Textural control of ionosilicas by ionic liquid templating.

Due to their unique self-assembly properties, ionic liquids (ILs) are versatile soft templates for the formation of mesoporous materials. Here, we report the use of ionic liquids as soft templates for the straightforward formation of mesoporous ionosilica phases. Ionosilicas are highly polyvalent functional materials that are constituted of ionic building blocks that are covalently immobilized within a silica hybrid matrix. Ionosilicas have attracted significant interest in the last few years due to their high potential for applications in water treatment and upgrading, separation and drug delivery. The straightforward and reproducible formation of mesoporous ionosilica phases is therefore highly desirable. In this context, we report the formation of mesoporous ionosilica phases via non-hydrolytic sol-gel procedures in the presence of ionic liquids. Ionic liquids appear as particularly versatile templates for mesoporous ionosilicas due to their high chemical similarity and affinity between ILs and silylated ionic precursors. We therefore studied the textures of the resulting ionosilica phases, after IL elimination, using nitrogen sorption, small angle X-ray scattering (SAXS) and transmission and scanning electron microscopies. All these techniques give concordant results and show that the textures of ionosilica scaffolds in terms of specific surface area, pore size, pore size distribution and connectivity can be efficiently controlled by the nature and the quantity of the ionic liquid that is used in the ionothermal sol-gel procedure.

Puberty is a critical window for the impact of diet on mammary gland development in the rabbit.

BACKGROUND: Nutritional changes can affect future lactation efficiency. In a rabbit model, an obesogenic diet initiated before puberty and pursued throughout pregnancy enhances mammary differentiation, but when started during the neonatal period can cause abnormal mammary development in early pregnancy. The aim of this study was to investigate the impact of an unbalanced diet administered during the pubertal period only. RESULTS: Consuming an obesogenic diet at puberty did not affect either metabolic parameters or certain maternal reproductive parameters at the onset of adulthood. In contrast, at Day 8 of pregnancy, epithelial tissue showed a lower proliferation rate in obesogenic-diet fed rabbits than in control-diet fed rabbits. Wap and Cx26 genes, mammary epithelial cell differentiation markers, were upregulated although Wap protein level remained unchanged. However, the expression of genes involved in lipid metabolism and in alveolar formation was not modified. CONCLUSION: Taken together, our results demonstrate that the consumption for 5 weeks of an obesogenic diet during the pubertal period initiates mammary structure modifications and affects mammary epithelial cell proliferation and differentiation. Our findings highlight the potentially important role played by unbalanced nutrition during critical early-life windows in terms of regulating mammary epithelial cell differentiation and subsequent function in adulthood.

Ethers as Oxygen Donor and Carbon Source in Non-hydrolytic Sol-Gel: One-Pot, Atom-Economic Synthesis of Mesoporous TiO2 -Carbon Nanocomposites.

Mesoporous TiO2 -carbon nanocomposites were synthesized using an original non-hydrolytic sol-gel (NHSG) route, based on the reaction of simple ethers (diisopropyl ether or tetrahydrofuran) with titanium tetrachloride. In this atom-economic, solvent-free process, the ether acts not only as an oxygen donor but also as the sole carbon source. Increasing the reaction temperature to 180 °C leads to the decomposition of the alkyl chloride by-product and to the formation of hydrocarbon polymers, which are converted to carbon by pyrolysis under argon. The carbon-TiO2 nanocomposites and their TiO2 counterparts (obtained by calcination) were characterized by nitrogen physisorption, XRD, solid state 13 C NMR and Raman spectroscopies, SEM, and TEM. The nanocomposites are mesoporous with surface areas of up to 75 m2 g-1 and pore sizes around 10 nm. They are composed of aggregated anatase nanocrystals coated by an amorphous carbon film. Playing on the nature of the ether and on the reaction temperature allows control over the carbon content in the nanocomposites. The nature of the ether also influences the size of the TiO2 crystallites and the morphology of the nanocomposite. To further characterize the carbon coating, the behavior of the carbon-TiO2 nanocomposites and bare TiO2 samples toward lithium insertion-deinsertion was investigated in half-cells. This simple NHSG approach should provide a general method for the synthesis of a wide range of carbon-metal oxide nanocomposites.

Multiwalled Carbon Nanotube/Cellulose Composite: From Aqueous Dispersions to Pickering Emulsions.

