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Abstract Background Traditional topical drug delivery for treating inflammatory skin diseases suffers from poor skin penetration and long-term side effects. Metal nanoparticles show promising application in topical drug delivery for inflammatory skin diseases. Methods Here, we synthesized a new type of nanoparticles, azelamide monoethanolamine-functionalized gold nanoparticles (Au-MEA NPs), based on citrate-capped gold nanoparticles (Au-CA NPs) via the ligand exchange method. The physical and chemical properties of Au-CA NPs and Au-MEA NPs were characterized. In vivo studies were performed using imiquimod-induced psoriasis and LL37-induced rosacea animal models, respectively. For in vitro studies, a model of cellular inflammation was established using HaCaT cells stimulated with TNF-α. In addition, proteomics, gelatin zymography, and other techniques were used to investigate the possible therapeutic mechanisms of the Au-MEA NPs. Results We found that Au-MEA NPs exhibited better stability and permeation properties compared to conventional Au-CA NPs. Transcutaneously administered Au-MEA NPs exerted potent therapeutic efficacy against both rosacea-like and psoriasiform skin dermatitis in vivo without overt signs of toxicity. Mechanistically, Au-MEA NPs reduced the production of pro-inflammatory mediators in keratinocytes by promoting SOD activity and inhibiting the activity of MMP9. Conclusion Au-MEA NPs have the potential to be a topical nanomedicine for the effective and safe treatment of inflammatory skin diseases.

“Tongguan Liqiao” acupuncture method established by Xuemin Shi, a master of traditional Chinese medicine in China and academician of the Chinese Academy of Engineering, derives from the famous “Xing Nao Kai Qiao” therapy (activating the brain and opening the orifices) acupuncture method. It fundamentally takes “adjusting the spirit” as the root of selecting acupoints based on syndrome differentiation. Neiguan (PC 6), Renzhong (DU 26), and Sanyinjiao (SP 6) are selected as the main acupoints to adjust the spirit and revive the brain, nourish the liver and kidney, which treats the root cause. Acupoints such as Lianquan (RN 23), Yifeng (SJ 17), Wangu (GB 12), and Fengchi (GB 20) in the neck region are selected for “unblocking orifices,” which relieves the symptoms. This acupuncture method features deep needling, which aligns with modern swallowing function anatomy. The method can improve the function of poststroke dysphagia by enhancing cerebral blood supply and metabolism and promoting neural functional remodeling.

Abstract Stabilizing active PtNi alloy catalyst toward oxygen reduction reaction is essential for fuel cell. Doping of specific metals is an empirical strategy, however, the atomistic insight into how dopant boosts the stability of PtNi catalyst still remains elusive. Here, with typical examples of Mo and Au dopants, we identify the distinct roles of Mo and Au in stabilizing PtNi nanowires catalysts. Specifically, due to the stronger interaction between atomic orbital for Ni-Mo and Pt-Au, the Mo dopant mainly suppresses the outward diffusion of Ni atoms while the Au dopant contributes to the stabilization of surface Pt overlayer. Inspired by this atomistic understanding, we rationally construct the PtNiMoAu nanowires by integrating the different functions of Mo and Au into one entity. Such catalyst assembled in fuel cell cathode thus presents both remarkable activity and durability, even surpassing the United States Department of Energy technical targets for 2025.

Nanozymes with superior antioxidant properties offer new hope for treating oxidative stress-related inflammatory skin diseases. However, lacking sufficient catalytic activity or having complex material designs limit the application of current metallic nanozymes in inflammatory skin diseases. Here, we report a simple and effective twin-defect platinum nanowires (Pt NWs) enzyme with multiple mimetic enzymes and broad-spectrum ROS scavenging capability for the treatment of inflammatory skin diseases in mice (including psoriasis and rosacea). Pt NWs with simultaneous superoxide dismutase, glutathione peroxidase and catalase mimetic enzyme properties exhibit cytoprotective effects against ROS-mediated damage at extremely low doses and significantly improve treatment outcomes in psoriasis- and rosacea-like mice. Meanwhile, these ultrasmall sizes of Pt NWs allow the nanomaterials to effectively penetrate the skin and do not produce significant biotoxicity. Therefore, Pt NWs have potential applications in treating diseases related to oxidative stress or inflammation.

