synthesizing capability suggested an innate potential for medium-chain-length monomers. Collectively, these results demonstrate the potential for PHA production from a feedstock without a strict nutrient limitation and the process's resilience against operational variability.

Effects of stereoisomeric structure and bond location on the ignition and reaction pathways of hexenes

AbstractThe current work presents new experimental autoignition and speciation data on the two cis‐hexene isomers: cis‐2‐hexene and cis‐3‐hexene. The new data provide insights on the effects of carbon‐carbon double bond location and stereoisomeric structures on ignition delay times and reaction pathways for linear hexene isomers. Experiments were performed using the University of Michigan rapid compression facility to determine ignition delay times from pressure‐time histories. Stoichiometric (ϕ = 1.0) mixtures at dilution levels of inert gas to O2 = 7.5:1 (mole basis) were investigated at an average pressure of 11 atm and temperatures from 809 to 1052 K. Speciation experiments were conducted at T = 900 K for the two cis‐hexene isomers, where fast‐gas sampling and gas chromatography were used to identify and quantify the two cis‐hexene isomers and stable intermediate species. The ignition delay time data showed negligible sensitivity to the location of the carbon‐carbon double bond and the stereoisomeric structure (cis‐trans), and the species data showed no correlation with the stereoisomeric structure, but there was a strong correlation of some of the measured species with the location of the double bond in the hexene isomer. In particular, 2‐hexene showed strong selectivity to propene, acetaldehyde, and 1,3‐butadiene, and 3‐hexene showed selectivity to propanal. Model predictions of ignition delay times were in excellent agreement with the experimental data. There was generally good agreement for the model predictions of the species data for 2‐hexene; however, the mechanism overpredicted some of the small aldehyde (C2‐C4) species for 3‐hexene. Reaction pathway analysis indicates the hexenes are almost exclusively consumed by H‐atom abstraction reactions at the conditions studied (P = 11 atm, T > 900 K), and not by C3‐C4 scission as observed in high‐temperature (>1300 K) hexene ignition studies. Improved estimates for 3‐hexene + OH reactions may improve model predictions for the species measured in this work.

Chemical effects of ferrocene and 2-ethylhexyl nitrate on a low-octane gasoline: An experimental and numerical RCM study

An in-depth understanding of fuel additives chemical effects is crucial for optimal use or additive design dedicated to more efficient and cleaner combustion. This study aims at investigating the effect of an organometallic octane booster additive named ferrocene on the combustion of a low-octane gasoline at engine-relevant conditions. Rapid compression machine experiments were carried out at 10 bar, from 675 to near 1000 K for stoichiometric (Φ = 1) and lean (Φ = 0.5) mixtures. The neat surrogate fuel was a blend of toluene and n-heptane whose research octane number was 84. The doping level of additive was set at 0.1% molar basis. Ferrocene does not show a remarkable effect on the 1st- stage ignition but presents a strong inhibiting effect on the main ignition of the surrogate fuel at both equivalence ratios. The inhibiting effect increases with temperature within the investigated range. The negative temperature coefficient (NTC) behavior of the surrogate fuel is enhanced by ferrocene. A kinetic model developed by literature data assembly as well as a novel sub-mechanism involving the formation of alcohols from the reactions of iron species is proposed. The kinetic model developed simulates the inhibiting effect of ferrocene reasonably well at both equivalence ratios. Thanks to the validated kinetic model, the chemical effect of ferrocene on the fuel combustion is explored and compared with 2-ethylhexyl nitrate (EHN), which is a conventional reactivity enhancer. Three major differences between the two additives were identified: the high-temperature stability of the fuel additive, the influence of additive on the toluene reactivity and the effect of the additive on the NTC behavior. The results presented in this study contribute to the in-depth comprehension of chemical effect of two fuel additives (ferrocene and EHN) having opposite effects on fuel reactivity.

