Construction and Function of Thiolate-Bridged Diiron NxHy Nitrogenase Model Complexes.

ConspectusBiological nitrogen fixation mediated by nitrogenases has garnered significant research interest due to its critical importance to the development of efficient catalysts for mild ammonia synthesis. Although the active center of the most studied FeMo-nitrogenases has been determined to be a complicated [Fe7S9MoC] hetero-multinuclear metal-sulfur cluster known as the FeMo-cofactor, the exact binding site and reduction pathway of N2 remain a subject of debate. Over the past decades, the majority of studies have focused on mononuclear molybdenum or iron centers as potential reaction sites. In stark contrast, cooperative activation of N2 through bi- or multimetallic centers has been largely overlooked and underexplored, despite the renewed interest sparked by recent biochemical and computational studies. Consequently, constructing bioinspired bi- or multinuclear metallic model complexes presents an intriguing yet challenging prospect. In this Account, we detail our long-standing research on the design and synthesis of novel thiolate-bridged diiron complexes as nitrogenase models and their application to chemical simulations of potential biological N2 reduction pathways.Inspired by the structural and electronic features of the potential diiron active center in the belt region of the FeMo-cofactor, we have designed and synthesized a series of new thiolate-bridged diiron nitrogenase model complexes, wherein iron centers with +2 or +3 oxidation states are coordinated by Cp* as carbon-based donors and thiolate ligands as sulfur donors. Through the synergistic interaction between the two iron centers, unstable diazene (NH═NH) species can be trapped to generate the first example of a [Fe2S2]-type complex bearing a cis-µ-η1:η1-NH═NH subunit. Significantly, this species can not only catalyze the reductive N-N bond cleavage of hydrazine to ammonia but also trigger a stepwise reduction sequence NH═NH → [NH2-NH]- → [NH]2-(+NH3) → [NH2]- → NH3. Furthermore, an unprecedented thiolate-bridged diiron µ-nitride featuring a bent Fe-N-Fe moiety was successfully isolated and structurally characterized. Importantly, this diiron µ-nitride can undergo successive proton-coupled electron transfer processes to efficiently release ammonia in the presence of separate protons and electrons and can even be directly hydrogenated using H2 as a combination of protons and electrons for high-yield ammonia formation. Based on combined experimental and computational studies, we proposed two distinct reductive transformation sequences on the diiron centers, which involve a series of crucial NxHy intermediates. Moreover, we also achieved catalytic N2 reduction to silylamines with [Fe2S2]-type complexes by ligand modulation.Our bioinspired diiron cooperative scaffold may provide a suitable model for probing the potential N2 stepwise reduction pathways from the molecular level. Different from the traditional alternating and distal pathways dominated by mononuclear iron or molybdenum complexes, our proposed alternating transformation route based on the diiron centers may not involve the N2H4 intermediate, and the convergence point of the alternating and terminal pathways is imide, not amide. Our research strategy could inform the design and development of new types of bioinspired catalysts for mild and efficient nitrogen reduction in the future.

Resilient Growth of a Highly Crystalline Topological Insulator-Superconductor Heterostructure Enabled by an Ex Situ Nitride Film.

Highly crystalline and easily feasible topological insulator-superconductor (TI-SC) heterostructures are crucial for the development of practical topological qubit devices. The optimal superconducting layer for TI-SC heterostructures should be highly resilient against external contamination and structurally compatible with TIs. In this study, we provide a solution to this challenge by showcasing the growth of a highly crystalline TI-SC heterostructure using refractory TiN (111) as the superconducting layer. This approach can eliminate the need for in situ cleavage or growth. More importantly, the TiN surface shows high resilience against contaminations during air exposure, as demonstrated by the successful recyclable growth of Bi2Se3. Our findings indicate that TI-SC heterostructures based on nitride films are compatible with device fabrication techniques, paving the way to the realization of practical topological qubit devices in the future.

Organocatalytic diastereo- and atropo-selective construction of eight-membered bridged (hetero)biaryls via asymmetric intramolecular [3 + 2] cycloaddition.

An unprecedented and straightforward route for the asymmetric construction of privileged atroposelective bridged (hetero)biaryl eight-membered scaffolds has been accomplished through chiral phosphoric acid catalyzed asymmetric intramolecular [3 + 2] cycloaddition of innovative (hetero)biaryl aldehydes with 3-aminooxindole hydrochlorides. A class of eight-membered bridged (hetero)biaryl lactones fused to spiro[pyrrolidine-oxindole] derivatives, possessing both chiral C-C/C-N axes and multiple contiguous stereocenters, were obtained in good yields with excellent enantioselectivities and diastereoselectivities in one step through this direct strategy. In addition, the good scalability and derivatization of the title compounds demonstrated their synthetic utility.

