Complex Arrays Research Articles

Formation of Radical-like NH Ligand from NH3 at Ambient Conditions Mediated by Dialkyl Rare-Earth Complexes.

Although intensive work on ammonia activation has been carried out in recent decades, generating nitrogen-centered radicals from NH3 under ambient conditions remains quite challenging. In the presented research, the conversion of NH3 to radical-like NH ligand has been achieved by the reactions of a series of dialkyl rare-earth (RE) complexes (1-RE, RE = Tb, Dy, Y, Ho, Er, Yb, and Lu) supported by β-diketiminate ligands with NH3 in n-hexane at room temperature, resulting in the formations of the radical-like μ3-NH ligands containing trinuclear RE complexes (2-RE). The radical-like feature of the μ3-NH ligand was revealed by electron paramagnetic resonance and magnetic measurements, radical trapping experiments, and computational spin density analysis. In addition, H2 was detected to form during the reaction of 1-RE with NH3, indicating that the radical-like μ3-NH ligand was likely to be generated via N-H bond homolysis. Moreover, the solvents and coordination pattern of β-diketiminate ligands are crucial for the formation of the radical-like μ3-NH ligand from NH3. When toluene instead of n-hexane was used in the reaction of 1-RE with NH3, an array of octaamido tetranuclear RE complexes (3-RE) was obtained. The reaction of the dialkyl yttrium complex (4-Y) bearing a modified β-diketiminate ligand, in which the two mesityl substituents are replaced by a 2,6-diisopropylphenyl group and a 2-(dimethylamino)ethyl group, with NH3 in both n-hexane and toluene only yielded a tetranuclear yttrium complex carrying the dianionic closed-shell μ3-NH ligands (5-Y).

Modular Synthesis of Monoanionic PN Ligands Leads to Unexpected Structural Diversity in Lanthanum Chemistry.

We report a new synthetic entry to a series of N-substituted anilidophosphine ligands (short HPNR, R = pTol (HPNTol), 3,5-dimethylphenyl (HPN3,5Me), 3,5-bis(trifluoromethyl)phenyl (HPN3,5CF3), 2-methoxyphenyl (HPNOMe), diisopropylphenyl (HPNDipp), and adamantyl (HPNAd)), allowing a detailed tuning of their steric (and electronic) properties. HPNR could be converted into their lithium salts LiPNR, which are effective precursors for salt metathesis reactions. The new ligands are used for the synthesis of an array of lanthanide complexes using LaCl3(THF)1.2 as a precursor. Depending on the steric bulk of the anilidophosphine ligand, either chloride-bridged dimers of the general formula [(PNR)2La(μ-Cl2)La(PNR)2] (R = pTol (3f), 3,5-dimethylphenyl (3d) and adamantyl (3a)) or mononuclear complexes of the general formula (PNR)2LaCl (R = diisopropylphenyl (3e)) are observed, if the complexation reaction is carried out in toluene. Contrary, if salt metathesis reactions are carried out in dimethoxyethane (DME) as a coordinating solvent, -ate complexes of the general formula [(PNR)2La(μ-Cl2)Li(DME)] (R = Adamantyl (4a) and R = 2-methoxyphenyl (4d)) or [Li(DME)3][(PNR)2LaCl2] (R = 3,5-bis(trifluoromethyl)phenyl (4b), R = pTol (4f) and R = 3,5-dimethylphenyl (4d)) are observed. All ligands and complexes have been thoroughly characterized by 1D and 2D NMR spectroscopy, IR, and X-ray crystallography. Finally, the steric demand of the new anilidophosphine ligands is evaluated using SambVca simulations.

Wave energy extraction from rigid rectangular compound floating plates

We present a theoretical model to analyse the hydrodynamics of wave energy converters (WECs) comprised of three-dimensional, rigid, floating, compound rectangular plates in the open sea. The hydrodynamic problem is solved by means of Green’s theorem and a free-surface Green’s function. Plate motion is predicted through decomposition into rigid natural modes. We first analyse the case of a single rectangular plate and validate our model against experimental results from physical model tests undertaken in the COAST laboratory at the University of Plymouth. Then we extend our theory to complex shapes and arrays of plates and examine how the geometry, incident wave direction and power take-off (PTO) coefficient affect the response of the platform and the consequent absorbed energy.