A mild and simple way to prepare stable aqueous colloidal suspensions of composite particles made of a cellulosic material (Sigmacell cellulose) and multiwalled carbon nanotubes (MWCNTs) is reported. These suspensions can be dried and redispersed in water at pH 10.5. Starting with rather crude initial materials, commercial Sigmacell cellulose and MWCNTs, a significant fraction of composite dispersed in water could be obtained. The solid composites and their colloidal suspensions were characterized by electronic microscopy, thermal analyses, FTIR and Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and light scattering. The composite particles consist of tenuous aggregates of CNTs and cellulose, several hundred nanometers large, and are composed of 55 wt % cellulose and 45 wt % CNTs. Such particles were shown to stabilize cyclohexane-in-water emulsions. The adsorption and the elasticity of the layer they form at interface were characterized by the pendant drop method. The stability of the oil-in-water emulsions was attributed to the formation of an elastic network of composite particles at interface. Cyclohexane droplet diameters could be tuned from 20 to 100 µm by adjusting the concentration of composite particles. This behavior was attributed to the limited coalescence phenomenon, just as expected for Pickering emulsions. Interestingly, cyclohexane droplets were stable over time and sustained pH modifications over a wide range, although acidic pH induced accelerated creaming. This study points out the possibility of combining crude cellulose and MWCNTs through a simple process to obtain colloidal systems of interest for the design of functional conductive materials.

Sustainable carbon materials.

Carbon-based structures are the most versatile materials used in the modern field of renewable energy (i.e., in both generation and storage) and environmental science (e.g., purification/remediation). However, there is a need and indeed a desire to develop increasingly more sustainable variants of classical carbon materials (e.g., activated carbons, carbon nanotubes, carbon aerogels, etc.), particularly when the whole life cycle is considered (i.e., from precursor "cradle" to "green" manufacturing and the product end-of-life "grave"). In this regard, and perhaps mimicking in some respects the natural carbon cycles/production, utilization of natural, abundant and more renewable precursors, coupled with simpler, lower energy synthetic processes which can contribute in part to the reduction in greenhouse gas emissions or the use of toxic elements, can be considered as crucial parameters in the development of sustainable materials manufacturing. Therefore, the synthesis and application of sustainable carbon materials are receiving increasing levels of interest, particularly as application benefits in the context of future energy/chemical industry are becoming recognized. This review will introduce to the reader the most recent and important progress regarding the production of sustainable carbon materials, whilst also highlighting their application in important environmental and energy related fields.

Selecting for function: solution synthesis of magnetic nanopropellers.

We show that we can select magnetically steerable nanopropellers from a set of carbon coated aggregates of magnetic nanoparticles using weak homogeneous rotating magnetic fields. The carbon coating can be functionalized, enabling a wide range of applications. Despite their arbitrary shape, all nanostructures propel parallel to the vector of rotation of the magnetic field. We use a simple theoretical model to find experimental conditions to select nanopropellers which are predominantly smaller than previously published ones.

Ionothermal Carbonization of Sugarcane Bagasse in 1-Alkyl-3-methylimidazolium Ionic Liquids: Insights into the Role of the Chloroferrate Anion.

We report the ionothermal carbonization (ITC) of lignocellulosic biomass in imidazolium tetrachloroferrate ionic liquids (ILs) as an advantageous approach for the preparation of nanostructured carbonaceous materials, namely, ionochars. In a previous study, we investigated the role of the imidazolium cation and demonstrated the possibility of controlling both the textural and morphological properties of ionochars by cation engineering. Although essential for providing intermediate Lewis acidity and relatively high thermal stability, the role of the chloroferrate anion is still open to debate. Herein, we investigated the ITC of sugarcane bagasse and its main component, cellulose, in 1-alkyl-3-methylimidazolium ILs with different chloroferrate anions. We identified anionic speciation and its impact on the properties of the IL by Raman spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The obtained ionochars were characterized by gas physisorption, electron microscopy, Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and 13C solid-state CP-MAS NMR spectroscopy. We show that the anionic species have a predominant impact on the textural and morphological properties of the ionochars.

Online headspace monitoring of volatile organic compounds using proton transfer reaction-mass spectrometry: Application to the multiphase atmospheric fate of 2,4-hexadienedial.

