Aggregation properties of mycolic acid molecules in monolayer films: a comparative study of compounds from various acid-fast bacterial species

AbstractThree kinds of mycolic acids (MAs) (α-, keto and methoxy-MAs) extracted from several species of mycobacteria were used to prepare monolayer films on water, and the surface pressure–area (π–A) isotherms of the monolayers have been compared, so that the monolayer characteristics of the MAs as in cell walls would be revealed, since the monolayer molecular aggregation is related to drug permeability via the molecular packing. It was expected that the limiting molecular areas of the isotherms would be changed only a little, which reflects the minor difference in chemical structure and conformation of the mycobacteria. Nevertheless, the results are largely different from the expectation, and two greatly different patterns of the limiting molecular area have been observed. In a new model for elucidation of the results, two parts in an MA molecule are separately considered, and both contributions to the molecular unfolding by the monolayer compression have been suggested. This model is found to be useful to totally understand the isotherm behaviors of MAs. The relationship between monolayer properties and chemical structures for MAs has been summarized for the first time

Visualization of artificial lignin supramolecular structures

In this paper we are presenting the results of our environmental scanning electron microscopy (ESEM) investigation of the lignin model compound-enzymatically polymerized coniferyl alcohol, also known as dehydrogenate polymer (DHP). The goals of this study were to visualize the supramolecular organization of DHP polymer on various substrates, namely graphite, mica, and glass, and to explore the influence of substrate surface properties and associated collective phenomena on the lignin self-assembled supramolecular structure. Based on results obtained with ESEM, combined with previously published results based on scanning tunneling microscopy (STM) and electron spin resonance (ESR) technique, we looked at Lignin structure ranging from a monomer on a fraction of nanometer scale to a large aggregate on a fraction of millimeter scale. therefore using six orders of magnitude range of size. Herein, we are presenting evidence that there are at least four different levels of the supramolecular structure of lignin, and that its supramolecular organization is well dependent on the substrate surface characteristics, such as hydrophobicity, delocalized orbitals, and surface-free entry

The Influence of Topology on Hydraulic Conductivity in a Sand-and-Gravel Aquifer

A field experiment consisting of geophysical logging and tracer testing was conducted in a single well that penetrated a sand-and-gravel aquifer at the U.S. Geological Survey Toxic Substances Hydrology research site on Cape Cod, Massachusetts. Geophysical logs and flowmeter/pumping measurements were obtained to estimate vertical profiles of porosity ϕ, hydraulic conductivity K, temperature, and bulk electrical conductivity under background, freshwater conditions. Saline-tracer fluid was then injected into the well for 2 h and its radial migration into the surrounding deposits was monitored by recording an electromagnetic-induction log every 10 min. The field data are analyzed and interpreted primarily through the use of Archie’s (1942) law to investigate the role of topological factors such as pore geometry and connectivity, and grain size and packing configuration in regulating fluid flow through these coarse-grained materials. The logs reveal no significant correlation between K and ϕ, and imply that groundwater models that link these two properties may not be useful at this site. Rather, it is the distribution and connectivity of the fluid phase as defined by formation factor F, cementation index m, and tortuosity α that primarily control the hydraulic conductivity. Results show that F correlates well with K, thereby indicating that induction logs provide qualitative information on the distribution of hydraulic conductivity. A comparison of α, which incorporates porosity data, with K produces only a slightly better correlation and further emphasizes the weak influence of the bulk value of ϕ on K

The Influence of Topology on Hydraulic Conductivity in a Sand-and-Gravel Aquifer

A field experiment consisting of geophysical logging and tracer testing was conducted in a single well that penetrated a sand-and-gravel aquifer at the U.S. Geological Survey Toxic Substances Hydrology research site on Cape Cod, Massachusetts. Geophysical logs and flowmeter/pumping measurements were obtained to estimate vertical profiles of porosity ϕ, hydraulic conductivity K, temperature, and bulk electrical conductivity under background, freshwater conditions. Saline-tracer fluid was then injected into the well for 2 h and its radial migration into the surrounding deposits was monitored by recording an electromagnetic-induction log every 10 min. The field data are analyzed and interpreted primarily through the use of Archie’s (1942) law to investigate the role of topological factors such as pore geometry and connectivity, and grain size and packing configuration in regulating fluid flow through these coarse-grained materials. The logs reveal no significant correlation between K and ϕ, and imply that groundwater models that link these two properties may not be useful at this site. Rather, it is the distribution and connectivity of the fluid phase as defined by formation factor F, cementation index m, and tortuosity α that primarily control the hydraulic conductivity. Results show that F correlates well with K, thereby indicating that induction logs provide qualitative information on the distribution of hydraulic conductivity. A comparison of α, which incorporates porosity data, with K produces only a slightly better correlation and further emphasizes the weak influence of the bulk value of ϕ on K

A resorcinarene for inhibition of Aβ fibrillation.

