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S-Adenosylmethionine (SAM) is an enzyme cofactor involved in methylation, aminopropyl transfer, and radical reactions. This versatility renders SAM-dependent enzymes of great interest in biocatalysis. The usage of SAM analogues adds to this diversity. However, high cost and instability of the cofactor impedes the investigation and usage of these enzymes. While SAM regeneration protocols from the methyltransferase (MT) byproductS-adenosylhomocysteine are available, aminopropyl transferases and radical SAM enzymes are not covered. Here, we report an efficient one-pot system to supply or regenerate SAM and SAM analogues for all three enzyme classes. The system’s flexibility is showcased by the transfer of an ethyl group with a cobalamin-dependent radical SAM MT usingS-adenosylethionine as a cofactor. This shows the potential of SAM (analogue) supply and regeneration for the application of diverse chemistry, as well as for mechanistic studies using cofactor analogues.

Late-stage methylation is a key technology in the development of pharmaceutical compounds. Methyltransferase biocatalysis may provide powerful options to insert methyl groups into complex molecules with high regio- and chemoselectivity. The challenge of a large-scale application of methyltransferases is their dependence on S-adenosylmethionine (SAM) as a stoichiometric, and thus exceedingly expensive co-substrate. As a solution to this problem, we and others have explored the use of methyl halides as reagents for the in situ regeneration of SAM. However, the need to handle volatile electrophiles, such as methyl iodide (MeI), may also hamper applications at scale. As a more practical solution, we have now developed an enzyme-catalyzed process for the regeneration of SAM with methyl toluene sulfonate. Herein, we describe enzymes from the thiopurine methyltransferase family that accept sulfate- and sulfonate-based methyl donors to convert S-adenosylhomocysteine into SAM with efficiencies that rival MeI-based reactions.

Humans and water are closely connected in large river basins and form social-ecological systems (SESs). However, cross-scale effect in SESs make it difficult to identify the key forces driving human-water connections at the community scale when ignoring the landscape context. Focusing on the incongruous human-water relationships in the lower reaches of the Yellow River, we built local resident perception-based networks linking the agricultural subsystem, environmental subsystem, and cultural subsystem by distributing farmer household questionnaires and extracted 13 indicators from 7 kinds of network metrics to indicate human-water connections. We applied analysis of variance (ANOVA), random forest (RF) and multilevel linear model (MLM) methods to identify the driving forces of perception-based human-water connections among 20 factors at both the community and landscape scales. The results showed that the perception-based network indicators were mainly directly influenced by community-level driving factors, especially the accessibility of information, such as the frequency of going out, the frequency of accessing the Yellow River channel, and the information source for the national policy on the Yellow River. The influences of community-level driving factors on network indicators were affected by landscape-level driving factors, e.g., the nighttime light, population density, gross domestic product and proportion of artificial land, thus indicating indirect influences from the landscape context. These analyses and findings can enrich the methods by which social, ecological and hydrological elements are structurally linked in sociohydrologic research and highlight the cross-scale effect of the landscape context on human-water systems at the community level.

The intramolecular Csp3–H and/or C–C bond amination is very important in modern organic synthesis due to its efficiency in the construction of diversified N-heterocycles. Herein, we report a novel intramolecular cyclization of alkyl azides for the synthesis of cyclic imines and tertiary amines through selective Csp3–H and/or C–C bond cleavage. Two C–N single bonds or a C Created by potrace 1.16, written by Peter Selinger 2001-2019 N double bond are efficiently constructed in these transformations. The carbocation mechanism differs from the reported metal nitrene intermediates and therefore enables metal-free and new transformation., A novel intramolecular cyclization of alkyl azides for the synthesis of cyclic imines and tertiary amines has been developed. The aliphatic C–H or C–C bond was selectively cleaved with the efficient formation of two C–N single bonds or a CN double bond.

In this study, the carbothermic reduction and nitridation mechanism of vanadium-bearing titanomagnetite concentrate are investigated in terms of phase transformation, microstructure transformation, and thermodynamic analyses. The differences in the reaction behavior of titanomagnetite and ilmenite in vanadium-bearing titanomagnetite concentrate, as well as the distribution characteristic of V in the roasted products, are emphatically studied. It is observed that the reaction sequences of titanomagnetite and ilmenite transformations into nitride are as follows: Fe3−xTixO4→Fe2TiO4→FeTiO3→M3O5→(Ti, V)(N, C), FeTiO3→M3O5→Ti(N, C). The reduction of M3O5 to TiN is the rate-limiting step of the entire reaction, and metal iron is an important medium for transferring C for the reduction of M3O5. Titanomagnetite is faster to convert into nitride than ilmenite is, and the reasons for this are discussed in detail. During the entire roasting process, V mainly coexists with Ti and seems to facilitate the conversion of titanium oxides into (Ti, V)(N, C).

