Hydrophilic Amine Research Articles

Disorders of carnitine biosynthesis and transport.

Carnitine is a hydrophilic quaternary amine that plays a number of essential roles in metabolism with the main function being the transport of long-chain fatty acids from the cytosol to the mitochondrial matrix for β-oxidation. Carnitine can be endogenously synthesized. However, only a small fraction of carnitine is obtained endogenously while the majority is obtained from diet, mainly animal products. Carnitine is not metabolized and is excreted in urine. Carnitine homeostasis is regulated by efficient renal reabsorption that maintains carnitine levels within the normal range despite variabilities in dietary intake. Diseases occurring due to primary defects in carnitine metabolism and homeostasis are comprised in two groups: disorders of carnitine biosynthesis and carnitine transport defect. While the hallmark of carnitine transport defect is profound carnitine depletion, disorders of carnitine biosynthesis do not cause carnitine deficiency due to the fact that both carnitine obtained from diet and efficient renal carnitine reabsorption can maintain normal carnitine levels with the absence of endogenously synthesized carnitine. Carnitine transport defect phenotype encompasses a broad clinical spectrum including metabolic decompensation in infancy, cardiomyopathy in childhood, fatigability in adulthood, or absence of symptoms. The phenotypes associated with the carnitine transport defect result from the unavailability of enough carnitine to perform its functions particularly in fatty acid β-oxidation. Carnitine biosynthetic defects have been recently described and the phenotypic consequences of these defects are still emerging. Although these defects do not result in carnitine deficiency, they still could be associated with pathological phenotypes due to excess or deficiency of intermediate metabolites in the carnitine biosynthetic pathway and potential carnitine deficiency in early stages of life when brain and other organs develop. In addition to these two groups of primary carnitine defects, several metabolic diseases and medical conditions can result in excessive carnitine loss leading to a secondary carnitine deficiency.

Bacterial response to different surface chemistries fabricated by plasma polymerization on electrospun nanofibers.

Control over bacterial attachment and proliferation onto nanofibrous materials constitutes a major challenge for a variety of applications, including filtration membranes, protective clothing, wound dressings, and tissue engineering scaffolds. To develop effective devices, the interactions that occur between bacteria and nanofibers with different morphological and physicochemical properties need to be investigated. This paper explores the influence of fiber surface chemistry on bacterial behavior. Different chemical functionalities were generated on the surface of electrospun polystyrene nanofibers through plasma polymerization of four monomers (acrylic acid, allylamine, 1,7-octadiene, and 1,8-cineole). The interactions of Escherichia coli with the surface modified fibers were investigated through a combination of scanning electron microscopy and confocal laser scanning microscopy. Fiber wettability, surface charge, and chemistry were found to affect the ability of bacterial cells to attach and proliferate throughout the nanofiber meshes. The highest proportion of viable cells attachment occurred on the hydrophilic amine rich coating, followed by the hydrophobic octadiene. The acrylic acid coating rich in carboxyl groups showed a significantly lower attraction of bacterial cells. The 1,8-cineole retained the antibacterial activity of the monomer, resulting with a high proportion of dead isolated cells attached onto the fibers. Results showed that the surface chemistry properties of nanofibrous membranes can be strategically tuned to control bacterial behavior.

Activation Effect of Fullerene C60 on the Carbon Dioxide Absorption Performance of Amine-Rich Polypropylenimine Dendrimers.

Converting amine-rich compounds into highly effective carbon dioxide (CO2 ) sorbents requires a better understanding and control of their properties. The reaction of fullerene C60 with polyethyleneimine converts the polymer into a high-performance CO2 sorbent. In this study, experimental evidence is reported for the activation effect of C60 on the amine moieties of the polymer. To do so, polypropylenimine (PPI) dendrimers that allowed for a systematic comparison of molecular composition and CO2 absorption were used. The addition of C60 to PPI to form PPI-C60 results in a reduction of the energy barrier of CO2 absorption, but also in a parallel decrease in the frequency of successful collisions between CO2 and PPI-C60 due to a possible disruption of the hydrogen-bonding network of amino groups and bound water in PPI. This finding supports the existence of a non-affinity "repulsive" effect between hydrophobic C60 and hydrophilic amines that forces them to be actively exposed to CO2.