Amyloid-β peptides (Aβ) fibrillation is the hallmark of Alzheimer's disease (AD). However, it has been challenging to discover potent agents in order to inhibit Aβ fibrillation. Herein, we demonstrated the effect of resorcinarene on inhibiting Aβ fibrillation in vitro via experimental and computational methods. Aβ were incubated with different concentrations of resorcinarene so as to monitor the kinetics by using thioflavin T binding assay. The results, which were further confirmed by far-UV CD spectroscopy and atomic force microscopy, strongly indicated that the higher concentration of resorcinarene, the more effective the inhibition of Aβ fibrillation. A cytotoxicity study showed that when sea urchin embryos were exposed to the resorcinarene, the majority survived due to the resorcinarene low toxicity. In addition, when the resorcinarene was added, the formation of toxic Aβ 42 species was delayed. Computational studies of Aβ fibrillation, including docking simulations and MD simulations, illustrated that the interaction between inhibitor resorcinarene and Aβ is driven by the non-polar interactions. These studies display a novel strategy for the exploration of promising antiamyloiddogenic agents for AD treatments

Determine both the conformation and orientation of a specific residue in α-synuclein(61–95) even in monolayer by ¹³C isotopic label and p-polarized multiple-angle incidence resolution spectrometry (pMAIRS)

Protein’s magic function stems from its structure and various analytical techniques have been developed for it. Among proteins, membrane proteins are encoded 20–30% of genomes, whereas cause challenges for many analytical techniques. For example, lots of membrane proteins cannot form single crystal structure required by X-ray crystallography. As for NMR, the measurements were hindered by the low tumbling rates of membrane (i.e., phospholipid bilayers) where membrane proteins exist. In addition, membrane proteins usually lay parallel to the surface of phospholipid bilayers or form transmembrane structure. No matter parallel or perpendicular to phospholipid bilayers surface, membrane proteins form monolayer structure which is also difficult for X-ray and NMR to provide high-resolution results. Because NMR and X-ray crystallography are the two major analytical techniques to address protein’s structure, membrane proteins only contribute 2.4% to the solved protein databank. Surface FT-IR techniques can evaluate the conformation and orientation of membrane proteins by amide I band. Specifically for α-helical peptides/proteins, the orientation of the axis is critical to decide whether proteins form transmembrane structure. Notice that the traditional FT-IR can only provide “low-resolution” results. Here, ¹³C isotope was introduced into the nonamyloid component (NAC), which spans residues 61–95 of α-synuclein (α-syn). Then, p-polarized multiple-angle incidence resolution spectrometry (pMAIRS) was used to determine the orientation of a specific residue of α-helical NAC in monolayer. In general, pMAIRS is a novel technique to work complementary with X-ray and NMR to address membrane peptides/proteins structure with high resolution even in monolayer

Nontoxic Carbon Dots Potently Inhibit Human Insulin Fibrillation

One prevention and therapeutic strategy for diseases associated with peptide or protein fibrillation is to inhibit or delay the fibrillation process. Carbon dots (C–Dots) have recently emerged as benign nanoparticles to replace toxic quantum dots and have attracted great attention because of their unique optical properties and potential applications in biological systems. However, the effect of C-Dots on peptide or protein fibrillation has not been explored. In this in vitro study, human insulin was selected as a model to investigate the effect of C-Dots on insulin fibrillation. Water-soluble fluorescent C-Dots with sizes less than 6 nm were prepared from carbon powder and characterized by UV–vis spectroscopy, fluorescence, Fourier transform infrared spectrophotometry, X-ray photoelectron spectrometry, transmission electron microscopy, and atomic force microscopy. These C-Dotswere able to efficiently inhibit insulin fibrillation in a concentration-dependent manner. Theinhibiting effect of C-Dots was even observed at 0.2 μg/mL. Importantly, 40 μg/mL of C-Dots prevent 0.2 mg/mL of human insulin from fibrillation for 5 days under 65 °C, whereas insulin denatures in 3 h under the same conditions without C-Dots. The inhibiting effect is likely due to the interaction between C-Dots and insulin species before elongation. Cytotoxicity study shows that these C-Dots have very low cytotoxicity. Therefore, these C-Dots have the potential to inhibit insulin fibrillation in biological systems and in the pharmaceutical industry for the processing and formulation of insulin