Akebia species, belonging to Lardizabalaceae, are widespread from subtropical to temperate environments of China, Japan, and Korea. All known Akebia species have medicinal and dietary value and have been widely cultivated as a new fruit crop in many areas of China. However, compared with other crop species, the breeding improvement and commercial cultivation of Akebia remain in their infancy. This review systematically introduces the present germplasm resources, geographical distribution, biological characteristics, interspecific and intraspecific cross compatibility, molecular biology, and breeding progress in Akebia species. Akebia plants are widely distributed in Shanxi, Henan, Sichuan, Chongqing, Hunan, Hubei, Jiangxi, Zhejiang, and Fujian provinces of China, and wild Akebia plants exhibit abundant phenotypic and genetic diversity due to their wide range of geographical distribution and high adaptability in different habitats. Interspecific artificial hybridization experiments have been conducted in our Akebia germplasm resources nursery. The results showed that there was no reproductive isolation between Akebia species, and fertile progeny could be produced. The synthesis of knowledge on these species provides insights for the rational development and utilization of these germplasm resources, and can facilitate the development of new breeding lines or varieties for commercial cultivation or production. Finally, perspectives on Akebia breeding research are discussed and conclusions are provided. This review provided breeders with new insights into Akebia domestication and breeding, and we also proposed five basic steps in the domestication of new fruit crops.

The kiwifruit, Actinidia genus, has emerged as a nutritionally rich and economically significant crop with a history rooted in China. This review paper examines the global journey of the kiwifruit, its genetic diversity, and the role of advanced breeding techniques in its cultivation and improvement. The expansion of kiwifruit cultivation from China to New Zealand, Italy, Chile and beyond, driven by the development of new cultivars and improved agricultural practices, is discussed, highlighting the fruit’s high content of vitamins C, E, and K. The genetic resources within the Actinidia genus are reviewed, with emphasis on the potential of this diversity in breeding programs. The review provides extensive coverage to the application of modern omics technologies, including genomics, transcriptomics, proteomics, and metabolomics, which have revolutionized the understanding of the biology of kiwifruit and facilitated targeted breeding efforts. It examines both conventional breeding methods and modern approaches, like marker-assisted selection, genomic selection, mutation breeding, and the potential of CRISPR-Cas9 technology for precise trait enhancement. Special attention is paid to interspecific hybridization and cisgenesis as strategies for incorporating beneficial traits and developing superior kiwifruit varieties. This comprehensive synthesis not only sheds light on the current state of kiwifruit research and breeding, but also outlines the future directions and challenges in the field, underscoring the importance of integrating traditional and omics-based approaches to meet the demands of a changing global climate and market preferences.

Abstract Background The base editors can introduce point mutations accurately without causing double-stranded DNA breaks or requiring donor DNA templates. Previously, cytosine base editors (CBEs) containing different deaminases are reported for precise and accurate base editing in plants. However, the knowledge of CBEs in polyploid plants is inadequate and needs further exploration. Results In the present study, we constructed three polycistronic tRNA-gRNA expression cassettes CBEs containing A3A, A3A (Y130F), and rAPOBEC1(R33A) to compare their base editing efficiency in allotetraploid N. benthamiana (n = 4x). We used 14 target sites to compare their editing efficiency using transient transformation in tobacco plants. The sanger sequencing and deep sequencing results showed that A3A-CBE was the most efficient base editor. In addition, the results showed that A3A-CBE provided most comprehensive editing window (C1 ~ C17 could be edited) and had a better editing efficiency under the base background of TC. The target sites (T2 and T6) analysis in transformed N. benthamiana showed that only A3A-CBE can have C-to-T editing events and the editing efficiency of T2 was higher than T6. Additionally, no off-target events were found in transformed N. benthamiana. Conclusions All in all, we conclude that A3A-CBE is the most suitable vector for specific C to T conversion in N. benthamiana. Current findings will provide valuable insights into selecting an appropriate base editor for breeding polyploid plants.

