Proton transfer pathway in anion channelrhodopsin-1

Anion channelrhodopsin from Guillardia theta (GtACR1) has Asp234 (3.2 Å) and Glu68 (5.3 Å) near the protonated Schiff base. Here, we investigate mutant GtACR1s (e.g., E68Q/D234N) expressed in HEK293 cells. The influence of the acidic residues on the absorption wavelengths was also analyzed using a quantum mechanical/molecular mechanical approach. The calculated protonation pattern indicates that Asp234 is deprotonated and Glu68 is protonated in the original crystal structures. The D234E mutation and the E68Q/D234N mutation shorten and lengthen the measured and calculated absorption wavelengths, respectively, which suggests that Asp234 is deprotonated in the wild-type GtACR1. Molecular dynamics simulations show that upon mutation of deprotonated Asp234 to asparagine, deprotonated Glu68 reorients toward the Schiff base and the calculated absorption wavelength remains unchanged. The formation of the proton transfer pathway via Asp234 toward Glu68 and the disconnection of the anion conducting channel are likely a basis of the gating mechanism.

Facile Preparation and Characteristic Analysis of Sulfated Cellulose Nanofibril via the Pretreatment of Sulfamic Acid-Glycerol Based Deep Eutectic Solvents

A deep eutectic solvent (DES) composed of sulfamic acid and glycerol allowed for the sustainable preparation of cellulose nanofibrils (CNF) with simultaneous sulfation. The reaction time and the levels of sulfamic acid demonstrated that fibers could be swelled and sulfated simultaneously by a sulfamic acid-glycerol-based DES and swelling also promoted sulfation with a high degree of substitution (0.12). The DES-pretreated fibers were further nanofibrillated by a grinder producing CNF with diameters from 10 nm to 25 nm. The crystallinity ranged from 53–62%, and CNF maintained the original crystal structure. DES pretreatment facilitated cellulose nano-fibrillation and reduced the energy consumption with a maximum reduction of 35%. The films prepared from polyvinyl alcohol (PVA) and CNF showed good UV resistance ability and mechanical properties. This facile and efficient method provided a more sustainable strategy for the swelling, functionalization and nano-fibrillation of cellulose, expanding its application to UV-blocking materials and related fields.

Proton-mediated gating mechanism of anion channelrhodopsin-1

Anion channelrhodopsin from Guillardia theta (GtACR1) has Asp234 (3.2 Å) and Glu68 (5.3 Å) near the protonated Schiff base. Here we investigate mutant GtACR1s (e.g., E68Q/D234N) expressed in HEK293 cells. The influence of the acidic residues on the absorption wavelengths were also analyzed, using a quantum mechanical/molecular mechanical approach. The calculated protonation pattern indicates that Asp234 is deprotonated and Glu68 is protonated in the original crystal structures. The D234E mutation and the E68Q/D234N mutation shortens and lengthens the measured and calculated absorption wavelengths, respectively, which suggests that Asp234 is deprotonated in the wild type GtACR1. Molecular dynamics simulations show that upon mutation of deprotonated Asp234 to asparagine, deprotonated Glu68 reorients towards the Schiff base and the calculated absorption wavelength remains unchanged. The formation of the proton transfer pathway via Asp234 toward Glu68 and the disconnection of the anion conducting channel are likely a basis of the gating mechanism.

Nitrate removal during Fe(III) bio-reduction in microbial-mediated iron redox cycling systems

Fe(III) bio-reduction provides a prospect of applying the iron redox cycle to nitrate remediation in the aquatic environment. The objective of this study was to realize multiple nitrate removals in the system containing Shewanella oneidensis MR-1 (S. oneidensis MR-1) and ferrihydrite or magnetite. The results showed that with three periods of 30 mg·L−1 NO3−-N addition, all nitrate reduction was completed within 170 h. In the first period (0–30 h) of nitrate addition, the main contribution of nitrate removal was due to the biological reduction process by S. oneidensis MR-1, accompanied by the reduction of Fe(III). During the second (45–90 h) and third periods (100–170 h) of nitrate addition, oxidation of biogenic Fe(II) coupled with the reduction of nitrate took place. This redox reaction resulted in the production of gaseous nitrogen of 47.33% and 16.8% for ferrihydrite/S. oneidensis MR-1 and magnetite/S. oneidensis MR-1 systems, respectively. In addition, nitrite, as an intermediate product, accumulated and negatively affected nitrate removal after the third addition of nitrate. By comparing the patterns of X-ray diffraction of the iron minerals before and after the bio-reduction, it was found that ferrihydrite was transformed into magnetite, while magnetite kept its original crystal form.

Preparation of anisole in phenol by Zn/HZSM-5 catalyst from walnut shell catalyzed liquefaction

The promotional effect of Zn was investigated relative to the calcining activation of HZSM-5. It was found that the lignin separated from walnut shell could be liquefied into small molecular ethers such as anisole by the promotional effect of the modified catalyst. Experimental results showed that, after the loading of Zn, the HZSM-5 catalyst retained its original crystal structure, which exhibited good metal dispersion. Besides, due to the existence of two interactions respectively of Zn with Al and Zn with a Brønsted-Lowry acid on the Zn/HZSM-5 catalyst surface, the remaining catalyst intergranular distance increased, particularly for the 2% Zn/HZSM-5 catalyst. The inside of the catalyst was in a state of spherical particle aggregation with a narrow pore size distribution and uniform particle size. The peak intensity of the Si-O stretching vibration was affected by the content of Zn, which was least affected for the 2% Zn/HZSM-5 catalyst. The signal peak of this small molecule ether was not found in the absence of the metal ions, and the catalytic effect of 2% Zn/HZSM-5 was more distinct. Calculated by the mass difference method, the yield of the liquid via the 2% Zn/HZSM-5 catalyst was 59.8%, including phenol and small molecule ethers represented by anisole.

