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1.
Proc Natl Acad Sci U S A ; 117(6): 2938-2947, 2020 02 11.
Article in English | MEDLINE | ID: mdl-31980523

ABSTRACT

The conformational changes required for activation and K+ conduction in inward-rectifier K+ (Kir) channels are still debated. These structural changes are brought about by lipid binding. It is unclear how this process relates to fast gating or if the intracellular and extracellular regions of the protein are coupled. Here, we examine the structural details of KirBac1.1 reconstituted into both POPC and an activating lipid mixture of 3:2 POPC:POPG (wt/wt). KirBac1.1 is a prokaryotic Kir channel that shares homology with human Kir channels. We establish that KirBac1.1 is in a constitutively active state in POPC:POPG bilayers through the use of real-time fluorescence quenching assays and Förster resonance energy transfer (FRET) distance measurements. Multidimensional solid-state NMR (SSNMR) spectroscopy experiments reveal two different conformers within the transmembrane regions of the protein in this activating lipid environment, which are distinct from the conformation of the channel in POPC bilayers. The differences between these three distinct channel states highlight conformational changes associated with an open activation gate and suggest a unique allosteric pathway that ties the selectivity filter to the activation gate through interactions between both transmembrane helices, the turret, selectivity filter loop, and the pore helix. We also identify specific residues involved in this conformational exchange that are highly conserved among human Kir channels.


Subject(s)
Bacterial Proteins/chemistry , Bacterial Proteins/metabolism , Potassium Channels, Inwardly Rectifying/chemistry , Potassium Channels, Inwardly Rectifying/metabolism , Bacterial Proteins/genetics , Catalytic Domain , Fluorescence Resonance Energy Transfer , Kinetics , Magnetic Resonance Spectroscopy , Models, Molecular , Phosphatidylcholines/chemistry , Phosphatidylcholines/metabolism , Phosphatidylglycerols/chemistry , Phosphatidylglycerols/metabolism , Potassium/metabolism , Potassium Channels, Inwardly Rectifying/genetics , Protein Conformation , Protein Domains , Protein Structure, Secondary
2.
Proc Natl Acad Sci U S A ; 117(28): 16363-16372, 2020 07 14.
Article in English | MEDLINE | ID: mdl-32601205

ABSTRACT

The epididymal lumen contains a complex cystatin-rich nonpathological amyloid matrix with putative roles in sperm maturation and sperm protection. Given our growing understanding for the biological function of this and other functional amyloids, the problem still remains: how functional amyloids assemble including their initial transition to early oligomeric forms. To examine this, we developed a protocol for the purification of nondenatured mouse CRES, a component of the epididymal amyloid matrix, allowing us to examine its assembly to amyloid under conditions that may mimic those in vivo. Herein we use X-ray crystallography, solution-state NMR, and solid-state NMR to follow at the atomic level the assembly of the CRES amyloidogenic precursor as it progressed from monomeric folded protein to an advanced amyloid. We show the CRES monomer has a typical cystatin fold that assembles into highly branched amyloid matrices, comparable to those in vivo, by forming ß-sheet assemblies that our data suggest occur via two distinct mechanisms: a unique conformational switch of a highly flexible disulfide-anchored loop to a rigid ß-strand and by traditional cystatin domain swapping. Our results provide key insight into our understanding of functional amyloid assembly by revealing the earliest structural transitions from monomer to oligomer and by showing that some functional amyloid structures may be built by multiple and distinctive assembly mechanisms.


Subject(s)
Amyloid/chemistry , Amyloidogenic Proteins/chemistry , Cystatins/chemistry , Amyloid/metabolism , Amyloid/ultrastructure , Amyloidogenic Proteins/metabolism , Animals , Crystallography, X-Ray , Cystatins/metabolism , Epididymis/metabolism , Magnetic Resonance Spectroscopy , Male , Mice , Models, Molecular , Protein Conformation , Protein Folding , Protein Multimerization
3.
J Am Chem Soc ; 142(33): 14102-14116, 2020 08 19.
Article in English | MEDLINE | ID: mdl-32702990