Fluorescence Spectroscopy in Structural Studies of Plant Cell Walls

Plant cell walls represent the most abundant, renewable and biodegradable composite on Earth. Its highly complex structure consists mainly of three organic compounds: cellulose, hemicelluloses, and lignin. Cell walls have wide applications in different industries, especially for biofuels and biomaterials. Fluorescence spectroscopy is the method allowing investigation of cell wall structure thought monitoring of lignin autoflorescence and thus interactions of lignin with the other cell wall constituents. Deconvolution of fluorescence spectra reveals the number and location of spectral component peaks by calculation of the approximation of the probability density (APD) of component positions. A characteristic of complex CW fluorescence is that the emission spectrum contains multiple log–normal components originating from different fluorophores, shorter wavelengths corresponding to phenolic structures and longer wavelengths to conjugated structures in lignin. Fluorescence spectroscopy has been used for fast screening of the cell wall properties from plants of different origin (hardwood, softwood and herbaceous plant), that may be important for selection of plants for possible applications. Fluorescence spectroscopy may be applicable in the investigation of the effect of stress on the cell wall. Lignin fluorescence emission spectra, peak intensities and shifts in the positions of the long-wavelength spectral components may be indicators of changes in cell wall structure during the stress. There is an increasing application of quantum dots (QDs) in plant science, as fluorescent markers. The isolated cell wall is an appropriate object for study of the interactions with nanoparticles. The results of different physico-chemical techniques including fluorescence spectroscopy combined with spectral deconvolution, show that in the cell walls, CdSe QDs predominantly bind to cellulose, via OH groups, and to lignin, via the conjugated C=C/C–C chains. Variability of bond types in lignin is related to the involvement of this polymer in plant response to various types of stress, by introducing local structural modifications in the cell wall. Different lignin model compounds have been used in order to reveal spectroscopic properties of lignin. Lignin model polymers were synthesized from three monomers, coniferyl alcohol, ferulic acid and p-coumaric acid mixed in various ratios, simulating lignin synthesis in the real cell walls. Further, by using fluorescence spectroscopy and appropriate mathematical methods, it is possible to get deeper insight into the structural characteristics of the molecule. Future investigations will be based on synthetic cell walls and on variation in a portion of all three main components: cellulose, hemicelluloses and lignin, also having in mind results of fine structural modifications in lignin model compounds

Influence of orange carbon dots on antioxidative activity in maize

Carbon dots (CDs) are spherical organic nanoparticles with a huge potential for application in various biomedical purposes such as sensing, bioimaging, and drug delivery, as well as in water remediation. The discovery of CDs was very popular in the 21th century because they can be used where metal nanoparticles cannot be applied, so they are considered as their green alternative. The main advantages of these nanoparticles are their ease of preparation, solubility in water, high photoluminescence, and biocompatibility. Having all these properties in mind, the main aim of this research was to investigate the effect of orange carbon dots (oCDs), synthesized from citric acid and o-phenylenediamine as precursors, on total antioxidative activity (TAA) in maize as a model plant and agricultural species. We tested antioxidative activity as an indicator of oxidative stress and metabolic disorder in plants. TAA mainly includes the contribution of different non-enzymatic components with antioxidant capacity (vitamins, phenolic acids, sugars, etc.). The maize plants were exposed to three different concentrations (1, 5, and 10 mg L-1) of oCDs nanoparticles via KNOP/2 hydroponic solution during growth under 16 h/8 h photoperiod. After the 2 week-growth, the leaves and roots of plants were separately harvested and collected. The results showed that oCDs did not induce any change in TAA in the leaves, but increased TAA in roots after the treatment of plants with 5 and 10 mg L-1 oCDs. It can be concluded that plant treatment with oCDs’ concentrations ≥ 5 mg L-1 leads to the increase of oxidative stress in roots as a plant organ more exposed to the nanoparticles. This research opens new possibilities in the uses of oCDs in agricultural applications

Dihydrolipoic Acid Conjugated Carbon Dots Accelerate Human Insulin Fibrillation

Protein fibrillation is believed to play an important role in the pathology and development of several human diseases, such as Alzheimer’s disease, Parkinson’s disease and type 2 diabetes. Carbon dots (CDs), as a new type of nanoparticle have recently been extensively studied for potential biological applications, but their effects on protein fibrillation remain unexplored. In reality, any application in biological systems will inevitably have “contact” between proteins and CDs. In this study, human insulin was selected as a model protein to study the effects of CDs on protein fibrillation, as proteins may share a common mechanism to form fibrils. Hydrophobic CDs were conjugated with dihydrolipoic acid (DHLA-CDs) to facilitate their water solubility. Characterizations from thioflavin T fluorescence, circular dichroism spectroscopy and atomic force microscopy demonstrate that the presence of DHLA-CDs results in a higher rate of human insulin fibrillation, accelerating the conformational changes of human insulin from α-helix to β-sheet. This promoting effect is likely associated with the locally increased concentration of human insulin adsorbed on the surface of DHLA-CDs