scholarly journals Proton Conductivity of Glycosaminoglycans

2018 ◽  
Author(s):  
John Selberg ◽  
Manping Jia ◽  
Marco Rolandi

AbstractProton (H+) conductivity is important in many natural phenomena including oxidative phosphorylation in mitochondria and archea, uncoupling membrane potentials by the antibiotic Gramicidin, and proton actuated bioluminescence in dinoflagellate. In all of these phenomena, the conduction of H+ occurs along chains of hydrogen bonds between water and hydrophilic residues. These chains of hydrogen bonds are also present in many hydrated biopolymers and macromolecule including collagen, keratin, chitosan, and various proteins such as reflectin. All of these materials are also proton conductors. Recently, our group has discovered that the jelly found in the Ampullae of Lorenzini-shark’s electrosensing organs- is the highest naturally occurring proton conducting substance. The jelly has a complex composition, but we attributed the conductivity to the glycosaminoglycan keratan sulfate (KS). Here, we have measured the proton conductivity of hydrated keratan sulfate using PdHx contacts to be 0.50 ± 0.11 mS cm -1- consistent to that of Ampullae of Lorenzini jelly, 2 ± 1 mS cm -1. Proton conductivity, albeit with lower values, is also shared by other glycosaminoglycans with similar chemical structures including dermatan sulfate, chondroitin sulfate A, heparan sulfate, and hyaluronic acid. This observation confirms the structure property relationship between proton conductivity and the chemical structure of biopolymers.

2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Nur Laila Hamidah ◽  
Masataka Shintani ◽  
Aynul Sakinah Ahmad Fauzi ◽  
Shota Kitamura ◽  
Elaine G. Mission ◽  
...  

AbstractWater electrolysis is an environment-friendly process of producing hydrogen with zero-carbon emission. Herein, we studied the water vapor electrolysis using a proton-conducting membrane composed of graphene oxide (GO) nanosheets intercalated with cations (Al3+ and Ce3+). We examined the effect of cation introduction on the physical and chemical structures, morphology, thermal and chemical stabilities, and the proton conductivity of stacked GO nanosheet membranes by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoemission spectroscopy (XPS), Raman spectroscopy, atomic force microscopy (AFM), dynamic light scattering (DLS), thermogravimetric-differential thermal analysis (TG-DTA), and electrochemical impedance spectroscopy (EIS). Concentration cell measurements revealed that the cation-modified membranes are pure proton conductors at room temperature. The proton conductivity of a GO membrane was much improved by cation modification. The cation-modified GO membranes, sandwiched with Pt/C electrodes as the cathode and anode, electrolyzed humidified air to produce hydrogen at room temperature, indicating the feasibility of this carbon-based electrochemical device.


2016 ◽  
Vol 2 (5) ◽  
pp. e1600112 ◽  
Author(s):  
Erik E. Josberger ◽  
Pegah Hassanzadeh ◽  
Yingxin Deng ◽  
Joel Sohn ◽  
Michael J. Rego ◽  
...  

In 1678, Stefano Lorenzini first described a network of organs of unknown function in the torpedo ray—the ampullae of Lorenzini (AoL). An individual ampulla consists of a pore on the skin that is open to the environment, a canal containing a jelly and leading to an alveolus with a series of electrosensing cells. The role of the AoL remained a mystery for almost 300 years until research demonstrated that skates, sharks, and rays detect very weak electric fields produced by a potential prey. The AoL jelly likely contributes to this electrosensing function, yet the exact details of this contribution remain unclear. We measure the proton conductivity of the AoL jelly extracted from skates and sharks. The room-temperature proton conductivity of the AoL jelly is very high at 2 ± 1 mS/cm. This conductivity is only 40-fold lower than the current state-of-the-art proton-conducting polymer Nafion, and it is the highest reported for a biological material so far. We suggest that keratan sulfate, identified previously in the AoL jelly and confirmed here, may contribute to the high proton conductivity of the AoL jelly with its sulfate groups—acid groups and proton donors. We hope that the observed high proton conductivity of the AoL jelly may contribute to future studies of the AoL function.