Asymmetric synthesis of atropisomeric arylpyrazoles via direct arylation of 5-aminopyrazoles with naphthoquinones.

Construction of axially chiral arylpyrazoles represents an attractive challenge due to the relatively low rotational barrier of biaryl structures containing five-membered heterocycles. This work describes the catalytic asymmetric construction of axially chiral arylpyrazoles using 5-aminopyrazoles and naphthoquinone derivatives. The chiral axis could be formed through a central-to-axial chirality relay step of the chiral phosphoric acid-catalyzed arylation reaction, which features excellent yields and enantioselectivities with a broad substrate scope under mild reaction conditions.

High-Performance Liquid Chromatographic Quantification of the Plant Hormone Abscisic Acid at ppb Levels in Plant Samples after a Single Immunoaffinity Column Cleanup.

High-performance liquid chromatography with ultraviolet detection (HPLC-UV) is a common analysis technique due to its high versatility and simple operation. In the present study, HPLC-UV detection was integrated with immunoaffinity cleanup (IAC) of the sample extracts. The matrix effect was greatly reduced, and the limit of detection was as low as 1 ng/g of free abscisic acid (ABA) in fresh plant tissues. A monoclonal antibody 3F1 (mAb 3F1) was developed to specifically recognize free ABA but not ABA analogues. The mAb 3F1-immobilized immunoaffinity column exhibited a capacity of 850 ng/mL and an elution efficiency of 88.8-105% for standards. The extraction recoveries of the column for ABA ranged from 80.4 to 108.9%. ABA content was detected in various plant samples with IAC-HPLC-UV. The results were verified with ultraperformance liquid chromatography-electrospray tandem mass spectrometry. IAC-HPLC-UV can be a sensitive and cost-efficient method for plant hormone analysis.

Solidification/stabilization and optimization of municipal solid waste incineration fly ash with aluminosilicate solid wastes.

Alkali-activation is an effective municipal solid waste incineration fly ash (MSWIFA) solidification/stabilization (S/S) technology. However, the characteristics of calcium-rich silica-poor aluminum phase in MSWIFA easily cause the structural instability and contamination of alkali activated MSWIFA S/S bodies. Therefore, the aluminosilicate solid wastes are used in this work to optimize the immobilization and structural properties. Results showed that incorporation of aluminosilicate solid wastes significantly improved the compressive strength and heavy metals pollution toxicity of MSWIFA S/S bodies. Compared to alkali activated MSWIFA, the compressive strength of S/S bodies with addition of coal fly ash, silica fume and granulated blast furnace slag improved by 31.0%, 47.6% and 50.8% when the curing time was 28 days, respectively. Leachability of Pb, Zn and Cd in these alkali activated MSWIFA S/S bodies was far below the threshold value specified in Standard GB16889. Aluminosilicate solid wastes provided abundant Si/Al structural units, and some new phases such as ettringite(AFt, 3CaO⋅Al2O3⋅3CaSO4⋅32H2O), calcium sulfoaluminate hydrate (3CaO⋅Al2O3⋅CaSO4⋅12H2O) and Friedel's salt (CaO⋅Al2O3⋅CaCl2⋅10H2O) can be detected in S/S matrix with aluminosilicate solid wastes, along comes increased the amount of the amorphous phases. Lower Ca/Si molar ratio tended to form the network structure gel similar to tobermorite with higher polymerization degree. Meanwhile, the silica tetrahedron of the gels changed from the oligomerization state like island to the hyperomerization state like chain, layer network or three-dimensional structure, and average molecular chain length increased. These findings provide theoretical basis for structural properties optimization and resource utilization of MSWIFA S/S matrices.

Migration pathway and solidification mechanism of heavy metal Pb during the conversion of municipal solid waste incineration fly ash into ettringite and simultaneously purification of chloride salts solution process.