A novel activation of acetonitrile for the construction of cyclobutenones by [2+2] cyclization was developed. Acetonitrile is utilized for the first time as two-carbon (C2) cyclization building block. The present protocol successfully inhibits the competitive cycloaddition with the C≡N bond of acetonitrile, but enables the in situ formation of an unsaturated carbon-carbon bond and the subsequent cycloaddition as a C2 unit. This chemistry features simple reaction conditions, high chemoselectivities, wide substrate scope, and offers a new and practical approach to cyclobutenones and cyclobuteneimines.

New types of remote sensed land cover datasets provide key evidence for understanding global environmental change. However, low data consistency makes understanding the changes unclear. China has become a hot spot of land cover change in the world due to climate change and a series of human measures, such as ecological engineering, land consolidation, and urbanization. However, due to the inconsistencies in interpretation of signs and thresholds, the understanding of yearly-continued land cover changes in China is still unclear. We aim to produce China’s land cover fraction dataset from 2001 to 2015 by weighted consistency analysis. We compare the Moderate-resolution Imaging Spectroradiometer land cover dataset (MCD12Q1), the Climate Change Initiative Land Cover (CCI-LC) datasets, and a new land cover fraction dataset named China-LCFMCD-CCI, produced with a 1 km resolution. The obvious increased forest areas only accounted for 4.6% of the total forest areas, and were mainly distributed in northeast China. Approximately 75.8% of the grassland and shrubland areas decreased in size, and these areas were relatively concentrated in northeast and south China. The obvious increased areas of cropland (3.7%) were equal to the obvious decreased areas (3.6%), and the increased cropland areas were in northwest China. The change in bare land was not obvious, as the obvious increased areas only accounted for 0.75% of the bare land areas. The results not only prove that the data fusion of the weighted consistency method is feasible to form a land cover fraction dataset, but also helps to fully reveal the trends in land cover fraction change in China.

The continued sprawl of modern cities can often threaten urban ecological space, and sustainable landscape patterns should be considered in urban landscape planning. The construction of ecological security patterns (ESPs) is regarded as an effective way to integrate landscape patterns and ecosystem services in an ecological connectivity perspective. Based on the content of ecological sources, pattern structures and barrier points from circuit theory, we aimed to improve the urban ecological space of central Wuhan City through ESP scenarios. Three ESP scenarios were developed to optimize the urban ecological spaces: the 1st, involved increasing the ecological sources; the 2nd, increasing the circle structures; and the 3rd, repairing the barrier points. The results showed that the current ESPs identified 17 ecological sources, which were primarily situated on the periphery of the city and included 760.152 km of ecological corridors (38 paths) and 39 barrier points. The 2nd scenario that was regarded as the best approach for Wuhan enhanced the resistance to outside interference and stability, with 17 ecological sources and 681.244 km ecological corridors (37 paths), and had the lowest cost of protection compared with the other two scenarios, as well as the current pattern in central Wuhan. This work methodologically contributed to the different methods including increasing the ecological sources, increasing the circle structure and repairing the barrier points for urban ecological space planning, and practically provided the best scenario to enhancing the urban ecological for landscape management.

Se-benzyl selenoimidazolium salts are characterized by remarkable alkyl-transfer potential under physiological conditions. Structure-activity relationship studies show that selective monoalkylation of primary amines depends on supramolecular interactions between the selenoimidazole leaving group and the target nucleophile. We demonstrate that these reagents can be used for site-selective and nearly quantitative modification of the model protein lysozyme on Lys13, bypassing the higher intrinsic reactivities of Lys1 and Lys33. These observations introduce selenoimidazolium salts as novel class of electrophiles for selective N-alkylation of native proteins.

Sourcing nitrogen from nitromethane Nitromethane is produced in bulk quantities for use as a solvent. Its applications as a reagent have focused mainly on the acidity of the methyl protons en route to modifying the carbon center. Liu et al. now report an alternative protocol that activates the nitrogen center to produce an aminating agent. An in situ reductive reaction with triflic anhydride, formic acid, and acetic acid yields an acetylated hydroxylamine, characterized by mass spectrometry. This nitrogen donor conveniently transforms a variety of ketones and aldehydes into amides. Science , this issue p. 281

Oximes and oxime ethers are privileged building blocks and can be conveniently converted to ketones, amines, hydroxylamines, and nitriles. We describe the catalytic decarboxylation of aliphatic carboxylic acids to oxime ethers. With AgNO3 as the catalyst, valuable oxime ethers bearing various substituents could be easily obtained. The broad substrate scope, easy accessibility of aliphatic carboxylic acids, and mild reaction conditions make this strategy immediately applicable to the synthesis, late-stage functionalization, and modification of biologically active compounds. Experimental studies show the reaction undergoes a radical process.

Aliphatic alcohols are common and bulk chemicals in organic synthesis. The site-selective functionalization of non-activated aliphatic alcohols is attractive but challenging. Herein, we report a silver-catalyzed δ-selective Csp3-H bond functionalization of abundant and inexpensive aliphatic alcohols. Valuable oximonitrile substituted alcohols are easily obtained by using well-designed sulphonyl reagents under simple and mild conditions. This protocol realizes the challenging δ-selective C–C bond formation of simple alkanols. Aliphatic alcohols usually require pre-activation for successful functionalization of their carbon chain. Here, the authors report a silver-catalyzed δ-selective functionalization of aliphatic alcohols via Csp3-H bond cleavage under mild conditions without the need of substrate pre-activation.