Study on the properties of modified starch and its feasibility in crystal dumpling skins

Four kinds of modified starches that are expected to improve the quality of crystal dumpling skins were selected, namely Potato acetate starch, Potato hydroxypropyl starch, Octenyl succinate starch sodium, Acetate cassava starch. Through the determination of the physical indicators of the above four modified starches, and then explore the feasibility of applying them to crystal dumpling skins to improve their quality. Studies have found that the light transmittance of the four modified starches is higher than that of the original crystal dumpling mixed starch, which verifies the feasibility of applying these four modified starches to the crystal dumpling skin to improve its transparency and other characteristics. At the same time, it provides a certain reference value for related research on improving the characteristics of crystal dumpling skin.

Origin, properties, and structure of breyite: The second most abundant mineral inclusion in super-deep diamonds

Earth's lower mantle most likely mainly consists of ferropericlase, bridgmanite, and a CaSiO3- phase in the perovskite structure. If separately trapped in diamonds, these phases can be transported to Earth's surface without reacting with the surrounding mantle. Although all inclusions will remain chemically pristine, only ferropericlase will stay in its original crystal structure, whereas in almost all cases bridgmanite and CaSiO3-perovskite will transform to their lower-pressure polymorphs. In the case of perovskite structured CaSiO3, the new structure that is formed is closely related to that of walstromite. This mineral is now approved by the IMA commission on new minerals and named breyite. The crystal structure is triclinic (space group: P1) with lattice parameters a0 = 6.6970(4) Å, b0 = 9.2986(7) Å, c0 = 6.6501(4) Å, α = 83.458(6)°, β = 76.226(6)°, γ = 69.581(7)°, and V = 376.72(4) Å. The major element composition found for the studied breyite is Ca3.01(2)Si2.98(2)O9. Breyite is the second most abundant mineral inclusion after ferropericlase in diamonds of super-deep origin. The occurrence of breyite has been widely presumed to be a strong indication of lower mantle (=670 km depth) or at least lower transition zone (=520 km depth) origin of both the host diamond and the inclusion suite. In this work, we demonstrate through different formation scenarios that the finding of breyite alone in a diamond is not a reliable indicator of the formation depth in the transition zone or in the lower mantle and that accompanying paragenetic phases such as ferropericlase together with MgSiO3 are needed.

The cardioprotective effects of the new crystal form of puerarin in isoproterenol-induced myocardial ischemia rats based on metabolomics

Puerarin has shown unique pharmacological effects on myocardial ischemia (MI). Changing the crystal form is an effective approach to improve the cardioprotective effects of puerarin. However, the mechanisms of the new crystal form of puerarin are unclear. In this study, an electrocardiogram, echocardiography, cardiac marker enzymatic activity, oxidative stress indices, and myocardial histology analysis of cardiac tissues were performed to evaluate the cardioprotective effects of the new crystal form of puerarin. Moreover, serum and cardiac tissue metabolomics based on nuclear magnetic resonance (NMR) were used to investigate the potential mechanism of the new crystal form. The results indicated that the new crystal form of puerarin (30 mg/kg) could improve oxidative stress indices, and these improvements were similar to those of the original crystal form of puerarin (120 mg/kg). The new crystal form of puerarin (30 mg/kg) could effectively improve the activities of cardiac marker enzymes, and the improvement effects were better than those of the original crystal form (120 mg/kg). Moreover, metabolomics analysis showed that amino acid metabolism, oxidative stress and energy metabolism were disturbed after MI and could be improved by puerarin. These results demonstrated that the new crystal form of puerarin was effective in treating MI.

Achieving delafossite analog by in situ electrochemical self-reconstruction as an oxygen-evolving catalyst

Development of novel and robust oxygen evolution reaction (OER) catalysts with well-modulated atomic and electronic structure remains a challenge. Compared to the well-known metal hydroxides or (oxyhydr)oxides with lamellar structure, delafossites (ABO2) are characterized by alternating layers of A cations and edge-sharing BO2octahedra, but are rarely used in OER due to their poor electron conductivity and intrinsic activity. Here, we propose a delafossite analog by mutation of metal oxyhydroxide and delafossite based on first-principles calculations. Modulation on the electronic structure due to distortion of the original crystal field of the BO2layers is calculated to enhance electron conductivity and catalytic activity. Inspired by the theoretical design, we have experimentally realized the delafossite analog by electrochemical self-reconstruction (ECSR).OperandoX-ray absorption spectroscopy and other experimental techniques reveal the formation of delafossite analog with Ag intercalated into bimetallic cobalt–iron (oxyhydr)oxide layers from a metastable precursor through amorphization. Benefitting from the featured local electronic and geometric structures, the delafossite analog shows superior OER activity, affording a current density of 10 mA⋅cm−2at an overpotential of 187 mV and an excellent stability (300 h) in alkaline conditions.