Experimental and numerical investigation of the promoting effect of a cetane booster in a low-octane gasoline fuel in a rapid compression machine: A study of 2-ethylhexyl nitrate

Modern societies require cleaner and more efficient internal combustion engines. Low-temperature combustion (LTC) has been proved to be a good step toward this goal. This study aims at investigating the promoting effect of a cetane booster additive named 2-ethylhexyl nitrate (EHN) on the reactivity of a low-octane gasoline at LTC-relevant conditions. Rapid compression machine experiments were conducted at 10 bar, from 675 to 960 K for stoichiometric mixtures. The neat fuel was a mixture of toluene and n-heptane whose research octane number is 84. The doping levels of the additive were set at 0.1 and 1% molar basis. At the experimental conditions, it is found that EHN provides a promoting effect on the surrogate reactivity over all the whole temperature range. This effect increases with EHN doping levels. The negative temperature coefficient (NTC) behavior of the surrogate fuel is mitigated by the presence of the additive. The EHN reactivity promoting effect is lowest around 710 K and then increases with temperature. Under some conditions, heat releases are observed during the compression process. The chemical reactivity of the fuel gas mixture during the piston movement has to be considered to get reliable simulations. Kinetic modeling works show a good agreement with experiments. The model of this study reproduces properly the EHN promoting effect over the whole range of investigated temperatures and doping levels. Numerical analyses were conducted. EHN can totally decompose during the compression process resulting in heat releases. EHN is less effective at low Tc (< 800 K) at lean condition than at stoichiometric condition. It is found that the EHN effect links to the OH radical formation and the NO2NO loop. The reactions between NO and n-heptyl peroxy radicals are found to be the main reason for the EHN effect in NTC region of the surrogate fuel oxidation.

Distribution of calcium, phosphorus, sulfur, magnesium, potassium, and sodium in major fractions of donkey milk

The aim of this study was to evaluate the concentrations of Ca, P, S, Mg, K, and Na, and their distribution in major fractions of donkey milk (i.e., fat, casein, whey proteins, and aqueous phase). Individual milk samples were collected by mechanical milking from 16 clinically healthy lactating donkeys. Milk yield per milking was recorded and milk gross composition, casein content, and pH were determined. Whole milk samples were centrifuged to separate fat and to obtain skim milk. Skim milk samples were ultracentrifuged to separate a sedimentable casein pellet and to obtain a supernatant whey (soluble) fraction, which was then ultrafiltered to obtain the aqueous phase of donkey milk. Whole milk and the processed samples were analyzed for the aforementioned elements by inductively coupled plasma-mass spectrometry. The concentration of elements associated with fat, casein, and whey proteins was then calculated. All the Na was present in the aqueous phase. The fat fraction in donkey milk carried very little or none of the investigated elements. The majority of Ca (62.9%) and P (53.1%) was associated with casein, and the rest of these elements was mostly present in the aqueous phase. The majority of Mg was present in the aqueous phase, but a relevant part (32.6%) was associated with the casein fraction. No K was associated with casein. On a molar basis, the ratio of colloidal Ca and P to casein (mmol/g of casein) was more than double the values reported in literature for cow milk. The correlation coefficient was negative between milk pH and P in the ultracentrifuged (r = -0.81) and ultrafiltered (aqueous) fraction (r = -0.66). Milk pH correlated positively with colloidal Ca (r = 0.59) and with the ratio of colloidal Ca to casein (mmol/g of casein; r = 0.68). Colloidal Ca and P were positively correlated (r = 0.64). These data suggest that the high ratio of colloidal Ca and P to donkey casein micelles is due to a larger amount of colloidal calcium phosphate bound to casein micelles compared with literature data on cow milk. The percentage of elements associated with whey proteins was less than 5% for Ca, P, and K, but Mg reached approximately 9% of total Mg. The majority of S (63.6%) was associated with whey proteins, and only one-fourth of this element was associated with casein, indicating a higher content of sulfur-containing amino acids in donkey whey proteins than in casein.

