Chemical Evolution of LiCoO2 and NaHSO4·H2O Mixtures with Different Mixing Ratios During Roasting Process

Mixtures of NaHSO4·H2O and LiCoO2 extracted from spent lithium-ion batteries were prepared with molar ratios of 1：1, 1：2 and 1：3. The chemical evolution of the LiCoO2 and NaHSO4-H20 mixtures during the roasting process was investigated by means of thermogravimetric analysis and differential scanning calorimetry （TG-DSC）, X-ray diffraction（XRD）, scanning electron （XPS）. The results show that the chemical reactions in microscopy（SEM）, and X-ray photoelectron spectroscopy the LiCoO2 and NaHSO4·H2O mixtures proceed during the roasting process. The Li element in the product of the roasting process is in the form of LiNa（SO4）. With the increase of the proportion of NaHSO4·H2O in the mixtures, the Co element evolves as follows： LiCoO2→Co3O4→Na6Co（SOa）4→Na2Co（SO4）2. The roasting products exhibit dense structures and irregular shapes, and the bonding energy of Co increases.

N-phosphoryl amino acid models for P–N bonds in prebiotic chemical evolution

Post-translational modification of proteins by N-phosphorylation of the basic amino acid residues plays important roles in biological processes. The high-energy P–N bond might have contributed to the evolution of prebiotic chemistry. N-phosphoryl amino acids(PAAs) can serve as interesting small molecular models for the study of P–N bonds in prebiotic chemical evolution. PAAs are capable of simultaneously producing several important biomolecules such as polypeptides and oligonucleotides under mild reaction conditions. In this review, we describe the chemistry of PAAs, discusse their likely prebiotic origins and their reactivity and how they relate to biological P–N bond species. We also depict a possible prebiotic scenario mediated by PAAs in which PAAs may have acted as one of the essential forces driving prebiotic biomolecules to the first protocell.

Phases of Environmental Evolution Indicated by Primary Chemical Elements and Paleontological Records in the Upper Pleistocene-Holocene Series for the Salawusu River Valley,China

Studies of lithology, sedimentary facies and the distribution regularity of SiO2 and Al2O3 contents and Al2O3/SiO2 ratio allow us to divide the Upper Pleistocene-Holocene Series represented by the MUanggouwan section in China＇s Salawnsu River valley into six segments： MGS1, MGS2, MGS3, MGS4, MGS5 and MGS6. The boundary ages for MGS1 （the Dishaogouwan and Dagouwan Formations）, MGS2 （the upper Chengchuan Formation）, MGS3 （the middle Chengchuan Formation）, MGS4 （the lower Chengchuan Formation）, MGS5 （most strata of the Salawusu Formation） and MGS6 （the bottom of the Salawusu Formation and the top of the Lishi Formation） correspond to those of MIS1, MIS2, MIS3, MIS4, MISS and MIS6, respectively, from deep sea sediments or continental glaciers. MGS5 can be subdivided into five subsegments （MGS5a, MGS5b, MGS5c, MGS5d and MGS5e） and the boundary ages of these subsegments correspond to those of MISSa, MISSb, MIS5c, MIS5d and MIS5e, respectively. Based on the paleoenvironment and paleoecology indicated by the primary chemical elements, fossil vertebrates, mollusks and pollen grains, we hypothesize that MGS1, MGS2, MGS3, MGS4, MGS5 and MGS6 and the subsegments of MGS5 match the corresponding stages for oxygen isotopes in the deep sea sediments and continental glaciers, and the substages of MIS5 in terms of climatic characters, further explaining the phenomena that determined the formation of the late Quaternary strata and the paleontology of the Salawusu River valley. These phenomena relate to fluctuations in the global climate （and particularly in the East Asian monsoon） during the glacial and interglacial periods.