ABSTRACT

Membrane proteins and lipids coevolved to yield unique coregulatory mechanisms. Inward-rectifier K+ (Kir) channels are often activated by anionic lipids endemic to their native membranes and require accessible water along their K+ conductance pathway. To better understand Kir channel activation, we target multiple mutants of the Kir channel KirBac1.1 via solid-state nuclear magnetic resonance (SSNMR) spectroscopy, potassium efflux assays, and Förster resonance energy transfer (FRET) measurements. In the I131C stability mutant (SM), we observe an open-active channel in the presence of anionic lipids with greater activity upon addition of cardiolipin (CL). The introduction of three R to Q mutations (R49/151/153Q (triple Q mutant, TQ)) renders the protein inactive within the same activating lipid environment. Our SSNMR experiments reveal a stark reduction of lipid-protein interactions in the TQ mutant explaining the dramatic loss of channel activity. Water-edited SSNMR experiments further determined the TQ mutant possesses greater overall solvent exposure in comparison to wild-type but with reduced water accessibility along the ion conduction pathway, consistent with the closed state of the channel. These experiments also suggest water is proximal to the selectivity filter of KirBac1.1 in the open-activated state but that it may not directly enter the selectivity filter. Our findings suggest lipid binding initiates a concerted rotation of the cytoplasmic domain subunits, which is stabilized by multiple intersubunit salt bridges. This action buries ionic side chains away from the bulk water, while allowing water greater access to the K+ conduction pathway. This work highlights universal membrane protein motifs, including lipid-protein interactions, domain rearrangement, and water-mediated diffusion mechanisms.


Subject(s)
Lipids/chemistry , Potassium Channels/metabolism , Fluorescence Resonance Energy Transfer , Nuclear Magnetic Resonance, Biomolecular , Potassium Channels/chemistry , Potassium Channels/genetics
4.
Small ; 16(12): e1901564, 2020 Mar.
Article in English | MEDLINE | ID: mdl-31166653

ABSTRACT

Polyanilines (pANIs), loaded with phosphotungstic acid (PTA), are pyrolyzed to get WO3 or W2 N (≈6 and ≈7 nm, respectively), which is well-dispersed on pANI-derived porous carbons (pDCs). Depending on the pyrolysis temperature, WO3 /pDC, W2 N/pDC, or W2 N-W/pDCs could be obtained selectively. pANI acts as both the precursor of pDC and the nitrogen source for the nitridation of WO3 into W2 N during the pyrolysis. Importantly, W2 N could be obtained from the pyrolysis without ammonia feeding. The obtained W2 N/pDC is applied as a heterogeneous catalyst for the oxidative desulfurization (ODS) of liquid fuel for the first time, and the results are compared with WO3 /pDC and WO3 /ZrO2 . The W2 N/pDC is very efficient in ODS with remarkable performance compared with WO3 /pDC or WO3 /ZrO2 , which is applied as a representative ODS catalyst. For example, W2 N/pDC shows around 3.4 and 2.7 times of kinetic constant and turnover frequency (based on 5 min of reaction), respectively, compared to that of WO3 /ZrO2 . Moreover, the catalysts could be regenerated in a facile way. Therefore, W2 N/pDC could be produced facilely from pyrolysis (without ammonia feeding) of PTA/pANI, and W2 N, well-dispersed on pDC, can be suggested as a very efficient oxidation catalyst for the desulfurization of liquid fuel.