Comparison of Complete Extractive and Azeotropic Distillation Processes for Anhydrous Ethanol Production Using Aspen Plus™ Simulator

Performance of the extractive and azeotropic distillation processes using ethylene glycol and cyclohexane as solvents, respectively, for anhydrous ethanol production, were investigated using 02 RadFrac columns each and solvent recycling streams via simulation in Aspen Plus™ Simulator. Both operate at 1 atm, and feed flow rate equals to 100 kmol.h-1 (ethanol – 0.896 and water – 0.104 in mole fractions at the azeotropic point). The NRTL-RK was the model used for extractive and azeotropic distillations. The anhydrous ethanol purity from top of the 1st column of the extractive distillation (22 stages) was 99.50 % (on a mole basis) and water with 99.20 % of purity at the top of the 2nd column. On the other hand, in the azeotropic distillation, the 1st column (30 stages) had a bottom product of anhydrous ethanol purity of 99.99 % and water with 99.99 % of purity in the 2nd column, also at the bottom. Both processes produced anhydrous ethanol with a high-grade purity required by the standard norms ASTM D4806, EN 15376, and ANP 36. However, the extractive distillation spent 1,928.2 kW in the reboilers against 4,680.3 kW in the azeotropic distillation, demonstrating extractive distillation is the most economical option. Consequently, the energy consumption is an essential analysis for choosing the type of distillation, when an azeotropic mixture needs a good separation task. Finally, the extractive distillation demonstrated to be much more competitive than azeotropic distillation for this type of mixture although azeotropic distillation obtained a higher purity of anhydrous ethanol.

Evaluation of dyes removal by beta-cyclodextrin adsorbent

This work was aimed at evaluating the adsorptive properties of beta-cyclodextrin (β-CD) adsorbent towards methylene blue and congo red dyes removal. The adsorbent was characterized for specific surface area and surface chemistry. The results show that the surface area of β-CD adsorbent is small at 0.1 m2/g and the surface chemistry is rich in acidic oxygen groups. The dyes adsorption onto β-CD is favourable. Congo red adsorption exhibits a greater rate constant of 0.103 min−1 and a relatively shorter time to reach equilibrium at 40 min as opposed to 1500 min for methylene blue. On a molar basis, both dyes display a comparable maximum capacity of 1.80 × 10−2 mmol/g, with β-CD shows a greater affinity for congo red. The congo red adsorption is governed by hydrophobic host-guest complex interactions, while that for methylene blue is thru weak electrostatic interactions at the hydrophilic exterior of β-CD. To conclude, β-CD could be a promising adsorbent candidate for the treatment of dyes wastewater, where future works will be centred in improving the versatility and performance of the material.

Urine glyphosate level as a quantitative biomarker of oral exposure.

Since the classification of glyphosate as a Group 2A substance "probably carcinogenic to humans" by the IARC in 2015, human health concerns have been raised regarding the exposure of operators, bystanders, and consumers. Urine measurement studies have been conducted, but since toxicokinetic data on glyphosate in humans is lacking, a meaningful interpretation of this data regarding exposure is not possible. This study aims to determine the fraction of glyphosate and AMPA excretion in urine after consuming ordinary food with glyphosate residue, to estimate dietary glyphosate intake. Twelve participants consumed a test meal with a known amount of glyphosate residue and a small amount of AMPA. Urinary excretion was examined for the next 48h. Only 1% of the glyphosate dose was excreted in urine. The urinary data indicated the elimination half-life was 9h. For AMPA, 23% of the dose was excreted in urine, assuming that no metabolism of glyphosate to AMPA occurred. If all of the excreted AMPA was a glyphosate metabolite, this corresponds to 0.3% of the glyphosate dose on a molar basis. This study provides a basis for estimating oral glyphosate intake using urinary biomonitoring data.

A parapithecid stem anthropoid of African origin in the Paleogene of South America.

Phylogenetic evidence suggests that platyrrhine (or New World) monkeys and caviomorph rodents of the Western Hemisphere derive from source groups from the Eocene of Afro-Arabia, a landmass that was ~1500 to 2000 kilometers east of South America during the late Paleogene. Here, we report evidence for a third mammalian lineage of African origin in the Paleogene of South America-a newly discovered genus and species of parapithecid anthropoid primate from Santa Rosa in Amazonian Perú. Bayesian clock-based phylogenetic analysis nests this genus (Ucayalipithecus) deep within the otherwise Afro-Arabian clade Parapithecoidea and indicates that transatlantic rafting of the lineage leading to Ucayalipithecus likely took place between ~35 and ~32 million years ago, a dispersal window that includes the major worldwide drop in sea level that occurred near the Eocene-Oligocene boundary.