A plausible pathway to prebiotic peptides via amino acid amides on the primordial Earth

The prebiotic synthesis of peptides prior to ribosome-catalyzed processes remains an enigma.The synthesis of abiotic peptides from amino acids(AAs)is primarily constrained by high activation energies and unfavorable thermodynamics,necessitating the identification of plausible prebiotic alternatives for synthesizing prebiotic peptides.Here we present a plausible pathway to the formation of prebiotic peptides,wherein oligopeptides,oligopeptide amides,and cyclic oligopeptides can be directly synthesized from amino acid amides(AA-NH2)under wet–dry cycle conditions without the need for any enhancers.The subsequent investigation revealed that AA-NH2 demonstrated more favorable thermodynamic reaction effects than AAs in peptide formation.In contrast to the polymerization of AAs,the process of peptide formation through the polymerization of AA-NH2 was significantly simplified.Additionally,AA-NH2 was discovered to function as a“bridge”for the formation of peptides from AAs,thereby facilitating their participation in the synthesis of intricate peptide structures.On the basis of these findings,a plausible mechanism for the prebiotic origin network of peptides under primordial Earth conditions has been proposed.Overall,this research presents a plausible pathway for the generation of prebiotic peptides and peptide libraries within prebiotic environments.

Discharge plasma for prebiotic chemistry: Pathways to life’s building blocks

Discharge plasmas, recognized as unique platforms for investigating the origins of chemical life, have garnered extensive interest for their potential to simulate prebiotic conditions. This paper embarks on a comprehensive overview of recent advancements in the plasma-enabled synthesis of life’s building blocks, charting the complex environmental parameters believed to have surrounded life’s inception. This discussion elaborates on the fundamental mechanisms of discharge plasmas and their likely role in fostering conditions necessary for the origin of life on early Earth. We consider a variety of chemical reactions facilitated by plasma, specifically the synthesis of vital organic molecules - amino acids, nucleobases, sugars, and lipids. Further, we delve into the impact of plasmas on prebiotic chemical evolution. We expect this review to open new horizons for future investigations in plasma-related prebiotic chemistry that could offer valuable insights for unraveling the mysteries of life's origin.

Promoting effect of nitrogen doping on carbon nanotube-supported RuO2 applied in the electrocatalytic oxygen evolution reaction

RuO2 nanoparticles supported on multi-walled carbon nanotubes（CNTs） functionalized with oxygen（OCNTs） and nitrogen（NCNTs） were employed for the oxygen evolution reaction（OER） in 0.1 M KOH.The catalysts were synthesized by metal-organic chemical vapor deposition using ruthenium carbonyl（Ru3（CO）（12）） as Ru precursor. The obtained RuO2/OCNT and RuO2/NCNT composites were characterized using TEM, H2-TPR, XRD and XPS in order probe structure–activity correlations, particularly, the effect of the different surface functional groups on the electrochemical OER performance. The electrocatalytic activity and stability of the catalysts with mean RuO2 particle sizes of 13–14 nm was evaluated by linear sweep voltammetry, cyclic voltammetry, and chronopotentiometry, showing that the generation of nitrogen-containing functional groups on CNTs was beneficial for both OER activity and stability. In the presence of RuO2, carbon corrosion was found to be significantly less severe.

Origins of building blocks of life: A review

How and where did life on Earth originate？ To date, various environments have been proposed as plausible sites for the origin of life. However, discussions have focused on a limited stage of chemical evolution, or emergence of a specific chemical function of proto-biological systems. It remains unclear what geochemical situations could drive all the stages of chemical evolution, ranging from condensation of simple inorganic compounds to the emergence of self-sustaining systems that were evolvable into modern biological ones. In this review, we summarize reported experimental and theoretical findings for prebiotic chemistry relevant to this topic, including availability of biologically essential elements（N and P） on the Hadean Earth, abiotic synthesis of life＇s building blocks（amino acids, peptides, ribose, nucleobases, fatty acids, nucleotides, and oligonucleotides）, their polymerizations to bio-macromolecules（peptides and oligonucleotides）, and emergence of biological functions of replication and compartmentalization. It is indicated from the overviews that completion of the chemical evolution requires at least eight reaction conditions of（1） reductive gas phase,（2） alkaline pH,（3） freezing temperature,（4）fresh water,（5） dry/dry-wet cycle,（6） coupling with high energy reactions,（7） heating-cooling cycle in water, and（8） extraterrestrial input of life＇s building blocks and reactive nutrients. The necessity of these mutually exclusive conditions clearly indicates that life＇s origin did not occur at a single setting; rather, it required highly diverse and dynamic environments that were connected with each other to allow intratransportation of reaction products and reactants through fluid circulation. Future experimental research that mimics the conditions of the proposed model are expected to provide further constraints on the processes and mechanisms for the origin of life.