2018 ◽  
Vol 21 (7) ◽  
pp. 533-542 ◽  
Author(s):  
Neda Ahmadinejad ◽  
Fatemeh Shafiei ◽  
Tahereh Momeni Isfahani

Aim and Objective: Quantitative Structure- Property Relationship (QSPR) has been widely developed to derive a correlation between chemical structures of molecules to their known properties. In this study, QSPR models have been developed for modeling and predicting thermodynamic properties of 76 camptothecin derivatives using molecular descriptors. Materials and Methods: Thermodynamic properties of camptothecin such as the thermal energy, entropy and heat capacity were calculated at Hartree–Fock level of theory and 3-21G basis sets by Gaussian 09. Results: The appropriate descriptors for the studied properties are computed and optimized by the genetic algorithms (GA) and multiple linear regressions (MLR) method among the descriptors derived from the Dragon software. Leave-One-Out Cross-Validation (LOOCV) is used to evaluate predictive models by partitioning the total sample into training and test sets. Conclusion: The predictive ability of the models was found to be satisfactory and could be used for predicting thermodynamic properties of camptothecin derivatives.


2021 ◽  
Vol 22 (9) ◽  
pp. 4808
Author(s):  
Nitza Soto ◽  
Karoll Ferrer ◽  
Katy Díaz ◽  
César González ◽  
Lautaro Taborga ◽  
...  

Brassinosteroids are polyhydroxysteroids that are involved in different plants’ biological functions, such as growth, development and resistance to biotic and external stresses. Because of its low abundance in plants, much effort has been dedicated to the synthesis and characterization of brassinosteroids analogs. Herein, we report the synthesis of brassinosteroid 24-nor-5β-cholane type analogs with 23-benzoate function and 22,23-benzoate groups. The synthesis was accomplished with high reaction yields in a four-step synthesis route and using hyodeoxycholic acid as starting material. All synthesized analogs were tested using the rice lamina inclination test to assess their growth-promoting activity and compare it with those obtained for brassinolide, which was used as a positive control. The results indicate that the diasteroisomeric mixture of monobenzoylated derivatives exhibit the highest activity at the lowest tested concentrations (1 × 10−8 and 1 × 10−7 M), being even more active than brassinolide. Therefore, a simple synthetic procedure with high reaction yields that use a very accessible starting material provides brassinosteroid synthetic analogs with promising effects on plant growth. This exploratory study suggests that brassinosteroid analogs with similar chemical structures could be a good alternative to natural brassinosteroids.


1999 ◽  
Vol 600 ◽  
Author(s):  
Yong-Il Park ◽  
Jae-Dong Kim ◽  
Masayuki Nagai

AbstractA drastic increase of electrical conductivity was observed in the composite of amorphous phosphate and ion-exchange resins (Nafion) as phosphorus concentration increased. Incorporation of amorphous phosphate into Nafion caused a large increase of conductivity to about 4×10−1S/cm at 23°C. However, the fabricated composite showed very low chemical stability.A high proton conductivity was also observed in a new inorganic-organic hybrids through incorporating PMA(molibdo-phosphoric acid)/PWA(tungsto-phosphoric acid) as a proton source in amorphous silicophosphate gel structure. Obtained gels were homogeneous and chemically stable. Resulting proton conductivity is very high (up to 5.5×10−3S/cm) compared to those of silicophosphate gels.


Polymers ◽  
2020 ◽  
Vol 13 (1) ◽  
pp. 130
Author(s):  
Carlos Corona-García ◽  
Alejandro Onchi ◽  
Arlette A. Santiago ◽  
Araceli Martínez ◽  
Daniella Esperanza Pacheco-Catalán ◽  
...  

The future availability of synthetic polymers is compromised due to the continuous depletion of fossil reserves; thus, the quest for sustainable and eco-friendly specialty polymers is of the utmost importance to ensure our lifestyle. In this regard, this study reports on the use of oleic acid as a renewable source to develop new ionomers intended for proton exchange membranes. Firstly, the cross-metathesis of oleic acid was conducted to yield a renewable and unsaturated long-chain aliphatic dicarboxylic acid, which was further subjected to polycondensation reactions with two aromatic diamines, 4,4′-(hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline and 4,4′-diamino-2,2′-stilbenedisulfonic acid, as comonomers for the synthesis of a series of partially renewable aromatic-aliphatic polyamides with an increasing degree of sulfonation (DS). The polymer chemical structures were confirmed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (1H, 13C, and 19F NMR) spectroscopy, which revealed that the DS was effectively tailored by adjusting the feed molar ratio of the diamines. Next, we performed a study involving the ion exchange capacity, the water uptake, and the proton conductivity in membranes prepared from these partially renewable long-chain polyamides, along with a thorough characterization of the thermomechanical and physical properties. The highest value of the proton conductivity determined by electrochemical impedance spectroscopy (EIS) was found to be 1.55 mS cm−1 at 30 °C after activation of the polymer membrane.