A South American anthropoid

Paleontology Although there are many primate lineages in the Old World, it is thought that the New World is home to just one group, the platyrrhine monkeys, which appear to have colonized the region during the Eocene. Seiffert et al. describe a new primate species on the basis of fossil molars found in the Peruvian Amazon that appears to belong to the Parapithecidae, a group of stem anthropoid primates best known from northern Africa (see the Perspective by Godinot). The fossils appear to be from a well-differentiated lineage, suggesting that this species had been evolving within South America for some time. It is likely that the ancestors of this new species arrived via a transatlantic rafting event when sea levels dropped at the Eocene–Oligocene transition ∼32 to 35 million years ago. Science , this issue p. [194][1]; see also p. [136][2] [1]: /lookup/doi/10.1126/science.aba1135 [2]: /lookup/doi/10.1126/science.abb4107

Flux Balance Analysis for Media Optimization and Genetic Targets to Improve Heterologous Siderophore Production.

SummarySiderophores are small molecule metal chelators secreted in sparse quantities by their native microbial hosts but can be engineered for enhanced production from heterologous hosts like Escherichia coli. These molecules have been proved to be capable of binding heavy metals of commercial and/or environmental interest. In this work, we incorporated, as needed, the appropriate pathways required to produce several siderophores (anguibactin, vibriobactin, bacillibactin, pyoverdine, and enterobactin) into the base E. coli K-12 MG1655 metabolic network model to computationally predict, via flux balance analysis methodologies, gene knockout targets, gene over-expression targets, and media modifications capable of improving siderophore reaction flux. E. coli metabolism proved supportive for the underlying production mechanisms of various siderophores. Within such a framework, the gene deletion and over-expression targets identified, coupled with complementary insights from medium optimization predictions, portend experimental implementation to both enable and improve heterologous siderophore production. Successful production of siderophores would then spur novel metal-binding applications.

Electronic and Catalytic Effects of Single-Atom Pd Additives on the Hydrogen Sensing Properties of Co3O4 Nanoparticle Films.

Atomically dispersed Pd additives significantly enhanced the hydrogen sensing performance of a Co3O4 nanoparticle film, and their electronic along with catalytic roles were comprehensively investigated based on a series of systematic experiments. Aggregates of Co3O4 nanoparticles (approximately 3 nm in size) with homogeneously dispersed Pd additives at concentrations in the range of 1-20% (on a molar basis with respect to Co) were generated in the gas phase via reactive pulsed laser ablation of Co-Pd alloy targets in He/O2 mixtures. The form of the Pd could be modified from single atoms to oxide clusters (1-2 nm), and the effects of these additives on the hydrogen sensing properties of thick films prepared by direct deposition were examined. The highest hydrogen sensing performance was obtained at 5% Pd loading, where single Pd atoms were present at the maximum density. Further Pd loading resulted in the formation of Pd oxide clusters and degraded the sensitivity. X-ray photoelectron spectroscopy and Pd K-edge X-ray absorption spectroscopy showed that single Pd atoms in the Pd4+ state at Co3+ sites on the Co3O4 nanoparticle surfaces donated electrons to the Co3O4 valence band. The greater concentration of free electrons led to an increase in the concentration of ionosorbed oxygen under dry air. Consequently, more ionosorbed oxygen was available for reaction with hydrogen, enhancing sensitivity. In situ X-ray absorption spectroscopy data confirmed that approximately 10% of the single Pd atoms in the Pd4+ state were reduced to Pd2+ during exposure to 1000 ppm H2, implying that a Pd4+ ↔ Pd2+ catalytic redox cycle accelerates the water formation reaction during hydrogen sensing. The present results provide deeper insights and understanding of the effects of noble metal additives on gas sensing, while highlighting the unique role of single-atom additives.