Exploitation of orientation of liquid crystals 5CB and DSCG near surfaces to detect low protein concentration

We report the alignment of 4-cyano-4-pentylbiphenyl (5CB), a thermotropic liquid crystal (LC), and disodium chromo glycate (DSCG), a lyotropic LC, on the hydrophobic head group containing dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (DMOAP) and hydrophilic amine head group. Based on the texture observed using a polarised microscope for modified surfaces, we propose the alignment of the LCs on the modified surfaces. It is further supported by Fourier transform infra-red spectroscopy (FTIR) data of the corresponding system. Next, the texture under a polarised microscope for the LCs on protein bovine serum albumin adsorbed over the amine and DMOAP surfaces was observed. The difference in texture of LCs over the proteins depends on its concentration in solution. The difference is due to the amount of adsorbed proteins present on the surface. Above a critical amount of protein at the surface, the LCs show homeotropic arrangement.

Rapid Screening of Immobilized Amine CO2 Sorbents for Steam Stability by Their Direct Contact with Liquid H2 O.

Rapid testing of hydrophilic and hydrophobic basic immobilized amine sorbents (BIAS) for CO2 capture stability under practical conditions was achieved by direct contact of the sorbents with flowing liquid water. Losses in both CO2 capture capacity and amine content of sorbents after exposure to 0.5 mL min(-1) of H2 O at 25 °C for 40 min followed similar trends as losses observed after exposure to N2 /steam (105 °C, 7 % H2 O) for 10 h. We also found that hydrophobic TMPED helped stabilize sorbents to H2 O, which was confirmed by DRIFTS and combined TGA-DSC.

Synthesis and characterization of robust double-networks based on end-linked, pH-responsive first networks

Fragile, end-linked hydrophilic tertiary amine based methacrylate (first) networks were mechanically reinforced using the double-network principle, via the introduction of a polyacrylamide second network. Reinforcement with the second network was performed on the first network both at its neutral and fully ionized states. Although significantly more polyacrylamide was introduced in to the ionized first networks (higher aqueous swelling degrees), better mechanical properties were also exhibited by the double-networks (DN) comprising neutral first networks. All DNs presented better mechanical properties than the methacrylate first networks, with the DNs based on neutral first networks displaying high compressive strain at break, and those based on ionized first networks displaying higher modulus in compression and higher fracture energy.

Pickering-Emulsion-Templated Encapsulation of a Hydrophilic Amine and Its Enhanced Stability Using Poly(allyl amine)

Efficient encapsulation of tetraethylenepentamine (TEPA), as an example aliphatic amine, was achieved by an emulsion-templated, in situ polymerization. Hydrophobically modified clay nanoplatelets were employed as emulsifiers to obtain water-in-oil (W/O) dispersions followed by interfacial polymerization between a portion of the TEPA cargo and polymethylene polyphenylene isocyanate (PMPPI). The resultant capsules exhibit spherical shape, desirable thermal stability, modest barrier properties, and shear-induced release in an epoxide monomer mixture. Most importantly, a significant gain in capsule barrier properties was realized by introducing poly(allyl amine) (pAAm) as an interface-selective reactive additive in the Pickering emulsions. In addition to the fundamental interest of pAAm localization and interface-selective reactivity, this microencapsulation system for aliphatic amines has technological potential in coating, self-healing, and drug-delivery applications.

Skin absorption of six performance amines used in metalworking fluids.