5.
Inorg Chem ; 55(21): 11362-11371, 2016 Nov 07.
Article in English | MEDLINE | ID: mdl-27763765

ABSTRACT

Two highly porous Co-based metal-azolate frameworks (MAFs), MAF-5(Co) and MAF-6(Co), which are isostructural with MAF-5(Zn) and MAF-6(Zn), respectively, were first synthesized in high yield and purity at room temperature. The syntheses compared two mixing methods, slow and fast, using cobalt acetate as the metal ion (Co2+) source and 2-ethylimidazole as the ligand. Triethylamine was applied as an additive/promoter in aqueous/ethanol solutions, and benzene and cyclohexane were used as hydrophobic templates. Phase-pure MAF-5(Co) and MAF-6(Co) were obtained in high yield by optimizing the mixing speed, reactant composition, and solvent/template ratio. It was found that fast mixing of the reactant mixtures was effective for synthesizing MAF(Co) materials. MAF-5(Co) and MAF-6(Co) were found to be very hydrophobic, similar to the MAFs composed of Zn, suggesting possible applications in water purification. MAF-5(Co) and MAF-6(Co) were then applied to adsorb n-octane as a model oil and nonpolar adsorbate from water, and the obtained results were compared to those of related materials, i.e., MAF-4(Co and Zn), MAF-5(Zn), and MAF-6(Zn), as well as with Cu-BTC (Cu-benzenetricarboxylate) and a conventional adsorbent, activated carbon. Surprisingly, despite having low porosity, MAF-5(Co) showed remarkable competitiveness among the typical porous materials for n-octane removal. The results suggest that the framework structure such as cavity and aperture sizes rather than surface area plays a significant role in n-octane removal. Moreover, MAF-5(Co) can easily be regenerated by simple evacuation and reused, and thus it was found to be a potential adsorbent for the removal of spilled oil from water. Additionally, MAFs were applied in the adsorption of diclofenac sodium from water, showing the competitiveness of MAFs in water purification probably because of hydrophobicity.

6.
Inorg Chem ; 54(23): 11498-504, 2015 Dec 07.
Article in English | MEDLINE | ID: mdl-26575418

ABSTRACT

Scandium-triflate (Sc(OTf)3) was introduced for the first time on metal-organic frameworks (MOFs), to utilize acidic Sc(OTf)3 for adsorptive desulfurization and denitrogenation of fuel containing benzothiophene (BT), dibenzothiophene (DBT), quinoline (QUI), and indole (IND). A remarkable improvement in the adsorption capacity (about 65% based on the weight of adsorbents; 90% based on the surface area of the adsorbents) was observed with the Sc(OTf)3/MOFs as compared to the virgin MOFs for the adsorption of BT from liquid fuel. The basic QUI was also adsorbed preferentially onto the acidic Sc(OTf)3/MOFs. However, nonsupported Sc(OTf)3 showed negligible adsorption capacities. The improved adsorptive performance for BT, DBT, and QUI might be derived from acid-base interactions between the acidic Sc(OTf)3 and basic adsorbates. On the other hand, the Sc(OTf)3, loaded on MOFs, reduced the adsorption capacity for neutral IND due to lack of interaction between the neutral adsorbate and acidic adsorbent and the reduced porosities of the modified adsorbents. The reusability of the adsorbents was found satisfactory up to the fourth run. On the basis of the result, it is suggested that metal-triflates, such as Sc(OTf)3, can be prospective materials for adsorptive desulfurization/denitrogenation of fuels when supported on porous materials such as MOFs.

7.
Chemistry ; 20(2): 376-80, 2014 Jan 07.
Article in English | MEDLINE | ID: mdl-24390909

ABSTRACT

Acidic ionic-liquids (IL) supported on metal-organic frameworks (MOFs) have been shown to be beneficial for adsorptive desulfurization. A remarkable improvement in the adsorption capacity (ca. 71%) was observed in for ILs supported on MIL-101 compared with virgin MIL-101. The improved adsorptive performance might be explained by the acid-base interactions between the acidic ionic liquid and basic benzothiophene (BT). Moreover, from this study, it can be suggested that porous MOFs, supported with ionic liquids, may introduce a new class of highly porous adsorbents for the efficient adsorption of various compounds.

8.
Inorg Chem ; 52(24): 14155-61, 2013 Dec 16.
Article in English | MEDLINE | ID: mdl-24299306

ABSTRACT

A highly porous metal-organic framework (MOF), MIL-101 (Cr-benzenedicarboxylate), was synthesized in the presence of graphite oxide (GO) to produce GO/MIL-101 composites. The porosity of the composites increased remarkably in the presence of a small amount of GO (<0.5% of MIL-101); however, further increases in GO reduced the porosity. GO also accelerated the synthesis of the MIL-101. The composites (GO/MIL-101) were used, for the first time, in liquid-phase adsorptions. The adsorptive removal of nitrogen-containing compounds (NCCs) and sulfur-containing compounds (SCCs) from model fuels demonstrated the potential applications of the composites in adsorptions, and the adsorption capacity was dependent on the surface area and pore volume of the composites. Most importantly, the GO/MIL-101 composite has the highest adsorption capacity for NCCs among reported adsorbents so far, partly because of the increased porosity of the composite. Finally, the results suggest that GO could be used in the synthesis of highly porous MOF composites, and the obtained materials could be used in various adsorptions in both liquid and gas/vapor phase (such as H2, CH4, and CO2 storage) adsorptions, because of the high porosity and functional GO.