2021 ◽  
pp. 095400832110130
Author(s):  
Hailong Li ◽  
Sipei Zhao ◽  
Li Pei ◽  
Zihe Qiao ◽  
Ding Han ◽  
...  

Polybenzoxazines are emerging as a class of high-performance thermoset polymers that can find their applications in various fields. However, its practical application is limited by its low toughness. The cyclic β-cyclodextrin and a newly synthesized derivative (β-cyclodextrin-MAH) were separately blended with benzoxazine to improve the toughness of polybenzoxazine. The results revealed that the maximum impact strength of the blend was 12.24 kJ·m−2 and 14.29 kJ·m−2 when 1 wt.% of β-Cyclodextrin and β-Cyclodextrin-MAH, respectively, were used. The strengths were 53% and 86% higher than that of pure polybenzoxazine. The curing reaction, possible chemical structures, and fractured surface were examined using differential scanning calorimetry, Fourier transform infrared spectroscopy, and scanning electron microscopy techniques to understand the mechanism of generation of toughness. The results revealed that the sea-island structure and the presence of hydrogen bonds between polybenzoxazine and β-cyclodextrin and β-cyclodextrin-MAH resulted in the generation of toughness. Furthermore, the curves generated during thermogravimetric analysis did not significantly change, revealing the good thermal properties of the system. The phase-separated structure and the hydrogen bonds present in the system can be exploited to prepare synergistically tough polybenzoxazine exhibiting excellent thermal properties. This can be a potential way of modifying the thermoset resins.


1993 ◽  
Vol 47 (7) ◽  
pp. 933-941 ◽  
Author(s):  
Karen L. Buchert ◽  
Jack L. Koenig ◽  
Shi-Qing Wang ◽  
John L. West

In samples of polymer-dispersed liquid crystals (PDLCs), submicron droplets of liquid crystal reside within a polymer matrix. By the use of the cross polarization technique for solid-state 13C NMR spectroscopy, the NMR spectrum of the liquid crystal can be obtained without interference from the polymer spectrum, even though the two materials have some similar chemical structures. Both 13C T1 and 13C T1 ρ relaxation experiments were performed on a PDLC system of 5CB in epoxy as a function of 5CB domain size. The 13C T1 relaxation constants and the localized motions they measure showed no significant change over the liquid crystal domain size studied. However, the 13C T1 ρ relaxation constants and the segmental motions of molecules they measure revealed a significant change over the liquid crystal domain size studied. Therefore, the 13C T1 ρ values can be used to determine the change in mobility of the molecular segments of the SCB molecules resulting from increased interaction between the liquid crystal and the polymer matrix and to further understand the importance of the molecular motions of the liquid crystal in the switching phenomenon for PDLC materials.


Polymers ◽  
2018 ◽  
Vol 10 (11) ◽  
pp. 1287 ◽  
Author(s):  
Wenmeng Zhang ◽  
Shaoyun Chen ◽  
Dongyang Chen ◽  
Zhuoliang Ye

Sterically hindered (S)-1,1′-binaphthyl-2,2′-diol had been successfully copolymerized with 4,4′-sulfonyldiphenol and 4,4′-difluorobenzophenone to yield fibrous poly(arylene ether ketone)s (PAEKs) containing various amounts of binaphthyl unit, which was then selectively and efficiently sulfonated using ClSO3H to yield sulfonated poly(arylene ether ketone)s (SPAEKs) with ion exchange capacities (IECs) ranging from 1.40 to 1.89 mmol·g−1. The chemical structures of the polymers were confirmed by 2D 1H–1H COSY NMR and FT-IR. The thermal properties, water uptake, swelling ratio, proton conductivity, oxidative stability and mechanical properties of SPAEKs were investigated in detail. It was found that the conjugated but non-coplanar structure of binaphthyl unit endorsed excellent solubility and film-forming capability to SPAEKs. The SPAEK-50 with an IEC of 1.89 mmol·g−1 exhibited a proton conductivity of 102 mS·cm−1 at 30 °C, much higher than that of the state-of-the-art Nafion N212 membrane and those of many previously reported aromatic analogs, which may be attributed to the likely large intrinsic free volume of SPAEKs created by the highly twisted chain structures and the desirable microscopic morphology. Along with the remarkable water affinity, thermal stabilities and mechanical properties, the SPAEKs were demonstrated to be promising proton exchange membrane (PEM) candidates for potential membrane separations.


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