Every year, 10 million workers are exposed to metalworking fluids (MWFs) that may be toxic. There are four types of MWFs: neat oils and three water-based MWFs (soluble oil, semisynthetic and synthetic), which are diluted with water and whose composition varies according to the mineral oils ratio. MWFs also contain various additives. To determine the absorption of six amines used as corrosion inhibitors and biocides in MWFs, porcine skin flow-through diffusion cell experiments were conducted with hydrophilic ethanolamines (mono-, di- and triethanolamine, MEA, DEA and TEA respectively) and a mixture of lipophilic amines (dibutylethanolamine, dicyclohexylamine and diphenylamine). The six amines were dosed in four vehicles (water and three generic water-based MWF formulations) and analyzed using a scintillation counter or gas chromatography/mass spectrometry. These 24 h studies showed that dermal absorption significantly (P < 0.05) increased from water for the six amines (e.g. 1.15 ± 0.29% dose; DEA in water) compared to other formulations (e.g. 0.13 ± 0.01% dose; DEA in semisynthetic MWF) and absorption was greatest for dibutylethanolamine in all the formulations. The soluble oil formulation tended to increase the dermal absorption of the hydrophilic amines. The permeability coefficient was significantly higher (P < 0.05) with TEA relative to the other hydrophilic amines (e.g. 4.22 × 10(-4) ± 0.53 × 10(-4) cm h(-1) [TEA in synthetic MWF] vs. 1.23 × 10(-4) ± 0.10 × 10(-4) cm h(-1) [MEA in synthetic MWF]), except for MEA in soluble oil formulation. Future research will confirm these findings in an in vivo pig model along with dermatotoxicity studies. These results should help MWF industries choose safer additives for their formulations to protect the health of metalworkers.

Adenoviral vectors coated with cationic PEG derivatives for intravaginal vaccination against HIV-1

Mucus layer coating the vaginal epithelium represents a barrier for intravaginally delivered recombined adenoviral (rAd) vectors, but it could be overcome by proper polyethylene glycol (PEG) modification. Here we synthesized two cationic PEG derivatives, amino-(EO)n/(AGE)m-Cyss (APCs). The polymers contained neutral linear PEG (2–5 kDa) to provide a hydrophilic surface and amine pendants to provide positive charge for coating negatively charged rAd by physical adsorption. Given proper molecular composition, the polymer (5k-APC) could coat rAd without causing aggregation, facilitating its mucus penetrating ability and enhancing gene expression both in vitro and in vivo. With HIVgag as the model antigen, the polymer-rAd complexes were administered intravaginally to elicit both systemic and mucosal immune responses. 5k-APC-rAd immunization elicited robust HIVgag-specific cellular responses and also induced higher antigen-specific serum IgG. More importantly, mice immunized with 5k-APC-rAd showed higher level of IgA in vaginal lavage fluid. These findings suggest that 5k-APC-rAd is a promising system for intravaginal immunization against infectious diseases such as HIV within the vaginal tract.

Temperature-Responsive Hyperbranched Amine-Based Polymers for Solid–Liquid Separation

Temperature-responsive hyperbranched polymers containing primary amines as pendent groups have been synthesized for solid-liquid separation of kaolinite clay suspension. The effects of temperature, polymer charge density, and polymer architecture on particle flocculation have been investigated. Suspensions treated with the temperature-responsive amine-based hyperbranched polymers showed remarkable separation of the fine particles at a low polymer dosage of 10 ppm and at testing temperatures of 40 °C. In comparison to other polymers studied (linear and hyperbranched homopolymers and copolymers), the temperature-responsive amine-based hyperbranched copolymers showed better particle flocculation at 40 °C, as evidenced by the formation of a thinner sediment bed without compromising the amount of clay particles being flocculated. This superior solid-liquid separation performance can be explained by the hydrophobic interaction of PNIPAM segments on particle surfaces or the capture of additional free particles or small floc due to the exposure of buried positive charges (because of the phase separation of the hydrophilic amines and hydrophobic PNIPAM part) at temperatures above the lower critical solution temperature (LCST).