Chemical processes in clouds have been suggested to contribute significantly to the mass of organic aerosol particles in the atmosphere. Experimental and theoretical evidence suggest that organic mass production in clouds can be substantial and depends on the concentration of organic precursor compounds available in the gas phase. The present study aims at studying the aqueous phase reactivity of one of these overlooked precursors, i.e. 2,4-hexadienedial, an important and toxic intermediate in the atmospheric oxidation of aromatic species. Cautious synthesis and purification of 2,4-hexadienedial was performed. Its effective Henry's law constant was measured using a new simple and fast method based on online flow-injection analysis. The reactivity of 2,4-hexadienedial in the aqueous phase relevant to atmospheric conditions was studied, including hydrate formation, photolysis, ∙OH- and SO4∙--oxidation as well as reaction with NH3. The results revealed a low hydration constant compared to other dicarbonyls (Khyd1 = 7 × 10-2) and no dihydrate formation, indicating in an intermediate solubility (KH = 1.0 × 104 M atm-1) and high absorption cross sections (σ278nm > 10-16 cm2 molecule-1). Compared to its gas phase photolysis, its aqueous phase photolysis showed low quantum yields (Φ290-380nm = 0.9 %), and a significant red shift of the absorbance maximum, leading to a fast aqueous photolysis kinetics (Jaq,atm = 8.7 × 10-5 s-1) under atmospheric solar radiation, but no triplet state formation was detected. Radical oxidation experiments revealed extremely rapid oxidation kinetics (k∙OH = 1.10 × 1010 M-1 s-1 and kSO4∙- = 1.4 × 109 M-1 s-1) driven by fast addition of the radicals to the unsaturated bonds. In contrast, the reaction with aqueous NH3 (kNH3 = 2.6 × 10-3 M-1 s-1) was found slower than glyoxal and 2-butenedial, likely due to the hyperconjugation of 2,4-hexadienedial. Using these new data complemented with assumed aqueous phase kinetics (for NO3, 3C* and 1O2 reactions) and previous gas-phase kinetic ones, the multiphase atmospheric fate of 2,4-hexadienedial was established under atmospheric conditions reported from previous field measurements and models. The results revealed a short day lifetime (∼1 h) and a long night lifetime (>12 h). It was shown that daytime atmospheric chemistry of 2,4-hexadienedial can be influenced by aqueous-phase reactivity during cloud events, up to ∼50 % under thick cloud conditions (Liquid Water Content >2000 g/m3), indicating that even a compound of intermediate solubility can be strongly affected by condensed-phase reactivity. Besides its fast aqueous phase reactivity towards ∙OH and photolysis, its daytime condensed-phase reactivity may be driven by reactions with dissolved triplet states (3C*), up to 35 %, highlighting the need to study further the kinetics, the nature and concentrations of dissolved 3C* under various atmospheric conditions. In addition, the molecular properties and atmospheric behavior of 2,4-hexadienedial were found different from those of glyoxal and 2-butenedial, highlighting the need for detailed atmospheric reactivity studies of polyfunctional compounds, in particular unsaturated compounds.

A novel three-dimensional macrocellular carbonaceous biofuel cell.

Here we report the first membrane-free biofuel cell obtained using three-dimensional carbonaceous foam electrodes. We first developed a new synthetic pathway to produce a new carbonaceous foam electrode material bearing porosity both on the meso and macroporous scales. We proved that by increasing the porosity of our three-dimensional foams we could increase the current density of our modified electrodes. Then, by choosing the right combination of enzyme and mediator, and the right loading of active components, we achieved high current densities for an anodic system. Finally, we combined the improved cathode and anode to build a new membrane-free hybrid enzymatic biofuel cell consisting of a mediated anode and a mediator-free cathode.

Hydrothermal carbon-based nanostructured hollow spheres as electrode materials for high-power lithium-sulfur batteries.

Carbon hollow spheres were produced using a sustainable approach, i.e. hydrothermal carbonization, using monosaccharides as carbon precursors and silica nanoparticles as hard-templates. Hydrothermal carbonization is an eco-efficient and cost-effective route to synthesize nanostructured carbonaceous materials from abundant biomass-derived molecules. After further thermal treatment under an inert atmosphere and removal of the silica-based core by chemical etching, porous hollow spheres depicting 5-8 nm thin shells were obtained. Subsequently, carbon-sulfur composites were synthesized via a melt diffusion method and used as nanostructured composites for cathodes in lithium-sulfur (Li-S) cells. The morphology of the hollow spheres was controlled and optimized to achieve improved electrochemical properties. Both high specific energies and high specific powers were obtained, due to the unique nanostructure of the hollow spheres. These results revealed that using optimized carbonaceous materials, it is possible to design sustainable Li-S cells showing promising electrochemical properties.