Synthesis, Photophysical, Antimicrobial Activity and In‐silico Study of Homoleptic Dithiocarbamate Complexes [MII{k2S^S‐S2CN(R)CH2C6H4OH}2] (R=2‐picolyl, 3‐picolyl; M=NiII, CuII, ZnII)

AbstractAn array of mononuclear dithiocarbamate complexes [MII{k2S^S‐S2CN(R)CH2C6H4OH}2] (R=2‐picolyl, M=NiII 1, CuII 2, ZnII 3, R=3‐picolyl, M=NiII 4, CuII 5, ZnII 6); incorporating heterocyclic backbone were synthesised from (2‐hydroxybenzyl)(2‐picolyl)amine (HL1) and (2‐hydroxybenzyl)(3‐picolyl)amine (HL2) precursors. The formulation of these complexes was examined using various spectroscopic and analytical techniques (1H NMR, 13C NMR, FTIR, UV‐visible, Fluorescence, TGA/DTA) and further corroborated by DFT level calculation. Notably, precursors HL1 and HL2 exhibits maximum emission in the visible nm region (ca 502 and 408 nm) upon excitation of ultraviolet radiation at ~280 nm with concomitant Stokes shift ca 220 and 128 nm, respectively. The emission properties of these evidently suppressed after complexation with metal ions. Stability of 1–6 were determined by thermogravimetric analysis. The magnetic moment along with UV‐visible of 1–6 suggests square‐planar environment around NiII and CuII and tetrahedral environment around ZnII in 1–6 which is in accord with their optimized geometries. Compounds were screened for in‐ vitro antimicrobial activity against E. coli, P. aeruginosa, S. aureus, S. pyogenes, C. albicans, A. niger, A. clavatus by broth dilution method. Molecular docking study was performed to rationalize the results.

A multipurpose organometallic pyridyl Schiff base-modified poly(divinylbenzene) matrix for the catalytic removal of nitrophenols and polycyclic pollutants

Widespread organic pollutants in wastewater include toxic nitrophenols and polycyclic molecules. Here, we aim to develop a single multipurpose catalyst capable of degrading these structurally dissimilar contaminants by preparing a pyridyl Schiff base-functionalized poly(divinylbenzene) porous organic polymer displaying Ag complexes (PDVB-PA@Ag). PDVB-PA@Ag hydrogenated 4-nitrophenol (4-NP) efficiently to valuable and less toxic 4-aminophenol with an optimized reaction rate of 45.4 × 10−3 s−1 and apparent activation energy of only 20.1 kJ mol−1. The same catalyst also readily hydrogenated the isomers of 4-NP as well as nitrophenols with several nitro groups and halogenated nitrophenols with reaction rates ranging from 4.0 to 20.3 × 10−3 s−1. In addition, the multiuse PDVB-PA@Ag was capable of carrying out a second type of reaction and degraded multiple polycyclic dyes commonly found in wastewater including auramine O, basic blue 17, aniline blue, and malachite green through Fenton-like oxidation. PDVB-PA@Ag-based degradation processes for the four toxic dyes evaluated were efficient with pseudo-first order reaction rates varying between 1.2 × 10−2 to 3.7 × 10−2 min−1. By coordinating an array of versatile catalytic complexes on an extensive and stable porous support, PDVB-PA@Ag was made highly performant at completing different essential water-cleaning processes.

Terpyridyl-Imidazole Based Ligand Coordinated to Ln(Hexafluoroacetyl acetonate)3 Core: Synthesis, Structural Characterization, Luminescence Properties, and Thermosensing Behaviors in Solution and PMMA Film.

A new array of ternary lanthanide complexes of the form [Ln(hfa)3(tpy-HImzphen)] have been synthesized and thoroughly characterized wherein Ln = LaIII (1), EuIII (2), SmIII (3), and TbIII (4); hfa = hexafluoroacetylacetonate; and tpy-HImzphen = 2-(4-[2,2':6',2″]terpyridin-4'-yl-phenyl)-1H-phenanthro[9,10-d]imidazole. Incorporation of tpy-HImzphen onto the Ln-hfa moiety induced a bathochromic shift of the absorption window of the complexes into the visible region. Extensive investigations of the luminescence characteristics have been conducted both at RT and at 77 K to understand the deactivation pathways of the complexes. Both steady-state and time-resolved emission spectral behaviors indicate four distinctive behaviors upon incorporation of tpy-HImzphen onto the lanthanide core, viz., a huge red-shift of the ligand-centered peak for LaIII; almost complete energy transfer for EuIII; very little energy transfer for SmIII, while reverse energy transfer in the case of TbIII. In addition, the EuIII-complex exhibits its excellence in luminescence thermometry in the solution state as well as in poly(methyl methacrylate) (PMMA) thin films. The thermosensitive luminescence response in solution was further utilized to mimic set-reset flip-flop logic operation. A plausible energy transfer scheme has been devised to explain dissimilar luminescence behaviors in the complexes. The role of LMCT was also considered for the observed thermosensing property of the Eu(III) complex.