Efficient synthesis of small-sized phosphonated dendrons: potential organic coatings of iron oxide nanoparticles

We report herein the synthesis of biocompatible small-sized phosphonated monomers and dendrons used as functional coatings of metal oxide nanoparticles, more specifically superparamagnetic iron oxides (SPIOs) for magnetic resonance imaging (MRI) and therapy through hyperthermia. The molecules were engineered to modulate their size, their hydrophilic and/or biocompatible character (poly(amido)amine versus oligoethyleneglycol), the number of anchoring phosphonate groups (monophosphonate versus phosphonic tweezers) and the number of peripheral functional groups for further grafting of dyes or specific vectors. Such a library of hydrophilic phosphonic acids opens new possibilities for the investigation of dendronized nanohybrids as theranostics.

Core–shell inversion by pH modulation in dynamic covalent micelles

Dynamic covalent surfactants have been obtained by the reversible condensation of a hydrophobic aldehyde (ended by an ionic tip) with various neutral polyethylene glycol based hydrophilic amines. In water, the duality between the two hydrophilic domains (charged and neutral) leads to their segregation when the surfactants are self-assembled within micelles. Depending on the number of polyethylene glycol units, a core-shell inversion leading to a switching orientation of the ionic tips from the inside to the outside of the micelles has been demonstrated by a combination of scattering techniques. In competition experiments, when several amines of different pKas and hydrophilic polyethylene glycol chains are competing for the same aldehyde, it becomes possible to trigger this core-shell inversion by pH modulation and associated dynamic constitutional reorganization.

Insight into Highly Efficient Coremoval of Copper and p-Nitrophenol by a Newly Synthesized Polyamine Chelating Resin from Aqueous Media: Competition and Enhancement Effect upon Site Recognition

Highly efficient coremoval of Cu(II) and p-nitrophenol (PNP) was accomplished using a newly synthesized polyamine chelating resin (CEAD) as compared to three other commercial resins. The mutual effects and inner mechanisms of their adsorption onto CEAD were systematically investigated by binary, preloading, thermodynamic, and dynamic adsorption procedures. PNP was adsorbed onto both hydrophobic and hydrophilic sites, while Cu(II) only interacted with hydrophilic amine group sites. In both preloading and binary systems, the adsorption of PNP was inhibited to the same degree by the presence of Cu(II) because of selective recognition and direct competition. On the other hand, the presence of PNP obviously enhanced the adsorption of Cu(II) by more than 7%, which was related to PNP loading on the hydrophobic surface. As proved by structural characterization, hydroxyl groups facing outward create new sites for coordination with Cu(II). Moreover, ionic strength exerted some positive influence on the properties of CEAD. Finally, more than 98% of PNP and 99% of Cu(II) could be sequentially recovered with dilute NaClO3 and HCl. These superior properties demonstrated with CEAD indicate that it could be applied to wastewaters containing both heavy metals and PNP, even for high saline aqueous media.

Effect of plasma surface functionalization on preosteoblast cells spreading and adhesion on a biomimetic hydroxyapatite layer formed on a titanium surface

This study examined the plasma surface modification of biomimetic hydroxyapatite (HAp) formed on a titanium (Ti) surface as well as its influence on the behavior of preosteoblast cells. Ti substrates pre-treated with a plasma-polymerized thin film rich in carboxyl groups were subjected to a biomimetic process in a simulated body fluid solution to synthesize the HAp. The HAp layer grown on Ti substrate was then coated with two types of plasma polymerized acrylic acid and allyl amine thin film. The different types of Ti substrates were characterized by attenuated total reflection Fourier transform infrared spectroscopy, energy dispersive spectroscopy and X-ray diffraction. HAp with a Ca/P ratio from 1.25 to 1.38 was obtained on the Ti substrate and hydrophilic carboxyl (COOH) and amine (NH2) functional groups were introduced to its surface. Scanning electron microscopy was used to observe the surface of the HAp coatings and the morphology of MC3T3-E1 cells. These results showed that the COOH-modified HAp surfaces promoted the cell spreading synergistically by changing the surface morphology and chemical state.NH2 modified HAp had the lowest cell spreading and proliferation compared to HAp and COOH-modified HAp. These results correspond to fluorescein analysis, which showed many more cell spreading of COOH/HAp/Ti surface compared to HAp and NH2 modified HAp. A MTT assay was used to evaluate cell proliferation. The results showed that the proliferation of MC3T3-E1 cells increased in the order of COOH/HAp/Ti>HAp/Ti>NH2/Ti>Ti, corresponding to the effect of cell spreading for 6 days. The change in morphology and the chemical surface properties of the biomaterial via plasma polymerization can affect the behavior of MC3T3-E1 cells.