The solidification/stabilization of heavy metals and valuable component recovery from municipal solid waste incineration (MSWI) fly ash are of great significance for its safe disposal. In this study, MSWI fly ash was transformed into a new solid phase mainly composed of ettringite, achieving the solidification of excessive heavy metal Pb while obtaining a mixed solution of sodium chloride and potassium chloride with extremely low impurity content, which can be recovered by evaporation-crystallization respectively. The solidification mechanism of heavy metal Pb by ettringite was investigated through a combination of DFT calculations and experiments. The results indicate that a high conversion rate of calcium ions (99.68%), separation rate of chloride (95.99%), and conversion rate of heavy metal Pb (99.42%) can be achieved by controlling the ions ratio of the MSWI fly ash reaction system to n(Ca2+):n(Al3+):n(SO42-) = 6:2:3. DFT calculations show that the reaction pathway of the formation of a vacancy-Pb entering the vacancy at the Ca-2 site of ettringite is more likely to occur. The substitution of heavy metal Pb at the Ca-2 site leads to an increase in the unit cell volume, redistribution of charges, and a decrease in the thermal stability of the ettringite. The solidified body of ettringite presents a promising potential for application in cement-based materials due to its negligible risk of heavy metals leaching and low chloride content.

Detection of ustilaginoidins in rice samples by immunoassay based on monoclonal antibodies prepared from hemiustilaginoidin-derived haptens.

Ustilaginoidins are a class of bis-naphtho-γ-pyrone mycotoxins to threaten humans, animals and environment. Ustilaginoidins are produced by Villosiclava virens, the rice false smut pathogen. To prepare antibodies for quantitatively analyzing ustilaginoidins in rice samples, hemiustilaginoidins D and F from the laccase gene deficiency mutant of V. virens respectively reacted with diazonium 4-aminobenzoic acid to obtain haptens with a carboxyl group, which further reacted with bovine serum albumin or ovalbumin to get their complete antigens. Two monoclonal antibodies (mAbs) designated as 4A12C6 and 5F4F6 were developed by immunization. The relationships between mAb sensitivity and 20 ustilaginoidins were described. 4A12C6 was chosen for further analysis as it could recognize main ustilaginoidins and was more sensitive than 5F4F6. The achieved indirect competitive enzyme-linked immunosorbent assay (icELISA) based on 4A12C6 had a half maximal inhibitory concentration (IC50) of 0.76 ng/mL and working range of 0.2-2.8 ng/mL to ustilaginoidin A. The results of ustilaginoidins-contaminated rice samples by icELISA detection were consistent with those determined by HPLC‒DAD detection. Therefore, we developed a new strategy to get haptens from the biosynthetic precursors with half structures of ustilaginoidins. The achieved icELISA was demonstrated as a convenient method to monitor ustilaginoidin content in rice samples, and showed that the contents of total ustilaginoidins from the rice cultivars with low resistance to rice false smut were more than those of high resistance cultivars.

Coronatine-Induced Maize Defense against Gibberella Stalk Rot by Activating Antioxidants and Phytohormone Signaling.

One of the most destructive diseases, Gibberella stalk rot (GSR), caused by Fusarium graminearum, reduces maize yields significantly. An induced resistance response is a potent and cost-effective plant defense against pathogen attack. The functional counterpart of JAs, coronatine (COR), has attracted a lot of interest recently due to its ability to control plant growth and stimulate secondary metabolism. Although several studies have focused on COR as a plant immune elicitor to improve plant resistance to pathogens, the effectiveness and underlying mechanisms of the suppressive ability against COR to F. graminearum in maize have been limited. We investigated the potential physiological and molecular mechanisms of COR in modulating maize resistance to F. graminearum. COR treatment strongly enhanced disease resistance and promoted stomatal closure with H2O2 accumulation, and 10 µg/mL was confirmed as the best concentration. COR treatment increased defense-related enzyme activity and decreased the malondialdehyde content with enhanced antioxidant enzyme activity. To identify candidate resistance genes and gain insight into the molecular mechanism of GSR resistance associated with COR, we integrated transcriptomic and metabolomic data to systemically explore the defense mechanisms of COR, and multiple hub genes were pinpointed using weighted gene correlation network analysis (WGCNA). We discovered 6 significant modules containing 10 candidate genes: WRKY transcription factor (LOC100279570), calcium-binding protein (LOC100382070), NBR1-like protein (LOC100275089), amino acid permease (LOC100382244), glutathione S-transferase (LOC541830), HXXXD-type acyl-transferase (LOC100191608), prolin-rich extensin-like receptor protein kinase (LOC100501564), AP2-like ethylene-responsive transcription factor (LOC100384380), basic leucine zipper (LOC100275351), and glycosyltransferase (LOC606486), which are highly correlated with the jasmonic acid-ethylene signaling pathway and antioxidants. In addition, a core set of metabolites, including alpha-linolenic acid metabolism and flavonoids biosynthesis linked to the hub genes, were identified. Taken together, our research revealed differentially expressed key genes and metabolites, as well as co-expression networks, associated with COR treatment of maize stems after F. graminearum infection. In addition, COR-treated maize had higher JA (JA-Ile and Me-JA) levels. We postulated that COR plays a positive role in maize resistance to F. graminearum by regulating antioxidant levels and the JA signaling pathway, and the flavonoid biosynthesis pathway is also involved in the resistance response against GSR.