Fatty acid based novel precursors for polyesteramide hot melt adhesive

Polyesteramide (PEA) based hot melt adhesive (HMA) was successfully designed containing a high content of renewable mass. The PEA HMA was synthesized based on dimer acid (DA), catechol, ethylenediamine (EDA), ricinoleic acid amide (RA amide) which was synthesized by using ricinoleic acid and diethanolamine. RA amide was reacted with dimer acid with a varying concentration of RA amide by 5%, 10%, 15% and 20% on a molar basis. Catechol was further added on the molar basis of 10%, 20%, and 30% as a partial replacement of ethylenediamine. The effect on the properties of the hot melt adhesive, such as mechanical properties: tensile strength, shore D hardness, elongation at break; thermal properties: glass transition temperature (Tg), melting temperature (Tm), heat of crystallization (Hc), crystallization temperature (Tc); adhesion properties: lap shear strength (LSS) and T-peel strength (TPS); rheological properties and degree of crystallinity was investigated. It was observed that the mechanical and thermal properties are increased with increasing concentration of RA amide and catechol. These HMA materials could hold potential for sustainability and high adhesive performance.

Extra-Small Gold Nanospheres Decorated With a Thiol Functionalized Biodegradable and Biocompatible Linear Polyamidoamine as Nanovectors of Anticancer Molecules.

Gold nanoparticles are elective candidate for cancer therapy. Current efforts are devoted to developing innovative methods for their synthesis. Besides, understanding their interaction with cells have become increasingly important for their clinical application. This work aims to describe a simple approach for the synthesis of extra-small gold nanoparticles for breast cancer therapy. In brief, a biocompatible and biodegradable polyamidoamine (named AGMA1-SH), bearing 20%, on a molar basis, thiol-functionalized repeat units, is employed to stabilize and coat extra-small gold nanospheres of different sizes (2.5, 3.5, and 5 nm in gold core), and to generate a nanoplatform for the link with Trastuzumab monoclonal antibody for HER2-positive breast cancer targeting. Dynamic light scattering, transmission electron microscopy, ultraviolet visible spectroscopy, X-ray powder diffraction, circular dichroism, protein quantification assays are used for the characterization. The targeting properties of the nanosystems are explored to achieve enhanced and selective uptake of AGMA1-SH-gold nanoparticles by in vitro studies against HER-2 overexpressing cells, SKBR-3 and compared to HER-2 low expressing cells, MCF-7, and normal fibroblast cell line, NIH-3T3. In vitro physicochemical characterization demonstrates that gold nanoparticles modified with AGMA1-SH are more stable in aqueous solution than the unmodified ones. Additionally, the greater gold nanoparticles size (5-nm) is associated with a higher stability and conjugation efficiency with Trastuzumab, which retains its folding and anticancer activity after the conjugation. In particular, the larger Trastuzumab functionalized nanoparticles displays the highest efficacy (via the pro-apoptotic protein increase, anti-apoptotic components decrease, survival-proliferation pathways downregulation) and internalization (via the activation of the classical clathrin-mediated endocytosis) in HER-2 overexpressing SKBR-3 cells, without eliciting significant effects on the other cell lines. The use of biocompatible AGMA1-SH for producing covalently stabilized gold nanoparticles to achieve selective targeting, cytotoxicity and uptake is completely novel, offering an important advancement for developing new anticancer conjugated-gold nanoparticles.

Coupling Chlorin e6 to the surface of Nanoscale Gas Vesicles strongly enhances their intracellular delivery and photodynamic killing of cancer cells

Protein-based nanobubbles such as halophilic archaeabacterial gas vesicles (GVs) represent a new class of stable, homogeneous nanoparticles with acoustic properties that allow them to be visualized by ultrasound (US) waves. To design GVs as theranostic agents, we modified them to respond to light, with a view to locally generate reactive oxygen species that can kill cancer cells. Specifically, up to 60,000 photoreactive chlorin e6 (Ce6) molecules were chemically attached to lysine ε-amino groups present on the surface of each purified Halobacterium sp. NRC-1 GV. The resulting fluorescent NRC-1 Ce6-GVs have dimensions comparable to that of native GVs and were efficiently taken up by human breast [MCF-7] and human hypopharyngeal [FaDu-GFP] cancer cells as monitored by confocal microscopy and flow cytometry. When exposed to light, internalized Ce6-GVs were 200-fold more effective on a molar basis than free Ce6 at killing cells. These results demonstrate the potential of Ce6-GVs as novel and promising nanomaterials for image-guided photodynamic therapy.