Nuclear geyser model of the origin of life:Driving force to promote the synthesis of building blocks of life

We propose the nuclear geyser model to elucidate an optimal site to bear the first life.Our model overcomes the difficulties that previously proposed models have encountered.Nuclear geyser is a geyser driven by a natural nuclear reactor,which was likely common in the Hadean Earth,because of a much higher abundance of 235U as nuclear fuel.The nuclear geyser supplies the following：（1）high-density ionizing radiation to promote chemical chain reactions that even tar can be used for intermediate material to restart chemical reactions,（2）a system to maintain the circulation of material and energy,which includes cyclic environmental conditions（warm/cool,dry/wet,etc.）to enable to produce complex organic compounds,（3）a lower temperature than 100℃ as not to break down macromolecular organic compounds,（4）a locally reductive environment depending on rock types exposed along the geyser wall,and（5）a container to confine and accumulate volatile chemicals.These five factors are the necessary conditions that the birth place of life must satisfy.Only the nuclear geyser can meet all five,in contrast to the previously proposed birth sites,such as tidal flat,submarine hydrothermal vent,and outer space.The nuclear reactor and associated geyser,which maintain the circulations of material and energy with its surrounding environment,are regarded as the nuclear geyser system that enables numerous kinds of chemical reactions to synthesize complex organic compounds,and where the most primitive metabolism could be generated.

Interaction between N-Phospho-Amino Acids and Nucleoside in Aqueous Medium

Nucleosides were phosphorylated with different N- (O, O-diisopropyl) phosphoryl amino acids to give nucleoside mono phosphates in aqueous solution. 2', 3', and 5'-isomers had been confirmed by comparison with authentic samples on the basis of HPLC analysis. The conversion percentage of nucleoside indicated that N- (O, O-diisopropyl) phosphoryl aspartic acid reacted with adenosine and guanosine at a much higher rate than other kinds of N- phosphoryl amino acids. while phosphorylation of cytidine and uridine was relatively easy by using N- (O, O-diisopropyl) phosphoryl threonine. The result could give some clue to the prebiotic code origin of nucleic acid and protein.

Potential Prebiotic Relevance of Glycine Single Crystals Enclosing Fluid Inclusions: An Experimental and Computer Simulation with Static Magnetic Fields

Glycine crystallizes into three different polymorphs called α, β and γ under standard physicochemical conditions. They have different features depending on their structural variations. The possible interaction of glycine with magnetic minerals in meteorites and comets or in the ancient Earth, paves the way to study the self-assembly and molecular behavior under irradiation and magnetic conditions. The magnetic field might induce the formation of a specific polymorph of glycine. To gain insight on the consequences of gamma irradiation with a gradient of static magnetic fields (0.06 T, 0.3 T, 0.42 T and 0.6 T) on the self-assembly of single macroscopic glycine crystals, we gamma irradiated the powdered amino acid and then assembled single crystals from water solutions. The preliminary results showed a stable formation of fluid inclusions in the single crystals and no straightforward effect on the self-assem- bly process after glycine gamma irradiation and interaction with static magnetic fields. The α glycine polymorph single crystals formed at 55° from the magnetic longitudinal axis and seemed to be enhanced by gamma radiation. The γ-glycine single crystals presented L and D circular dichroism signals, whereas the irradiated samples presented no circular dichroism bands. Com- puter simulations suggest different catalytic properties from α and γ glycine crystals.

Chromosomal Engineering of Escherichia coli for Efficient Production of Coenzyme Q_(10)

The plasmid-expression system is routinely plagued by potential plasmid instability. Chromosomal integration is one powerful approach to overcome the problem. Herein we report a plasmid-free hyper-producer E.coli strain for coenzyme Q10 production. A series of integration expression vectors, pxKC3T5b and pxKT5b, were constructed for chemically inducible chromosomal evolution(multiple copy integration) and replicon-free and markerless chromosomal integration(single copy integration), respectively. A coenzyme Q10 hyper-producer Escherichia coli TBW20134 was constructed by applying chemically inducible chromosomal evolution,replicon-free and markerless chromosomal integration as well as deletion of menaquinone biosynthetic pathway.The engineered E. coli TBW20134 produced 10.7 mg per gram of dry cell mass(DCM) of coenzyme Q10 when supplemented with 0.075 g·L-1of 4-hydroxy benzoic acid; this yield is unprecedented in E. coli and close to that of the commercial producer Agrobacterium tumefaciens. With this strain, the coenzyme Q10 production capacity was very stable after 30 sequential transfers and no antibiotics were required during the fermentation process. The strategy presented may be useful as a general approach for construction of stable production strains synthesizing natural products where various copy numbers for different genes are concerned.