9.
J Nanosci Nanotechnol ; 13(4): 2789-94, 2013 Apr.
Article in English | MEDLINE | ID: mdl-23763161

ABSTRACT

Adsorptive removal of bisphenol-A (BPA) using a MOF, Cr-benzenedicarboxylate (MIL-53), has been studied to understand the applicability of MOFs for the removal of hazardous endocrine disturbing chemicals from water. MIL-53 shows very fast adsorption in an hour and the adsorption capacity of MIL-53 is higher than that of activated carbon. Importantly, the adsorption of BPA over MIL-53 is very favorable especially at very low concentrations of BPA. Therefore, MOFs such as MIL-53 can be one of adsorbents that may be used in the adsorptive removal of BPA from contaminated water.


Subject(s)
Benzene/chemistry , Benzhydryl Compounds/isolation & purification , Chromium/chemistry , Dicarboxylic Acids/chemistry , Metals/chemistry , Organic Chemicals/chemistry , Phenols/isolation & purification , Water Pollutants, Chemical/isolation & purification , Adsorption , X-Ray Diffraction
10.
J Safety Res ; 80: 97-108, 2022 02.
Article in English | MEDLINE | ID: mdl-35249632

ABSTRACT

INTRODUCTION: This study develops an injury severity model that demonstrates level of pedestrians' injury severity during pedestrian-vehicle collisions, specifically those involving distracted driving. METHOD: It uses data from a police-reported collision database that contains pedestrian-vehicle collision information in Nova Scotia, Canada. A latent segmentation-based ordered logit (LSOL) model is developed in this paper that comprehensively examines the influence of built environment characteristics on pedestrian injury severity. It estimates a latent segment allocation model within LSOL modeling framework to capture unobserved heterogeneity across pedestrians. Two latent segments, high- and low-risk segments, are identified probabilistically based on pedestrian characteristics and action, driver action, and collision attributes. RESULTS: Results suggest that higher mixed land-use, transit stop density, length of sidewalk in the collision locations, and collisions occurring near schools yield lower pedestrian injury severity. In contrast, pedestrian-vehicle collisions in arterial roads, curved roads, sloped roads, and roundabouts tend to result in severe injuries. Interactions between distracted driving type and built environment characteristics are examined in this study. For example, using a communication device while driving on straight roads increases likelihood of higher pedestrian injury severity. This study also confirms the existence of heterogeneity across latent segments. For instance, higher percentage of people commuting by walking in the collision areas yield severe pedestrian injury in high-risk segments and lower injury severity in low-risk segments. Practical applications: The findings of this study will assist transportation planners and road safety stakeholders in developing effective and prioritized policies to reduce pedestrian injury severity involving distracted driving incidents.


Subject(s)
Automobile Driving , Distracted Driving , Pedestrians , Wounds and Injuries , Accidents, Traffic , Built Environment , Humans , Walking/injuries
11.
Chemistry ; 17(23): 6437-42, 2011 May 27.
Article in English | MEDLINE | ID: mdl-21547968

ABSTRACT

Chemical and thermal stabilities of isotypic metal-organic frameworks (MOFs) like Al-BDC (Al-benzenedicarboxylate called MIL-53-Al), Cr-BDC (MIL-53-Cr) and V-BDC (MIL-47-V), after purification to remove uncoordinated organic linkers, have been compared to understand the effect of the central metal ions on the stabilities of the porous MOF-type materials. Chemical stability to acids, bases, and water decreases in the order of Cr-BDC>Al-BDC>V-BDC, suggesting stability increases with increasing inertness of the central metal ions. However, thermal stability decreases in the order of Al-BDC>Cr-BDC> V-BDC, and this tendency may be explained by the strength of the metal-oxygen bond in common oxides like Al(2)O(3), Cr(2)O(3), and V(2)O(5). In order to evaluate precisely the stability of a MOF, it is necessary to remove uncoordinated organic linkers that are located in the pores of the MOF, because a filled MOF may be more stable than the same MOF after purification.