Solidification of municipal solid waste incineration fly ash with alkali-activated technology.

Alkali-activation is effective municipal solid waste incineration fly ash (MSWIFA) solidification/stabilization (S/S) technology. Percolation and migration of heavy metals in MSWIFA S/S matrix is a complicated and slow process. Here, several alkali-activated MSWIFA samples are selected to comparatively investigate the long-term leaching behavior and environmental availability of Pb, Zn and Cd when exposed in different erosion environment. Acid environment posed the more serious destroy to MSWIFA S/S matrices. RAC demonstrated that potential risk level of heavy metals is higher in acid rain environment, and Cd, Zn showed the prominent risk. When soaked in acid rain solution, the surface of alkali-activated MSWIFA S/S matrices was cracked seriously and a large number of hardened slurry peeled off. However, more stable structural properties and lower heavy metal leachability can be found in alkali-activated MSWIFA/aluminosilicate. The immobilization efficiency of Pb, Zn and Cd were all above 99.0%. Microstructure and morphology results indicated that there is new phase Friedel's salts generated and much more amorphous substance such as C-(A)-S-H gel with incorporation of aluminosilicate, which all contributed much to the formation of compact and stable microstructure, then significantly facilitated the encapsulation of heavy metal. These findings will provide theoretical basis and new insight for resource utilization and security landfill of MSWIFA.

Unusual Hydrogenation Reactivities of a Thiolate-Bridged Dicobalt µ-Nitride Featuring a Bent {CoIII-N-CoIII} Core.

Transition metal nitrides have received considerable attention owing to their crucial roles in nitrogen fixation and nitrogen atom transfer reactions. Compared to the early and middle transition metals, it is much more challenging to access late transition metal nitrides, especially cobalt in group 9. So far, only a handful of cobalt nitrides have been reported; consequently, their hydrogenation reactivity is largely unexplored. Herein, we present a structurally and spectroscopically well-characterized thiolate-bridged dicobalt µ-nitride [Cp*CoIII(µ-SAd)(µ-N)CoIIICp*] (2) featuring a bent {CoIII(µ-N)CoIII} core. Remarkably, complex 2 can realize not only direct hydrogenation of nitride to amide but also stepwise N-H bond formation from nitride to ammonia. Specifically, 2 can facilely activate dihydrogen (H2) at mild conditions to generate a dicobalt µ-amide [Cp*CoII(µ-SAd)(µ-NH2)CoIICp*] (4) via an unusual mechanism of two-electron oxidation of H2 as proposed by computational studies; in the presence of protons (H+) and electrons, nitride 2 can convert to dicobalt µ-imide [Cp*CoIII(µ-SAd)(µ-NH)CoIIICp*][BPh4] (3[BPh4]) and to CoIICoII µ-amide 4, and finally release ammonia. In contrast to 2, the only other structurally characterized dicobalt µ-nitride Na(THF)4{[(ketguan)CoIII(N3)]2(µ-N)} (ketguan = [(tBu2CN)C(NDipp)2]-, Dipp = 2,6-diisopropylphenyl) (e) that possesses a linear {CoIII(µ-N)CoIII} moiety cannot directly react with H2 or H+. Further in-depth electronic structure analyses shed light on how the varying geometries of the {CoIII(µ-N)CoIII} moieties in 2 and e, bent vs linear, impart their disparate reactivities.

Squaramide-catalyzed asymmetric regioselective allylic alkylation of 4-aminopyrazolones with Morita-Baylis-Hillman carbonates.

An efficient squaramide-catalyzed asymmetric allylic alkylation of 4-aminopyrazolones with various MBH carbonates via different pathways has been described. This method provides access to a series of pyrazolone derivatives bearing a nitrogen-containing quaternary stereocenter in high yields with excellent enantioselectivities and regioselectivities under mild conditions. In addition, we utilized the target products to construct a range of bi-heterocyclic skeletons through [3 + 2] cycloadditions. These novel hybrid heterocycles would be promising candidates for drug-discovery programs and chemical biology.