Silicon and Germanium Nanoparticles with Tailored Surface Chemistry as Novel Inorganic Fiber Brightening Agents

Low-molecular-weight organic molecules, such as coumarins and stilbenes, are used commercially as fluorescent whitening agents (FWAs) to mask photoyellowing and to brighten colors in fabrics. FWAs achieve this by radiating extra blue light, thus changing the hue and also adding to the brightness. However, organic FWAs can rapidly photodegrade in the presence of ultraviolet (UV) radiation, exacerbating the yellowing process through a reaction involving singlet oxygen species. Inorganic nanoparticles, on the other hand, can provide a similar brightening effect with the added advantage of photostability. We report a targeted approach in designing new inorganic silicon- and germanium-based nanoparticles, functionalized with hydrophilic (amine) surface terminations as novel inorganic FWAs. When applied on wool, by incorporation in a sol-gel Si matrix, the inorganic FWAs improved brightness properties, demonstrated enhanced photostability toward UV radiation, especially the germanium nanoparticles, and also generated considerably lower levels of reactive oxygen species compared to a commercial stilbene-based organic FWA, Uvitex NFW.

Synthesis, characterization, and surface wettability properties of amine functionalized graphene oxide films with varying amine chain lengths

Surface functionalization of graphene oxide (GO) an important graphene precursor using alkylamines of varying chain lengths followed by thermal treatment resulted in the formation of superhydrophobic surfaces. Alkylamines consisting of hydrophobic long chain alkyl groups and hydrophilic amine groups were chemically reacted to the GO surface via two types of reactions viz. (i) amidation reaction between amine groups and carboxylic acid sites of GO and (ii) nucleophilic substitution reactions between amine and epoxy groups on GO surface. Successful grafting of alkylamines was confirmed using Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (1H NMR), and thermogravimetric analysis (TGA). Alkylamine-modified GO surfaces showed enhanced roughness, and this effect was more pronounced with increasing amine chain length. Water contact angle measurements revealed that the hydrophobic nature of graphene depended on the chain length of the grafted alkylamines, and this fact may be corroborated to the decrease in the surface energy values. Our results indicate that superhydrophobic graphene films can be produced by thermal treatment of hexadecylamine- and octadecylamine-grafted GO films. These results will provide valuable guidance for the design and manufacture of graphene-based biomaterials, medical instruments, structural composites, electronics, and renewable energy devices.

Properties of Adsorbed Bovine Serum Albumin and Fibrinogen on Self-Assembled Monolayers

We have studied kinetics of adsorption and properties of adsorbed bovine serum albumin (BSA) and fibrinogen (Fb) on a hydrophobic octyl surface, a hydrophilic amine surface, and a mixture of octyl and amine self-assembled monolayer (SAM) and newly synthesized hybrid SAM by using quartz crystal microbalance (QCM). In addition, we have proposed a combined kinetic and mass transfer constrained protein adsorption model. The model is fitted to a change in resonance frequency, ΔFn/n versus time data obtained from QCM to get the kinetic rate constants, mass transfer coefficient, and spreading of adsorbed proteins. Initial rate of adsorption increases with a decrease in surface energy of the substrate. The equilibrium adsorbed amount of BSA on the hybrid surface is less than that on the mixed surface and lies in between that on octyl and amine surfaces and that of Fb is the least on hybrid surface. The analysis of variation of the dissipation factor, ΔD, with ΔFn/n indicates that BSA is more flexible than Fb and the adsorbed layer of both proteins is softest on the hybrid surface. The relaxation times of adsorbed proteins are the slowest on the octyl surface, while those on the hybrid surface are the fastest. The analysis of secondary structures of proteins using ATR-FTIR suggests secondary structures of the proteins change during adsorption. The content of α-helix of the proteins increases due to adsorption on the amine surface, while that decreases on all other surfaces. The total content of α-helix and β-sheet strongly depends on the adsorbed mass of the proteins and is weakly dependent related to elasticity and viscosity of the adsorbed proteins, respectively.