Abstract Background Human-guided crop domestication has lasted for more than 10,000 years. In terms of the domestication and breeding of vegetables, cellulose content in edible tissues is one of the most important traits. Primulina eburnea is a recently developed calcium-rich vegetable with a high soluble and bioavailable calcium content in its leaves. However, the high cellulose content in the leaves hampers the taste, and no research has been reported on the genetic basis of cellulose biosynthesis in this calcium-rich vegetable. Results We identified 36 cellulose biosynthesis-involved genes belonging to eight gene families in the P. eburnea genome. The cellulose accumulated decreasingly throughout leaf development. Nineteen genes were considered core genes in cellulose biosynthesis, which were highly expressed in buds but lowly expressed in mature leaves. In the nitrogen fertilization experiment, exogenous nitrogen decreased the cellulose content in the buds. The expressing pattern of 14 genes were consistent with phenotypic variation in the nitrogen fertilization experiment, and thus they were proposed as cellulose toolbox genes. Conclusions The present study provides a strong basis for the subsequent functional research of cellulose biosynthesis-involved genes in P. eburnea, and provides a reference for breeding and/or engineering this calcium-rich vegetable with decreased leaf cellulose content to improve the taste.

High temperatures have a significant impact on plant growth and metabolism. In recent years, the fruit industry has faced a serious threat due to high-temperature stress on fruit plants caused by global warming. In the present study, we explored the molecular regulatory mechanisms that contribute to high-temperature tolerance in kiwifruit. A total of 36 Hsf genes were identified in the A. chinensis (Ac) genome, while 41 Hsf genes were found in the A. eriantha (Ae) genome. Phylogenetic analysis revealed the clustering of kiwifruit Hsfs into three distinct groups (groups A, B, and C). Synteny analysis indicated that the expansion of the Hsf gene family in the Ac and Ae genomes was primarily driven by whole genome duplication (WGD). Analysis of the gene expression profiles revealed a close relationship between the expression levels of Hsf genes and various plant tissues and stress treatments throughout fruit ripening. Subcellular localization analysis demonstrated that GFP-AcHsfA2a/AcHsfA7b and AcHsfA2a/AcHsfA7b -GFP were localized in the nucleus, while GFP-AcHsfA2a was also observed in the cytoplasm of Arabidopsis protoplasts. The results of real-time quantitative polymerase chain reaction (RT-qPCR) and dual-luciferase reporter assay revealed that the majority of Hsf genes, especially AcHsfA2a, were expressed under high-temperature conditions. In conclusion, our findings establish a theoretical foundation for analyzing the potential role of Hsfs in high-temperature stress tolerance in kiwifruit. This study also offers valuable information to aid plant breeders in the development of heat-stress-resistant plant materials.

Summary: T cell activation is a key event in adaptive immunity. However, the dynamics and influencing factors of T cell activation remain unclear. Here, we analyzed CD4 T cells that were stimulated with anti-CD3/CD28 under several conditions to explore the factors affecting T cell activation. We found a stimulated T subset (HSPhi T) highly expressing heat shock proteins, which was derived from stimulated naive T. We identified and characterized inert T, a stimulated T cell subset in transitional state from resting T to activated T. Interestingly, resting CXCR4low T responded to stimulation more efficiently than resting CXCR4hi T. Furthermore, stimulation of CD4 T in the presence of CD8 T resulted in more effector T and more homogeneous expressions of CD25, supporting that presence of CD8 T reduces the extreme response of T cells, which can be explained by regulation of CD4 T activation through CD8 T-initiated cytokine signaling and FAS/FASLG signaling.

The basal eudicot Epimedium (Barrenwort) exhibits innovative floral morphology in the form of petal spurs filled with nectar and petaloid sepals. The B-class MADS-box genes APETALAS3 (AP3) and PISTILLA (PI) determine sepal and petal identity while the C-class gene AGAMOUS (AG) determines carpel and stamen identity in Arabidopsis. Complex histories of gene duplication resulted in subsequent subfunctionalization or neofunctionalization of paralogs. Here, a total of four B- and two C-class genes were successfully isolated from E. sagittatum. Phylogenetic analysis showed that EsAP3-1, EsAP3-2, and EsAP3-3 are part of the AP3 clade; EsPI is part of the PI group; and EsAG and EsAG11 clustered into the AG and AG11 groups, respectively. Quantitative real-time PCR was utilized to detect the expression patterns of these genes, and all B-class genes except for EsAP3-3 were found to be universally expressed. The transcribed EsAG and EsAG11 genes were confined to reproductive organs. In addition, yeast three and two hybrid assays were used to explore the status of protein complexes. EsAP3-1 was found to have broadly interactive partners, and EsPI can form a heterodimer with EsAP3-1 and EsAP3-2. Transgenic EsAG overexpression in wild-type Arabidopsis confirmed the conserved function determining carpel development.