A fast and efficient method for the analysis of α-dicarbonyl compounds in aqueous solutions: Development and application.

Among the highly oxygenated species formed in situ in the atmosphere, α-dicarbonyl compounds are the most reactive species, thus contributing to the formation of secondary organic aerosols that affect both air quality and climate. They are ubiquitous in the atmosphere and are easily transferred to the atmospheric aqueous phase due to their high solubility. In addition, α-dicarbonyl compounds are toxic compounds found in food in biochemistry studies as they can be produced endogenously through various pathways and exogenously through the Maillard reaction. In this work, we take advantage of the high reactivity of α-dicarbonyl compounds in alkaline solutions (intramolecular Cannizzaro reaction) to develop an analytical method based on high performance ion chromatography. This fast and efficient method is suitable for glyoxal, methylglyoxal and phenylglyoxal which are detected as glycolate, lactate and mandelate anions respectively, with 100% conversion at pH > 12 and room temperature for exposure times to hydroxide ranging from 5 min to 4 h. Diacetyl is detected as 2,4-dihydroxy-2,4-dimethyl-5-oxohexanoate due to a base-catalysed aldol reaction that occurs before the Cannizzaro reaction. The analytical method is successfully applied to monitor glyoxal consumption during aqueous phase HO∙-oxidation, an atmospherically relevant reaction using concentrations that can be observed in fog and cloud water. The method also reveals potential analytical artifacts that can occur in the use of ion chromatography for α-hydroxy carboxylates measurements in complex matrices due to α-dicarbonyl conversion during the analysis time. An estimation of the artifact is given for each of the studied α-hydroxy carboxylates. Other polyfunctional and pH-sensitive compounds that are potentially present in environmental samples (such as nitrooxycarbonyls) can also be converted into α-hydroxy carboxylates and/or nitrite ions within the HPIC run. This shows the need for complementary analytical measurements when complex matrices are studied.

Long-term stable solid concentrated graphene dispersion assisted by a highly aromatic ionic liquid.

HYPOTHESIS: The sonochemical exfoliation of graphite in solution has been demonstrated as a promising and easy technique for producing graphene dispersions. This is usually done in organic solvents and leads to unstable dispersions with very low graphene concentration. Ionic liquids (ILs) represent a versatile and safe alternative to traditional organic solvents. A few recent studies reported the use of commercial ILs with bulky anions, such as bis(trifluoromethylsulfonyl)imide, and aromatic cations, such as imidazolium, which favour the exfoliation of graphite through π-π and cation-π interactions. Although recently investigated, the role of aromatic groups on imidazolium cations is still controversial and systematic studies are still necessary. Besides, these studies were limited to liquid dispersions at room temperature. EXPERIMENTS: Herein, we prepared four highly aromatic imidazolium-based ILs, including the newly reported 1-(naphthylmethyl)-3-benzylimidazolium bis(trifluoromethanesulfonyl)imide, [(Np)(Bn)im][NTf2]. These ILs were used for the sonochemical exfoliation of graphite and compared with a commercial benchmark, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][NTf2]. FINDINGS: Interestingly, [(Np)(Bn)im][NTf2] allowed reaching solid dispersions at room temperature containing thin few layer graphene sheets with long-term stability (up to 2 years) and high concentration (3.6 mg/mL). Such graphene dispersion combines long-term stability in the solid-state and high processability in the liquid state, by a simple heating above 60 °C.

Hybrid foams, colloids and beyond: from design to applications.

Highly internal phase emulsion (polyHIPE) materials are promising macrocellular foams bearing versatile applications ranging from catalysis, optics, filtration, insulator and so forth. In this critical review water-in-oil HIPE, oil-in-water HIPE and Pickering-based HIPE are discussed. Also in each above-mentioned HIPE family, declination between the organic, inorganic or hybrid-organic foams chemical nature is proposed. The polyHIPE audience is thereby strongly interdisciplinary in nature crossing boundaries of physical chemistry, colloids, polymer science, sol-gel chemistry, hybrid materials, biology and beyond (114 references).