From WSI-level to patch-level: Structure prior-guided binuclear cell fine-grained detection.

Accurate and quick binuclear cell (BC) detection plays a significant role in predicting the risk of leukemia and other malignant tumors. However, manual counting of BCs using microscope images is time consuming and subjective. Moreover, traditional image processing approaches perform poorly due to the limitations in staining quality and the diversity of morphological features in binuclear cell (BC) microscopy whole-slide images (WSIs). To overcome this challenge, we propose a multi-task method inspired by the structure prior of BCs based on deep learning, which cascades to implement BC coarse detection at the WSI level and fine-grained classification at the patch level. The coarse detection network is a multitask detection framework based on circular bounding boxes for cell detection and central key points for nucleus detection. Circle representation reduces the degrees of freedom, mitigates the effect of surrounding impurities compared to usual rectangular boxes and can be rotation invariant in WSIs. Detecting key points in the nucleus can assist in network perception and be used for unsupervised color layer segmentation in later fine-grained classification. The fine classification network consists of a background region suppression module based on color layer mask supervision and a key region selection module based on a transformer due to its global modeling capability. Additionally, an unsupervised and unpaired cytoplasm generator network is first proposed to expand the long-tailed distribution dataset. Finally, experiments are performed on BC multicenter datasets. The proposed BC fine detection method outperforms other benchmarks in almost all evaluation criteria, providing clarification and support for tasks such as cancer screenings.

DMAP-Catalyzed [4+3] Spiroannulation of Pyrazolone-Derived Morita-Baylis-Hillman Carbonates with N-(o-Chloromethyl)aryl Amides to Forge Spiro[pyrazolone-azepine] Scaffolds.

A novel DMAP-catalyzed [4+3] spiroannulation of pyrazolone-derived Morita-Baylis-Hillman carbonates with N-(o-chloromethyl)aryl amides was developed. This reaction led to the assembly of medicinally relevant pyrazolone and azepine nuclei into a structurally new spirocyclic scaffold, and a diverse array of spiro[pyrazolone-azepine] products were afforded in good to excellent yields (up to 93%) with a wide substrate scope (23 examples) under mild conditions. Moreover, a gram-scale reaction and product transformations were conducted, which further increased the diversity of products.

Desymmetrization of Prochiral N-Pyrazolyl Maleimides via Organocatalyzed Asymmetric Michael Addition with Pyrazolones: Construction of Tri-N-Heterocyclic Scaffolds Bearing Both Central and Axial Chirality.

The desymmetrization of N-pyrazolyl maleimides was realized through an asymmetric Michael addition by using pyrazolones under mild conditions, leading to the formation of a tri-N-heterocyclic pyrazole-succinimide-pyrazolone assembly in high yields with excellent enantioselectivities (up to 99% yield, up to 99% ee). The use of a quinine-derived thiourea catalyst was essential for achieving stereocontrol of the vicinal quaternary-tertiary stereocenters together with the C-N chiral axis. Salient features of this protocol included a broad substrate scope, atom economy, mild conditions and simple operation. Moreover, a gram-scale experiment and derivatization of the product further illustrated the practicability and potential application value of this methodology.

Fabrication of Mechanically Strong Silica Aerogels with the Thermally Induced Phase Separation (TIPS) Method of Poly(methyl methacrylate).

Constructing and maintaining a three-dimensional network structure with high porosity is critical to the preparation of silica aerogel materials because this structure provides excellent properties. However, due to the pearl-necklace-like structure and narrow interparticle necks, aerogels have poor mechanical strength and a brittle nature. Developing and designing lightweight silica aerogels with distinct mechanical properties is significant to extend their practical applications. In this work, thermally induced phase separation (TIPS) of poly(methyl methacrylate) (PMMA) from a mixture of ethanol and water was used to strengthen the skeletal network of aerogels. Strong and lightweight PMMA-modified silica aerogels were synthesized via the TIPS method and supercritically dried with carbon dioxide. The cloud point temperature of PMMA solutions, physical characteristics, morphological properties, microstructure, thermal conductivities, and mechanical properties were investigated. The resultant composited aerogels not only exhibit a homogenous mesoporous structure but also achieve a significant improvement in mechanical properties. The addition of PMMA increased the flexural strength and compressive strength by as much as 120% and 1400%, respectively, with the greatest amount of PMMA (Mw = 35,000 g/mole), while the density just increased by 28%. Overall, this research suggests that the TIPS method has great efficiency in reinforcing silica aerogels with less sacrifice of low density and large porosity.