Attaining high selectivity for CO2 electroreduction in acid is usually difficult due to competing hydrogen evolution. Here, the authors demonstrate efficient CO2 reduction to multicarbon products in strongly acidic medium (pH ≤ 1) on a porous Cu catalyst by combining confinement and cation effects.

Abstract Despite of superior performance of the oxide‐derived copper (OD‐Cu) in producing valuable hydrocarbons during CO2RR, its fabrication process is still ambiguous and complicated. In this work, we develop a simple microwave‐assisted method to synthesize the oxide‐derived Cu nanosheet (OD‐Cu NS) and reveal that the oxidation state of Cu species is controlled by varying the Cu precursor amount. Notably, the simultaneous formation of nano‐sized Cu domains influence the surface roughness of OD‐Cu NS. The partially oxidized Cu surface exhibits a superior faradaic efficiency (FE) of C2+ products up to 72%, along with a partial current density of 55 mA cm−2 in a neutral KHCO3 solution. More importantly, the as‐obtained OD‐Cu NS shows a synergetic effect on dissociating of CO2 molecules by the strong binding energy and promoting of C2+ compounds productivity by the enlarged electrochemical surface area. This work provides a new insight for designing efficient OD‐Cu catalysts toward CO2RR.

IntroductionFlower color is an ideal trait for studying the molecular basis for phenotypic variations in natural populations of species. Epimedium (Berberidaceae) species exhibit a wide range of flower colors resulting from the varied accumulation of anthocyanins and other pigments in their spur-like petals and petaloid sepals.MethodsIn this work, the anthocyanidins of eight different Epimedium species with different floral pigmentation phenotypes were analyzed using HPLC. Twelve genes involved in anthocyanin biosynthesis were cloned and sequenced, and their expression was quantified.ResultsThe expression levels of the catalytic enzyme genes DFR and ANS were significantly decreased in four species showing loss of floral pigmentation. Complementation of EsF3’H and EsDFR in corresponding Arabidopsis mutants together with overexpression of EsF3’5’H in wild type Arabidopsis analysis revealed that these genes were functional at the protein level, based on the accumulation of anthocyanin pigments.DiscussionThese results strongly suggest that transcriptional regulatory changes determine the loss of anthocyanins to be convergent in the floral tissue of Epimedium species.

Abstract The current kiwifruit industry is mainly based on the cultivars derived from the species Actinidia chinensis (Ac) which may bring risks such as canker disease. Introgression of desired traits from wild relatives is an important method for improving kiwifruit cultivars. Actinidia eriantha (Ae) is a particularly important taxon used for hybridization or introgressive breeding of new kiwifruit cultivars because of its valued species-specific traits. Here, we assembled a chromosome-scale high-quality genome of a Ae sample which was directly collected from its wild populations. Our analysis revealed that 41.3% of the genome consists of repetitive elements, comparable to the percentage in Ac and Ae cultivar “White” genomes. The genomic structural variation, including the presence/absence-variation (PAV) of genes, is distinct between Ae and Ac, despite both sharing the same two kiwifruit-specific whole genome duplication (WGD) events. This suggests that a post-WGD divergence mechanism occurred during their evolution. We further investigated genes involved in ascorbic acid biosynthesis and disease-resistance of Ae, and we found introgressive genome could contribute to the complex relationship between Ae and other representative kiwifruit taxa. Collectively, the Ae genome offers valuable genetic resource to accelerate kiwifruit breeding applications.

The differences between the “Tong Guan Li Qiao” acupuncture therapy and the conventional and current other acupuncture methods for poststroke dysphagia are as follows: first, it adheres to the basic idea of “Xing Nao Kai Qiao” acupuncture therapy in selecting and combining acupoints, centers on the brain, and combines the dysphagia symptoms of the mouth, tongue, and throat-related orifices with the root cause of “brain”; second, there are strict and standard requirements in the acupuncture operation, that is, manipulation quantification. In addition to standardized twirling, lifting, and thrusting, the techniques of deep needling on the acupoints in the neck region, blood-letting puncturing at the posterior wall of the pharynx, and the needling sensation of “like a fishbone getting stuck in the throat” are all unique.