Panoply of P: An Array of Rhenium-Phosphorus Complexes Generated from a Transition Metal Anion.

We expand upon the synthetic utility of anionic rhenium complex Na[(BDI)ReCp] (1, BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) to generate several rhenium-phosphorus complexes. Complex 1 reacts in a metathetical manner with chlorophosphines Ph2PCl, MeNHP-Cl, and OHP-Cl to generate XL-type phosphido complexes 2, 3, and 4, respectively (MeNHP-Cl = 2-chloro-1,3-dimethyl-1,3,2-diazaphospholidine; OHP-Cl = 2-chloro-1,3,2-dioxaphospholane). Crystallographic and computational investigations of phosphido triad 2, 3, and 4 reveal that increasing the electronegativity of the phosphorus substituent (C < N < O) results in a shortening and strengthening of the rhenium-phosphorus bond. Complex 1 reacts with iminophosphane Mes*NPCl (Mes* = 2,4,6-tritert-butylphenyl) to generate linear iminophosphanyl complex 5. In the presence of a suitable halide abstraction reagent, 1 reacts with the dichlorophosphine iPr2NPCl2 to afford cationic phosphinidene complex 6+. Complex 6+ may be reduced by one electron to form 6•, a rare example of a stable, paramagnetic phosphinidene complex. Spectroscopic and structural investigations, as well as computational analyses, are employed to elucidate the influence of the phosphorus substituent on the nature of the rhenium-phosphorus bond in 2 through 6. Furthermore, we examine several common analogies employed to understand metal phosphido, phosphinidene, and iminophosphanyl complexes.

High-Throughput Multitarget Molecular Detection in an Automatic Light-Addressable Photoelectrochemical Sensing Platform.

Successively emerged high-throughput multitarget molecular detection methods bring significant development tides in chemical, biological, and environmental fields. However, several persistent challenges of intricate sample preparation, expensive instruments, and tedious and skilled operations still need to be further addressed. Here, we propose an automatic light-addressable photoelectrochemical (ALA-PEC) sensing platform for sensitive and selective detection of multitarget molecules. With Au nanoparticle-decorated TiO2 nanotube photonic crystals (Au-TiO2 NTPCs) as a photoelectrode and 8 kinds of antibiotics as target molecules, the ALA-PEC sensing system implements automatic detection of multimolecules in a short time with high sensitivity and good selectivity. Random samples with different amounts of antibiotics have been well-distinguished in the ALA-PEC system, and both the chemical components and concentrations have been well-illustrated in a pattern recognition model. It is worth noting that 8 samples are not the limit of the ALA-PEC sensing platform, which can be easily expanded to more complex detection arrays based on practical needs. The emerging ALA-PEC sensing platform provides a new solution for rapid screening and detection of multitarget and high-throughput substances and potentially brings the automatic, portable, sensitive, high-throughput, and cost-effective detection technique to an entire new realm.

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions.

1,10-Phenanthroline (phen) is one of the most popular ligands ever used in coordination chemistry due to its strong affinity for a wide range of metals with various oxidation states. Its polyaromatic structure provides robustness and rigidity, leading to intriguing features in numerous fields (luminescent coordination scaffolds, catalysis, supramolecular chemistry, sensors, theranostics, etc.). Importantly, phen offers eight distinct positions for functional groups to be attached, showcasing remarkable versatility for such a simple ligand. As a result, phen has become a landmark molecule for coordination chemists, serving as a must-use ligand and a versatile platform for designing polyfunctional arrays. The extensive use of substituted phenanthroline ligands with different metal ions has resulted in a diverse array of complexes tailored for numerous applications. For instance, these complexes have been utilized as sensitizers in dye-sensitized solar cells, as luminescent probes modified with antibodies for biomaterials, and in the creation of elegant supramolecular architectures like rotaxanes and catenanes, exemplified by Sauvage's Nobel Prize-winning work in 2016. In summary, phen has found applications in almost every facet of chemistry. An intriguing aspect of phen is the specific reactivity of each pair of carbon atoms ([2,9], [3,8], [4,7], and [5,6]), enabling the functionalization of each pair with different groups and leading to polyfunctional arrays. Furthermore, it is possible to differentiate each position in these pairs, resulting in non-symmetrical systems with tremendous versatility. In this Review, the authors aim to compile and categorize existing synthetic strategies for the stepwise polyfunctionalization of phen in various positions. This comprehensive toolbox will aid coordination chemists in designing virtually any polyfunctional ligand. The survey will encompass seminal work from the 1950s to the present day. The scope of the Review will be limited to 1,10-phenanthroline, excluding ligands with more intracyclic heteroatoms or fused aromatic cycles. Overall, the primary goal of this Review is to highlight both old and recent synthetic strategies that find applicability in the mentioned applications. By doing so, the authors hope to establish a first reference for phenanthroline synthesis, covering all possible positions on the backbone, and hope to inspire all concerned chemists to devise new strategies that have not yet been explored.