12.
Chemistry ; 16(3): 1046-52, 2010 Jan 18.
Article in English | MEDLINE | ID: mdl-20014080

ABSTRACT

A metal-organic framework material named MIL-53(Fe), iron terephthalate, has been synthesized sovothermally at a relatively low temperature by not only conventional electric (CE) heating, but also by irradiation under ultrasound (US) and microwave (MW) conditions to gain an understanding of the accelerated syntheses induced by US and MW. The kinetics for nucleation and crystal growth were analyzed by measuring the crystallinity of MIL-53(Fe) under various conditions. The nucleation and crystal growth rates were estimated from crystallization curves of the change in crystallinity with reaction time. The activation energies and pre-exponential factors were calculated from Arrhenius plots. It was confirmed that the rate of crystallization (both nucleation and crystal growth) decreases in the order US>MW>>CE, and that the accelerated syntheses under US and MW conditions are due to increased pre-exponential factors rather than decreased activation energies. It is suggested that physical effects such as hot spots are more important than chemical effects in the accelerated syntheses induced by US and MW irradiation. The syntheses were also conducted in two steps to understand quantitatively the acceleration induced by MW and it was found that the acceleration in crystal growth is more important than the acceleration in nucleation, even though both processes are accelerated by MW irradiation.

13.
Phys Chem Chem Phys ; 12(11): 2625-31, 2010 Mar 20.
Article in English | MEDLINE | ID: mdl-20200739

ABSTRACT

A typical MOF material, Cu-BTC has been synthesized with microwave and conventional electric heating in various conditions to elucidate, for the first time, the quantitative acceleration in the synthesis of a MOF by microwaves. The acceleration by microwaves is mainly due to rapid nucleation rather than rapid crystal growth, even though both stages are accelerated. The acceleration in the nucleation stage by microwaves is due to the very large pre-exponential factor (about 1.4 x 10(10) times that of conventional synthesis) in the Arrhenius plot. However, the activation energy for the nucleation in the case of microwave synthesis is higher than the activation energy of conventional synthesis. The large acceleration in the nucleation, compared with that in the crystal growth, is observed once again by the syntheses in two-steps (changing heating methods from microwave into conventional heating or from conventional heating into microwave heating just after the nucleation is completed). The crystal size of Cu-BTC obtained by microwave-nucleation is generally smaller than the Cu-BTC made by conventional-nucleation, probably due to rapid nucleation and the small size of nuclei with microwave-nucleation.

14.
Beilstein J Nanotechnol ; 11: 597-605, 2020.
Article in English | MEDLINE | ID: mdl-32318320

ABSTRACT

Polyaniline-derived carbon (PDC) was obtained via pyrolysis of polyaniline under different temperatures and applied for the purification of water contaminated with dye molecules of different sizes and charge by adsorption. With increasing pyrolysis temperature, it was found that the hydrophobicity, pore size and mesopore volume increased. A mesoporous PDC sample obtained via pyrolysis at 900 °C showed remarkable performance in the adsorption of dye molecules, irrespective of dye charge, especially in the removal of bulky dye molecules, such as acid red 1 (AR1) and Janus green B (JGB). For example, the most competitive PDC material showed a Q 0 value (maximum adsorption capacity) 8.1 times that of commercial, activated carbon for AR1. The remarkable adsorption of AR1 and JGB over KOH-900 could be explained by the combined mechanisms of hydrophobic, π-π, electrostatic and van der Waals interactions.