Herein, the preparation of AuAgPt alloy yolk‐shell nanostructures with tunable elemental compositions and morphologies by conducting the mild, successive galvanic replacement reaction (GRR) between Au@Ag core‐shell nanocubes and H2PtCl6 is reported. In particular, the resulting products can be featured with well‐defined cubic frames and the distribution of all the three metals over the whole particle, which is enabled by the unique “etching and regrowth” mechanism. Due to the strong absorbance in visible region, the current products exhibit superb performances in two localized surface plasmon resonance (LSPR)‐based applications, photothermal heat conversion, and plasmon‐enhanced catalytic reduction of 4‐nitrophenol (4‐NP). In particular, the optimized photothermal heat conversion efficiency and the apparent rate constant of photocatalytic 4‐NP reduction reach 12.9% and 0.155 min−1, respectively, for the sample AuAgPt‐6 and AuAgPt‐12, respectively. Herein the present study, a feasible strategy for fabrication of plasmonic‐active multimetallic alloy nanocrystals with yolk‐shell structure and cubic frame‐like edges is offered and their promising use in photothermal heat conversion and photocatalysis is validated, which could be extended to other alloys or material combinations for rational design of nanoscale materials with plasmon‐enhanced properties.

Elaeagnus L. is found in wild or grown as ornamental plants and is increasingly regarded as underutilized berry shrubs by breeders. This genus has cosmopolitan distribution with various species widely distributed in China, Europe, the United States, and Canada. Interspecific hybrids, which have been reported several times, have attracted intense interest from plant breeders attempting to develop a fruit crop of Elaeagnus. Orthogonal projections to latent structures discriminant analysis (OPLS-DA) is a powerful statistical modeling tool that provides insights into separations between experimental groups. In this study, the molecular phylogeny of Elaeagnus species was first discussed using the ITS and matK sequences for guiding the construction of a genetic basis pool. A morphological OPLS-DA clustering model based on the genetic divergence was also constructed for the first time, which effectively realized the morphological grouping of Chinese Elaeagnus species. The results showed that a total of 10 wild species widely distributed in China have the potential to develop fruit crops. Particularly, Elaeagnus conferta has the potential to provide a founder species with a large fruit size, while Elaeagnus Gonyanthes has the potential to provide important genetic resources with long pedicel. Elaeagnus lanceolata and Elaeagnus delavayi could be used to domesticate hybrids without spines, and the other five climbing shrubs could be used to develop high-yield crown-type commercial cultivars for automated field management. The top five contributing morphological traits affecting the current clustering model were V9 (flower color), V1 (flowering), V5 (evergreen or deciduous), V3 (leaf size), and V2 (fruiting). Furthermore, the grouping analysis indicated that the V9 was the most important factor affecting morphological clustering. Thereafter, the temporally calibrated phylogeny inferred from the matK sequence was used to reconstruct the origin and evolution of the genus Elaeagnus, and the results inferred an interesting geographic distribution pattern and potential cross-species interactions of Elaeagnus species at low latitudes in China. Our study also highlighted dispersal pattern investigation and genetic background analysis to improve future practices and policies related to species introduction of genetic basis pool.

The STAY-GREEN (SGR) proteins play an important role in chlorophyll (Chl) degradation and are closely related to plant photosynthesis. However, the availability of inadequate studies on SGR motivated us to conduct a comprehensive study on the identification and functional dissection of SGR superfamily members in kiwifruit. Here, we identified five SGR genes for each of the kiwifruit species [Actinidia chinensis (Ac) and Actinidia eriantha (Ae)]. The phylogenetic analysis showed that the kiwifruit SGR superfamily members were divided into two subfamilies the SGR subfamily and the SGRL subfamily. The results of transcriptome data and RT-qPCR showed that the expression of the kiwifruit SGRs was closely related to light and plant developmental stages (regulated by plant growth regulators), which were further supported by the presence of light and the plant hormone-responsive cis-regulatory element in the promoter region. The subcellular localization analysis of the AcSGR2 protein confirmed its localization in the chloroplast. The Fv/Fm, SPAD value, and Chl contents were decreased in overexpressed AcSGR2, but varied in different cultivars of A. chinensis. The sequence analysis showed significant differences within AcSGR2 proteins. Our findings provide valuable insights into the characteristics and evolutionary patterns of SGR genes in kiwifruit, and shall assist kiwifruit breeders to enhance cultivar development.