Nanotribological properties of silicon with silane derived surface modification

Silicon substrates were modified with octadecyltrichlorosilane and 3-Aminopropyl-triethoxysilane molecules by chemical adsorption process. The surface properties, morphology and composition were characterised by means of contact angle measurement, atomic force microscopic (AFM) analysis and X-ray photoelectron spectroscopy. To achieve quantitative results, it is important to implement the proper force calibration in AFMs. Both the lateral and the normal spring constants of the AFM cantilever were calibrated. The nanotribological properties including adhesion, friction and antiwear of silane derived surface modification are comparatively studied with the calibrated AFM cantilever. The results demonstrated that the silane derived surface modification reduces adhesion and friction. Hydrophobic methyl terminated modification possesses better friction reduction and antiwear capacity than hydrophilic amine terminated surface.

Metabolomics for the Quality Assessment ofLycium chinenseFruits

Lycium chinense has been used as a traditional medicine for centuries in Asia because of its positive effects on health. However, its functional components have not been elucidated. This study determines the levels of health-promoting lipophilic compounds, including carotenoids, tocopherols, and phytosterol, and those of 42 hydrophilic metabolites, including sugars, organic acids, alcohols, amines, and amino acids, in L. chinense fruit from 11 cultivars. The metabolite profiles were subjected to a principal component analysis (PCA), Pearson correlation analysis, and hierarchical clustering analysis (HCA). PCA showed the Cheongdang (LM-3) cultivar to be distinct from the others. The correlation results for a total of 55 compounds revealed strong correlations between the metabolites that participated on closely related pathways. The Cheongdang cultivar appears to be most suited for functional food production because of its high carotenoid, tocopherol, and phytosterol levels. These results indicate the usefulness of metabolite profiling as a tool for assessing the quality of food.

Gold surface supported spherical liposome–gold nano-particle nano-composite for label free DNA sensing

Immobilization of 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) liposome–gold nano-particle (DOPE–AuNP) nano-composite covalently on 3-mercaptopropionic acid (MPA) on gold surface is demonstrated for the first time for electrochemical label free DNA sensing. Spherical nature of the DOPE on the MPA monolayer is confirmed by the appearance of sigmoidal voltammetric profile, characteristic behavior of linear diffusion, for the MPA–DOPE in presence of [Fe(CN)6]3−/4− and [Ru(NH3)6]3+ redox probes. The DOPE liposome vesicle fusion is prevented by electroless deposition of AuNP on the hydrophilic amine head groups of the DOPE. Immobilization of single stranded DNA (ssDNA) is made via simple gold–thiol linkage for DNA hybridization sensing in the presence of [Fe(CN)6]3−/4−. The sensor discriminates the hybridized (complementary target hybridized), un-hybridized (non-complementary target hybridized) and single base mismatch target hybridized surfaces sensitively and selectively without signal amplification. The lowest target DNA concentration detected is 0.1×10−12M. Cyclic voltammetry (CV), electrochemical impedance (EIS), differential pulse voltammetry (DPV) and quartz crystal microbalance (QCM) techniques are used for DNA sensing on DOPE–AuNP nano-composite. Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Atomic Force Microscopy (AFM), Dynamic Light Scattering (DLS) and Ultraviolet–Visible (UV) spectroscopic techniques are used to understand the interactions between the DOPE, AuNP and ssDNA. The results indicate the presence of an intact and well defined spherical DOPE–AuNP nano-composite on the gold surface. The method could be applied for fabrication of the surface based liposome–AuNP–DNA composite for cell transfection studies at reduced reagents and costs.