15.
ACS Omega ; 5(35): 22356-22366, 2020 Sep 08.
Article in English | MEDLINE | ID: mdl-32923793

ABSTRACT

Cu-doped Mn3O4 and Mn-doped CuO (CMO@MCO) mixed oxides with isolated phases together with pristine Mn3O4 (MO) and CuO (CO) have been synthesized by a simple solution process for applications in electrochemical supercapacitors. The crystallographic, spectroscopic, and morphological analyses revealed the formation of all of the materials with good crystallinity and purity with the creation of rhombohedral-shaped MO and CMO and a mixture of spherical and rod-shaped CO and MCO nanostructures. The ratio of CMO and MCO in the optimized CMO@MCO was 2:1 with the Cu and Mn dopants percentages of 12 and 15%, respectively. The MO-, CO-, and CMO@MCO-modified carbon cloth (CC) electrodes delivered the specific capacitance (C s) values of 541.1, 706.7, and 997.2 F/g at 5 mV/s and 413.4, 480.5, and 561.1 F/g at 1.3 A/g, respectively. This enhanced C s value of CMO@MCO with an energy density and a power density of 78.0 Wh/kg and 650.0 W/kg, respectively, could be attributed to the improvement of electrical conductivity induced by the dopants and the high percentage of oxygen vacancies. This corroborated to a decrease in the optical band gap and charge-transfer resistance (R ct) of CMO@MCO at the electrode/electrolyte interface compared to those of MO and CO. The net enhancement of the Faradaic contribution induced by the redox reaction of the dopant and improved surface area was also responsible for the better electrochemical performance of CMO@MCO. The CMO@MCO/CC electrode showed high electrochemical stability with a C s loss of only ca. 4.7%. This research could open up new possibilities for the development of doped mixed oxides for high-performance supercapacitors.

16.
Chemistry ; 15(43): 11730-6, 2009 Nov 02.
Article in English | MEDLINE | ID: mdl-19806621

ABSTRACT

A facile purification method for metal-organic frameworks (MOFs), especially the ones containing insoluble 1,4-benzenedicarboxylic acid (terephthalic acid) in the pore, has been suggested. The purification method consists of the treatment of the MOF with amides such as N,N-dimethylformamide, especially under ultrasound treatment. The purification is completed within 1 h at 70 degrees C as has been confirmed by XRD, nitrogen adsorption, FTIR and TGA measurements. The purification method proved to be simple, one-step, fast and energy-efficient. The MOFs purified by the proposed method show high surface area and micropore volume, confirming the efficiency of the method. The proposed method will lead to a new access to activate (for example, to remove carboxylic acids) MOFs that are unstable above around 100 degrees C. Additionally, the method may be used to transform a non-porous MOF-type material into a porous MOF structure. However, adequate solvents will be necessary for the facile purification of MOFs.


Subject(s)
Formamides/chemistry , Metals/chemistry , Phthalic Acids/chemistry , Ultrasonics , Dimethylformamide , Porosity , Spectroscopy, Fourier Transform Infrared , Surface Properties , Temperature , X-Ray Diffraction
17.
PLoS One ; 14(4): e0214440, 2019.
Article in English | MEDLINE | ID: mdl-31009467

ABSTRACT

The hydrolysis of ß-lactam antibiotics by ß-lactamase enzymes is the most prominent antibiotic resistance mechanism for many pathogenic bacteria. Out of this broad class of enzymes, metallo-ß-lactamases are of special clinical interest because of their broad substrate specificities. Several in vitro inhibitors for various metallo-ß-lactamases have been reported with no clinical efficacy. Previously, we described a 10-nucleotide single stranded DNA aptamer (10-mer) that inhibits Bacillus cereus 5/B/6 metallo-ß-lactamase very effectively. Here, we find that the aptamer shows uncompetitive inhibition of Bacillus cereus 5/B/6 metallo-ß-lactamase during cefuroxime hydrolysis. To understand the mechanism of inhibition, we report a 2.5 Å resolution X-ray crystal structure and solution-state NMR analysis of the free enzyme. Chemical shift perturbations were observed in the HSQC spectra for several residues upon titrating with increasing concentrations of the 10-mer. In the X-ray crystal structure, these residues are distal to the active site, suggesting an allosteric mechanism for the aptamer inhibition of the enzyme. HADDOCK molecular docking simulations suggest that the 10-mer docks 26 Å from the active site. We then mutated the three lysine residues in the basic binding patch to glutamine and measured the catalytic activity and inhibition by the 10-mer. No significant inhibition of these mutants was observed by the 10-mer as compared to wild type. Interestingly, mutation of Lys50 (Lys78; according to standard MBL numbering system) resulted in reduced enzymatic activity relative to wild type in the absence of inhibitor, further highlighting an allosteric mechanism for inhibition.