The exploration and use of wild plant resources goes back to our rooted history of human civilization over about 20,000 years ago, before Ancient Mesopotamia in the Valley of the Tigris and Euphrates where barley, lentil and wheat were first domesticated [...]

Light-harvesting chlorophyll a/b-binding (LHC) protein is a superfamily that plays a vital role in photosynthesis. However, the reported knowledge of LHCs in kiwifruit is inadequate and poorly understood. In this study, we identified 42 and 45 LHC genes in Actinidia chinensis (Ac) and A. eriantha (Ae) genomes. Phylogenetic analysis showed that the kiwifruit LHCs of both species were grouped into four subfamilies (Lhc, Lil, PsbS, and FCII). Expression profiles and qRT-PCR results revealed expression levels of LHC genes closely related to the light, temperature fluctuations, color changes during fruit ripening, and kiwifruit responses to Pseudomonas syringae pv. actinidiae (Psa). Subcellular localization analysis showed that AcLhcb1.5/3.1/3.2 were localized in the chloroplast while transient overexpression of AcLhcb3.1/3.2 in tobacco leaves confirmed a significantly increased content of chlorophyll a. Our findings provide evidence of the characters and evolution patterns of kiwifruit LHCs genes in kiwifruit and verify the AcLhcb3.1/3.2 genes controlling the chlorophyll a content.

Akebia trifoliata is a high-value medicinal and edible fruit crop in China, and it has begun to be widely cultivated as a new fruit crop in many areas of China. Its fruits crack longitudinally when fully ripe and should be harvested before fruit cracking. Physicochemical characteristics and nutritional composition of the ripening process are prerequisites to establishing proper harvest maturity windows. In the current study, we have investigated the fruit quality characteristics of two A. trifoliata clonal lines (‘Luqing’ and ‘Luyu’) that were harvested at four time points (S1: 120 days after full bloom (DAFB), S2: 134 DAFB, S3: 148 DAFB, S4: 155 DAFB). An increase in fruit size (fruit weight, fruit length, and fruit diameter) was associated with delayed harvest maturity. The firmness of A. trifoliata fruit exhibited a decreasing trend with delaying the harvest stage. In particular, the firmness decreased sharply from S2 to S3 stage. The TSS, fructose, and glucose content in A. trifoliata fruit continuously increased from the S1 to S4 stage and accumulated sharply from S2 to S3 stage. However, the sucrose and starch content showed an increasing trend from the S1 to S2 stage but declined sharply in the S3 or S4 stage. Ascorbic acid progressively increased with the advancement of A. trifoliata maturity stages, while total phenolics and total flavonoids levels declined with fruit ripening. Considering the results of all quality parameters mentioned above, the A. trifoliata fruit harvested at the S3 maturity stage was the ideal harvest maturity for long-distance transportation and higher consumer acceptability before fruit cracking. Our research reveals the dynamic changes in physicochemical characteristics and nutritional composition during fruit ripening of A. trifoliata. Results in this study reflect the importance of maturity stages for fruit quality and provide basic information for optimal harvest management of A. trifoliata.

Selective electroreduction of carbon dioxide (CO2RR) into ethanol at an industrially relevant current density is highly desired. However, it is challenging because the competing ethylene production pathway is generally more thermodynamically favored. Herein, we achieve a selective and productive ethanol production over a porous CuO catalyst that presents a high ethanol Faradaic efficiency (FE) of 44.1 ± 1.0% and an ethanol-to-ethylene ratio of 1.2 at a large ethanol partial current density of 501.0 ± 15.0 mA cm-2, in addition to an extraordinary FE of 90.6 ± 3.4% for multicarbon products. Intriguingly, we found a volcano-shaped relationship between ethanol selectivity and nanocavity size of porous CuO catalyst in the range of 0 to 20 nm. Mechanistic studies indicate that the increased coverage of surface-bounded hydroxyl species (*OH) associated with the nanocavity size-dependent confinement effect contributes to the remarkable ethanol selectivity, which preferentially favors the *CHCOH hydrogenation to *CHCHOH (ethanol pathway) via yielding the noncovalent interaction. Our findings provide insights in favoring the ethanol formation pathway, which paves the path toward rational design of ethanol-oriented catalysts. [ABSTRACT FROM AUTHOR]