Low-α metal-rich stars with sausage kinematics in the LAMOST survey: Are they from the Gaia-Sausage-Enceladus galaxy?

We search for metal-rich Sausage-kinematic(MRSK)stars with[Fe/H]>−0.8 and−100<Vϕ<50 km/s in LAMOST DR5 in order to investigate the influence of the Gaia-Sausage-Enceladus(GSE)merger event on the Galactic disk.For the first time,we find a group of low-αMRSK stars,and classify it as a metal-rich tail of the GSE galaxy based on the chemical and kinematical properties.This group has slightly larger R_(apo),Z_(max) and Etot distributions than a previously-reported high-αgroup.Its low-αratio does not allow for an origin resulting from the splash process of the GSE merger event,as is proposed to explain the high-αgroup.A hydrodynamical simulation by Amarante et al.provides a promising solution,in which the GSE galaxy is a clumpy Milky-Way analogue that develops a bimodal disk chemistry.This scenario explains the existence of MRSK stars with both high-αand low-αratios found in this work.It is further supported by another new feature that a clump of MRSK stars is located at Z_(max)=3-5 kpc,which corresponds to the widely adopted disk-halo transition at|Z|∼4 kpc.We suggest that a pile-up of MRSK stars at Zmax contributes significantly to this disk-halo transition,an interesting imprint left by the GSE merger event.These results also provide an important implication on the connection between the GSE and the Virgo Radial Merger.

Nucleosynthesis in thermonuclear supernovae

We review our understanding of the nucleosynthesis that occurs in thermonuclear supernovae and their contribution to Galactic Chemical evolution. We discuss the prospects to improve the modeling of the nucleosynthesis within simulations of these events.

Mechanism of Lithium and Cobalt Recovery from Spent Lithium-ion Batteries by Sulfation Roasting Process

Diflerent from the traditional pyTometallurgical recovery process of Li and Co from spent lithium-ion batteries,a new recovery method for Li and Co was established by converting LiCoO2 into water-soluble metal sul-fates by roasting a mixture of LiCoO2 and NaHSO4-H2O.The evolution law of the mixture with increased roasting temperature was investigated by thennogravimetry-diflerential scamiing calorimetry(TG-DSC),in situ X-ray diflrac-tion(XRD),XRD,and X-ray photoelectron spectroscopy(XPS).The results show that the phase transition of LiCoO2 mixed with NaHSO4 H2O with increased temperature proceeded as follows:LiCoO2,NaHSO4 H2O→LiCo02,NaHSO4→Lil-xCo02,LiNaSO4,Na2S2O7,Na2SO4→Li1-xCoCO2,Co3O4,LiNaSO4,Na2SO4→Co3O4,LiNaSO4.The reaction mechanism of this roasting process may be as follows:LiCoO2+NaHSO4-H2O→l/2Li2SO4+l/2Na2SO4+l/3Co3O4+l/12O2+3/2H2O,Li2SO4+Na2SO4=2LiNaSO4.

The TMRT K band observations towards 26 infrared dark clouds:NH_3, CCS, and HC_3N

We present one of the first Shanghai Tian Ma Radio Telescope (TMRT) K Band observations towards a sample of 26 infrared dark clouds (IRDCs).We observed the (1,1),(2,2),(3,3),and (4,4) transitions of NH_(3) together with CCS (2_(1)–>1_(0)) and HC_(3)NJ=2-1,simultaneously.The survey dramatically increases the existing CCS-detected IRDC sample from 8 to 23,enabling a better statistical study of the ratios of carbon-chain molecules (CCM) to N-bearing molecules in IRDCs.With the newly developed hyperfine group ratio (HFGR) method of fitting NH_(3) inversion lines,we found the gas temperature to be between 10 and18 K.The column density ratios of CCS to NH_(3) for most of the IRDCs are less than 10^(-2),distinguishing IRDCs from low-mass star-forming regions.We carried out chemical evolution simulations based on a three-phase chemical model NAUTILUS.Our measurements of the column density ratios between CCM and NH_(3) are consistent with chemical evolutionary ages of 10^(5) yr in the models.Comparisons of the data and chemical models suggest that CCS,HC_(3)N,and NH_(3) are sensitive to the chemical evolutionary stages of the sources.