Effect and mechanism of nano-alumina on early hydration properties and heavy metals solidification/stabilization of alkali-activated MSWI fly ash solidified body.

Municipal solid waste incineration (MSWI) fly ash has serious pollution. It needs to be solidification/stabilization (S/S) to sanitary landfill as quickly as possible. In order to achieve the objective, the early hydration properties of alkali-activated MSWI fly ash solidified body were investigated in this paper. Meanwhile, nano-alumina was utilized as an agent to optimize the early performance. Therefore, the mechanical properties, environmental safety, hydration process and mechanisms of heavy metals S/S were explored. The results showed that after adding nano-alumina, the leaching concentration of Pb and Zn in solidified bodies after 3 d curing was significantly reduced by 49.7-63% and 65.8-76.1%, respectively, and the compressive strength was enhanced by 10.2-55.9%. Nano-alumina improved the hydration process, and the predominant hydration products in solidified bodies were C-S-H gels and C-A-S-H gels. Meanwhile, nano-alumina could obviously increase the most stable chemical speciation (residual state) ratio of heavy metals in solidified bodies. Pore structure data showed that, due to the filling effect and pozzolanic effect of nano-alumina, the porosity has been reduced and the ratio of harmless pore structure has been increased. Therefore, it can be concluded that solidified bodies mainly solidify MSWI fly ash by physical adsorption, physical encapsulation and chemical bonding.

Palladium-Catalyzed Stereoselective Construction of 1,3-Stereocenters Displaying Axial and Central Chirality via Asymmetric Alkylations.

The concurrent construction of 1,3-stereocenters remains a challenge. Herein, we report the development of stereoselective union of a point chiral center with allenyl axial chirality in 1,3-position by Pd-catalyzed asymmetric allenylic alkylation between racemic allenyl carbonates and indanone-derived ß-ketoesters. Various target products bearing a broad range of functional groups were afforded in high yield (up to 99%) with excellent enantioselectivities (up to 98% ee) and good diastereoselectivities (up to 13:1 dr).

Isolation of atrazine nanobodies enhanced by depletion of anti-carrier protein phages and performance comparison between the nanobody and monoclonal antibody derived from the same immunogen.

Nanobody, a single domain antibody, has been shown a great promise for immunoassay (IA) applications. To improve the panning efficiency so as to obtain a valuable nanobody, anti-carrier protein phages in a phage display library were depleted to enhance the selection of nanobodies against the herbicide atrazine by using immunomagnetic beads conjugated with bovine serum albumin (IMB-BSA). The depletion of anti-carrier protein phages from the atrazine phage display library tripled the number of atrazine positive phage clones after four rounds of panning. One of the most sensitive phage clones Nb3 selected from the IMB-BSA depleted library was used to compare the performance with the monoclonal antibody (mAb 5D9) developed from the same immunogen. The Nb3-based IA exhibited similar specificity with the mAb 5D9-based IA, but greater thermostability and organic solvent tolerance. The half-maximum inhibition concentration (IC50) of the former was 3.5-fold greater than that of the latter (36.7 ng/mL versus 10.2 ng/mL). Because the Nb3-based IA was more robust than the mAb 5D9-based IA, the method detection limit of the two assays was 7.8 ng/mL of atrazine in river samples. The depletion strategy can increase the chance to acquire high quality nanobody and can be applicable for effective development of nanobodies against other small molecules.

Pipeline Leakage Detection Based on Secondary Phase Transform Cross-Correlation.

Leaks from pipes and valves are a reputational issue in industry. Maintenance of pipeline integrity is becoming a growing challenge due to the serious socioeconomic consequences. This paper presents a secondary phase transform (PHAT) cross-correlation method to improve the performance of the acoustic methods based on cross-correlation for pipeline leakage detection. Acoustic emission signals generated by pipe leakage are first captured by the sensors at different locations, and are subsequently analyzed using the cross-correlation curve to determine whether leakage is occurring. When leakage occurs, time delay estimation (TDE) is further carried out by peak search in the cross-correlation curve between the two sensor signals. In the analysis, the proposed method calculates the secondary cross-correlation function before the PHAT operation. A sinc interpolation method is then introduced for automatic searching the peak value of the cross-correlation curve. Numerical simulations and experimental results confirm the improved performance of the proposed method for noise suppression and accurate TDE compared to the basic cross-correlation method, which may be beneficial in engineering applications.