Subject(s)
Anti-Bacterial Agents/pharmacology , Aptamers, Nucleotide/chemistry , beta-Lactamase Inhibitors/pharmacology , beta-Lactamases/metabolism , Allosteric Site , Bacillus cereus/drug effects , Bacillus cereus/enzymology , Catalysis , Catalytic Domain , Crystallography, X-Ray , Kinetics , Magnetic Resonance Spectroscopy , Molecular Docking Simulation , Mutagenesis, Site-Directed , Protein Binding , Substrate Specificity , beta-Lactamases/genetics
18.
Sci Rep ; 9(1): 9210, 2019 06 25.
Article in English | MEDLINE | ID: mdl-31239483

ABSTRACT

An amyloid matrix composed of several family 2 cystatins, including the reproductive cystatin CRES, is an integral structure in the mouse epididymal lumen and has proposed functions in sperm maturation and protection. Understanding how CRES amyloid assembles in vitro may provide clues on how the epididymal amyloid matrix forms in vivo. We therefore purified full-length CRES under nondenaturing conditions and followed its aggregation from monomer to amyloid under conditions that may approximate those in the epididymal lumen. CRES transitioned into a metastable oligomer that was resistant to aggregation and only over extended time formed higher-ordered amyloids. High protein concentrations facilitated oligomer assembly and also were required to maintain the metastable state since following dilution the oligomer was no longer detected. Similar to other amyloid precursors, the formation of CRES amyloids correlated with a loss of α-helix and a gain of ß-sheet content. However, CRES is unique in that its amyloids are rich in antiparallel ß-sheets instead of the more common parallel ß-sheets. Taken together, our studies suggest that early metastable oligomers may serve as building blocks for functional amyloid assembly and further reveal that antiparallel ß-sheet-rich amyloids can be functional forms.


Subject(s)
Amyloid/chemistry , Cystatins/chemistry , Protein Multimerization , Animals , Epididymis/metabolism , Heat-Shock Response , Male , Mice , Models, Molecular , Protein Conformation, alpha-Helical , Protein Conformation, beta-Strand , Stress, Mechanical
19.
ACS Appl Mater Interfaces ; 10(41): 35639-35646, 2018 Oct 17.
Article in English | MEDLINE | ID: mdl-30256614

ABSTRACT

Polyaniline-encapsulated metal-organic frameworks (MOFs; MIL-101, Cr-benzenedicarboxylate) were prepared via a ship-in-bottle strategy and applied in liquid phase adsorptions. The modified MIL-101s showed record-high adsorptions for both basic and neutral nitrogen-containing compounds (NCCs) from liquid model fuel. For example, the maximum adsorption capacities ( Qo) of the protonated polyaniline (pANI)@MIL-101 for the basic quinoline and neutral indole from n-octane were 556 and 602 mg/g, respectively. The plausible adsorption mechanisms such as hydrogen bonding, acid-base interaction, and cation-π interaction were proposed to explain the extraordinary adsorptions of the studied adsorbates. Moreover, the adsorbents could be recycled via a simple approach and reused in adsorptions without noticeable decrease in performances. Therefore, the pANI-encapsulated MOFs could be recommended as a new type of adsorbents for very efficient removal of both basic and neutral NCCs from liquid fuel.

20.
J Hazard Mater ; 360: 163-171, 2018 10 15.
Article in English | MEDLINE | ID: mdl-30099359

ABSTRACT

Polyaniline (pANI) was pyrolyzed under a nitrogen atmosphere to get porous pANI-derived carbons (PDCs). To increase the porosity of the carbons further, the PDCs were activated at 600-800 °C in the presence of KOH. The obtained PDCs were firstly applied in liquid-phase adsorptions in order to remove hazardous organics from both water and fuel effectively via adsorption. PDC-700, activated at 700 °C, showed record high adsorption capacities from water for the removal of hazardous organics such as diethyl phthalate and Janus Green B, as representative organics for industrial chemicals (endocrine disturbing agent) and organic dyes, respectively. Moreover, PDC-700 had record high adsorption capacity for the removal of 4,6-dimethyldibenzothiophene from a model fuel. The plausible mechanisms were also suggested to explain the remarkable adsorptions both from water and fuel. The adsorbents could be regenerated in a facile way and reused in adsorption up to several cycles. Therefore, the PDCs could be suggested as a new class of adsorbents for the purification of both water contaminated with organics and fuel having a high concentration of thiophenics.

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