A novel metal-free allylic C-C σ-bond cleavage of simple olefins to give valuable cinnamyl aldehydes is reported. 1,2-Aryl or alkyl migration through allylic C-C bond cleavage occurs in this transformation, which is assisted by an alkyl azide reagent. This method enables O-atom incorporation into simple unfunctionalized olefins to construct cinnamyl aldehydes. The reaction features simple hydrocarbon substrates, metal-free conditions, and high regio- and stereoselectivity.

C-N Bond formation is of great significance due to the ubiquity of nitrogen-containing compounds. Here, a mild and efficient Rh(III) -catalyzed C(sp(3) )-H aryl amination reaction is reported. Anthranil is employed as the nitrogen source with 100 % atom efficiency. This C-H amination reaction exhibits broad substrate scope without using any external oxidants. Mechanistic studies including rhodacycle intermediates, H-D exchange, kinetic isotope effect (KIE) experiments, and in situ IR are presented.

Identifying the factors and patterns of coordinated development in the tourism industry, urbanization, and the ecological environment sheds light on how to ensure the high-quality and sustainable development of the regional economy, but the research on this issue is relatively insufficient. Taking Shaanxi Province as an example, this paper analyzes the spatiotemporal coupling characteristics between the tourism industry, urbanization and ecological environment in cities of Shaanxi Province from 2000 to 2017. After identifying the leading factors of coupling of the three systems, the paper summarizes the coupling development mode in each city under the leading factors. The coupling between the tourism industry, urbanization and ecological environment in various cities has realized the fundamental transformation from incoordination to coordination and finally, formed a spatial development pattern featuring strong central regions, and weak southern and northern regions. Before 2010, ecological environment factors dominated the coupling between the tourism industry, urbanization, and ecological environment in Shaanxi&rsquo, s cities, while after 2010, urbanization and tourism industry gradually became the leading factors of the coupling development of the three systems. The coupling development mode in each city has generally undergone an evolution process of &ldquo, ecological environment mode--urbanization mode--tourism industry mode&rdquo, A coupling development mode dominated by urbanization has formed in cities in Northern Shaanxi, a coupling development mode dominated by mixed urbanization and the tourism industry has formed in the Guanzhong Region, and a coupling development mode dominated by the tourism industry has formed in cities in Southern Shaanxi. This paper provides theoretical and practical references for promoting the precise macro-control of cities and guaranteeing the high-quality development of the regional economy.

C-N Bond formation is of great significance due to the ubiquity of nitrogen-containing compounds. Here, a mild and efficient Rh(III) -catalyzed C(sp(3) )-H aryl amination reaction is reported. Anthranil is employed as the nitrogen source with 100 % atom efficiency. This C-H amination reaction exhibits broad substrate scope without using any external oxidants. Mechanistic studies including rhodacycle intermediates, H-D exchange, kinetic isotope effect (KIE) experiments, and in situ IR are presented.

A novel process for preparing direct reduction iron (DRI) and titanium nitride (TiN) from Panzhihua titanomagnetite concentrate is proposed. This process involves pelletizing, direct reduction roasting and magnetic separation. The effects of reduction temperature, coal dosage and reduction time on the phase transformation of composite pellets were investigated by X-ray diffraction. Results show that TiN formation proceeds less easily than metallic iron formation. Increasing the reduction temperature, reduction time and coal dosage can promote the transformation of titanium to TiN. Titanium was almost completely transformed into TiN under the conditions of 1300 °C reduction temperature, 26 wt % coal dosage and 90 min reduction time. The scanning electron microscopy (SEM) analysis showed that near-spherical metallic iron particles with diameters from dozens of microns to about 300 μm were formed in the reduced pellets, whereas the TiN particles generally measured less than 10 μm. The energy dispersive spectroscopy (EDS) results revealed that the TiN phase contains a certain amount of vanadium and carbon, and traces of other impurities. The reduced composite pellets under the optimum conditions were processed by grinding and subsequent magnetic separation. As a result, a DRI with 92.88 wt % Fe, 1.00 wt % Ti, and 0.13 wt % V was obtained, and the recoveries of Fe, Ti, and V were 92.85 wt %, 9.00 wt %, and 19.40 wt %, respectively. 91.00 wt % Ti and 80.60 wt % V were concentrated in the rough TiN concentrate.

In this paper, a scheme which can be used in multi-user quantum digital signature is proposed. The scheme of signature and verification is based on the characters of GHZ (Greenberger-Horne-Zeilinger) states and controlled quantum teleportation. Different from the digital signatures based on computational complexity, this scheme is unconditional secure, and compared to the former presented quantum signature scheme, it does not rely on an arbitrator to verify the signature and realize a message can be signed by multi-user together.