Experimental and modeling of tetracycline degradation in water in a flow-through enzymatic monolithic reactor.

In this work, the laccase from Trametes versicolor was immobilized in highly porous silica monoliths (0.6-cm diameter, 0.5-cm length). These monoliths feature a unique homogeneous network of interconnected macropores (20 µm) with mesopores (20 nm) in the skeleton and a high specific surface area (330 m2/g). The enzymatic monoliths were applied to degrade tetracycline (TC) in model aqueous solutions (20 ppm). For this purpose, a tubular flow-through reactor (FTR) configuration with recycling was built. The TC degradation was improved with oxygen saturation, presence of degradation products, and recirculation rate. The TC depletion reaches 50% in the FTR and 90% in a stirred tank reactor (CSTR) using crushed monoliths. These results indicate the importance of maintaining a high co-substrate concentration near active sites. A model coupling mass transfers with a Michaelis-Menten kinetics was applied to simulate the TC degradation in real wastewaters at actual TC concentration (2.8 10-4 ppm). Simulation results show that industrial scale FTR reactor should be suitable to degrade 90% of TC in 5 h at a flow rate of 1 mL/min in a single passage flow configuration. Nevertheless, the process could certainly be further optimized in terms of laccase activity, oxygen supply near active sites, and contact time.

When graphene meets ionic liquids: a good match for the design of functional materials.

Graphene is an attractive material that is characterized by its exceptional properties (i.e. electrical, mechanical, thermal, optical, etc.), which have pushed researchers to attach high interest to its production and functionalization processes to meet applications in different fields (electronics, electromagnetics, composites, sensors, energy storage, etc.). The synthesis (bottom-up) of graphene remains long and laborious, at the same time expensive, and it is limited to the development of this material in low yield. Hence, the use of graphite as a starting material (top-down through exfoliation or oxidation) seems a promising and easy technique for producing a large quantity of graphene or graphene oxide (GO). On the one hand, GO has been extensively studied due to its ease of synthesis, processing and chemical post-functionalization. One the other hand, "pristine" graphene sheets, obtained through exfoliation, are limited in processability but present enhanced electronic properties. Both types of materials have been of great interest to design functional nanomaterials. Ionic liquids (ILs) are task-specific solvents that exhibit tunable physico-chemical properties. ILs have many advantages as compared with conventional solvents, such as high thermal and chemical stability, low volatility, excellent conductivity and inherent polarity. In the last decade, ILs have been widely employed for the preparation and stabilization of various nanomaterials. In particular, the combination of ILs and graphene, including GO and pristine graphene sheets, has been of growing interest for the preparation, processing and functionalization of hybrid nanomaterials. Understanding the structure and properties of the graphene/IL interface has been of considerable interest for a large panel of applications ranging from tribology to energy storage.

TinO2n-1 Suboxide Phases in TiO2/C Nanocomposites Engineered by Non-hydrolytic Sol-Gel with Enhanced Electrocatalytic Properties.

We report a non-hydrolytic sol-gel (NHSG) route to engineer original mesoporous TinO2n-1@TiO2/C nanocomposites. The synthetic approach is straightforward, solvent-free, additive-free, and meets the challenge of atom economy, as it merely involves TiCl4 and THF in stoichiometric amounts. We found that these nanocomposites present enhanced electrocatalytic properties towards the oxygen reduction reaction (ORR) in 0.1 M KOH. We believe that these preliminary results will open a window of opportunity for the design of metal suboxides/carbon nanocomposites through NHSG routes.

Genomic DNA PCR analysis to assess xenograft development in mouse mammary gland.

The mouse transplantation model remains the most relevant methodology to assess the functional capacities of mammary cells and is particularly appropriate for investigations regarding mammary stem cells, whatever the species studied. Following xenotransplantation in mice mammary fat pad, the development of the xenograft is commonly evaluated by immunohistology. Here, we present a simple and rapid method to control the species specificity of a xenograft based on genomic DNA PCR amplification. DNA is extracted from the fixed samples intended for histology, thus allowing the reuse of precious samples. Standard and digital droplet PCR (requiring low DNA quantities) methods have been used to make the present method suitable for the analysis of xenotransplanted samples.

Self-Limited Grafting of Sub-Monolayers via Diels-Alder Reaction on Glassy Carbon Electrodes: An Electrochemical Insight.

The grafting of molecular monolayers is critical for the functionalization of surfaces. In molecular electrochemistry, the surface modification of electrodes and the way molecules are attached to the electrode surface are highly critical to electron transfers and electrochemical reactions. In this paper, sub-monolayers were covalently grafted onto glassy carbon (GC) electrodes via Diels-Alder cycloaddition with two soluble dienophiles, that is, propargyl bromide and ethynyl ferrocene. Such an approach is clean (no by-product, no catalyst/additive) and occurs under mild conditions by heating at 50 °C in toluene for few hours. The as-modified electrodes were thoroughly characterized by FTIR, XPS, and cyclic voltammetry using both millimetric GC electrodes and ultra-microelectrodes. Cyclic voltammetry gave access to surface coverage and clearly evidenced the covalent grafting of sub-monolayers. The grafting of functional sub-monolayers via Diels-Alder cycloaddition could be easily extended to various functionalities and carbons to prepare electrochemical sensors or electrocatalytic surfaces.

Dehydration of Alginic Acid Cryogel by TiCl4 vapor: Direct Access to Mesoporous TiO2 @C Nanocomposites and Their Performance in Lithium-Ion Batteries.

A new strategy for the synthesis of mesoporous TiO2 @C nanocomposites through the direct mineralization of seaweed-derived alginic acid cryogel by TiCl4 through a solid/vapor reaction pathway is presented. In this synthesis, alginic acid cryogel can have multiple roles; i) mesoporous template, ii) carbon source, and iii) oxygen source for the TiO2 precursor, TiCl4 . The resulting TiO2 @alginic acid composite was transformed either into pure mesoporous TiO2 by calcination or into mesoporous TiO2 @C nanocomposites by pyrolysis. By comparing with a nonporous TiO2 @C composite, the importance of the mesopores on the performance of electrodes for lithium-ion batteries based on mesoporous TiO2 @C composite was clearly evidenced. In addition, the carbon matrix in the mesoporous TiO2 @C nanocomposite also showed electrochemical activity versus lithium ions, providing twice the capacity of pure mesoporous TiO2 or alginic acid-derived mesoporous carbon (A600). Given the simplicity and environmental friendliness of the process, the mesoporous TiO2 @C nanocomposite could satisfy the main prerequisites of green and sustainable chemistry while showing improved electrochemical performance as a negative electrode for lithium-ion batteries.

Impact of exposure to diesel exhaust during pregnancy on mammary gland development and milk composition in the rabbit.

Exposure to fine-particulate air pollution is a major global health concern because it is associated with reduced birth weight and an increased risk of cardiovascular disease. Here we have investigated the potential for exposure to diesel exhaust during pregnancy to influence mammary gland development and milk composition. Female rabbits were therefore exposed by nose-only inhalation to either diluted diesel exhaust fumes (1 mg/m3) or clean air for 2h/day, 5 days/week, from the 3rd to the 27th days of pregnancy. On Day 28 of pregnancy, mammary glands were collected from twelve females (six controls and six diesel-exposed) and assessed for morphological and functional alterations. Milk samples were collected from eighteen dams (nine controls and nine diesel-exposed) during early (days 2 to 4) and established (days 13 to 16) lactation to verify the composition of fatty acids and major proteins and leptin levels. The mammary alveolar lumina contained numerous fat globules, and stearoyl CoA reductase expression was higher in mammary epithelia from diesel exhaust-exposed rabbits, which together suggested increased mammary lipid biosynthesis. Gas chromatography analysis of the composition of milk fatty acids revealed a sharp rise in the total fatty acid content, mainly due to monounsaturated fatty acids. Liquid chromatography-mass spectrometry analysis of milk samples enabled identification and quantification of the main rabbit milk proteins and their main phosphorylated isoforms, and revealed important changes to individual casein and whey protein contents and to their most phosphorylated isoforms during early lactation. Taken together, these findings suggest that repeated daily exposure to diesel exhaust fumes during pregnancy at urban pollution levels can influence lipid metabolism in the mammary gland and the lipid and protein composition of milk. As milk may contribute to metabolic programming, such alterations affecting milk composition should be taken into account from a public health perspective.