International Legal Regulation of Activities of States in the Great Mediterranean Region

INTRODUCTION. In modern international and domestic maritime law, regional fragmentation of legal regulation is becoming more and more noticeable, which, in turn, objectifies and actualizes the formation of complex arrays of legal norms, united by the consistency of the political and legal positions of the contracting states that have national interests in the relevant water area, primarily-coastal states extending their state sovereignty to certain areas of maritime space. In this context, the Greater Mediterranean region should be considered as one of the most important in the world merchant shipping and naval support of international peace and security, as a basin that optimally connects the Atlantic and Indian Oceans from the point of view of logistics, which requires the formation of an appropriate scientific and methodological basis for full implementation of the fundamental principle of international cooperation in the maritime policy of the states of the region.MATERIALS AND METHODS. To substantiate the expediency of singling out the Greater Mediterranean as an independent object of legal regulation, general and special international legal treaties, the domestic legislation of the Mediterranean states, as well as political and legal documents indicating the existence of certain disputes and situations around certain zones of the Mediterranean water area, primarily – in the Eastern Mediterranean region. To obtain reliable and substantiated results of the study, methods of scientific knowledge were used: formal-legal, logical, historical-legal, system-structural analysis. Thus, the formal legal method made it possible to clarify the content and meaning of international legal treaties concluded at different times and aimed at regulating public relations in the maritime sphere. The logical method made it possible to substantiate the need for comprehensive international cooperation of the coastal states of the Greater Mediterranean. With the help of the historical and legal method, an overview was made of both the world, Soviet and Russian practice of applying the norms of domestic and international law on issues related to ensuring international law and order in the Greater Mediterranean region. The logical method made it possible to build the necessary connections and patterns of development of international legal regulation in the Greater Mediterranean region in the general context of ongoing universal and regional political and legal processes and transformations. Using the method of system-structural analysis, it was possible to display a holistic picture of law-making and law enforcement of the Mediterranean states, aimed at the formation of unified principles and norms for the exercise of the sovereign rights of coastal states.RESEARCH RESULTS. International maritime merchant shipping seems to be a very complex area of public relations with a large number of entities that have different legal status and, accordingly, are related to each other in a very different way.DISCUSSION AND CONCLUSIONS. This work is devoted to the study of the main trends in the development of the Greater Mediterranean region in terms of formulating key international legal guidelines and rules of conduct for its constituent states. The object of the study is the legal relations carried out in the maritime spaces of the Greater Mediterranean as one of the key regions, which, along with its economic and political significance, is an integral zone for the implementation of the national interests of the Russian Federation, extending to the entire World Ocean.

Underwater double vortex generation using 3D printed acoustic lens and field multiplexing

The generation of acoustic vortex beams has attracted an increasing amount of research attention in recent years, offering a range of functions, including acoustic communication, particle manipulation, and biomedical ultrasound. However, incorporating more vortices and broadening the capacity of these beams and associated devices in three dimensions pose challenges. Traditional methods often necessitate complex transducer arrays and are constrained by conditions such as system complexity and the medium in which they operate. In this paper, a 3D printed acoustic lens capable of generating a double vortex pattern with an optional focusing profile in water was demonstrated. The performance of the proposed lens was evaluated through computational simulations using finite element analysis and experimental tests based on underwater measurements. The results indicate that by altering the positioning of the vortices’ axes, it is possible to control both the intensity and the location of the pressurized zone. The proposed approach shows promise for enhancing the effectiveness and versatility of various applications by generating a larger number of vortices and freely tailoring the focal profile with a single lens, thereby expanding the practical uses of acoustic vortex technology.

Unveiling the impact of axial ligands on Fe-N-C complexes through DFT simulation and machine learning analysis

Single-atom catalysts (SACs), featuring isolated metal atoms embedded in graphitic carbon materials, have attracted considerable research interest due to their cost-effectiveness, high catalytic activity, and customizable functionality across various catalytic reactions. Among SACs, the Fe-N4-C class has garnered significant attention. Tailoring the properties of Fe-N4 sites through localized chemical modifications stands as a key strategy for catalyst engineering. Recent experimental and computational investigations have underscored the distinct influence of axial ligands on Fe in modulating the oxygen reduction reaction (ORR) activity. However, the precise quantitative structure-property relationship between ligands and the catalytic properties of the Fe center remains elusive. In this study, we combined the density functional theory (DFT) simulations and machine learning (ML) models to unravel the relationship between the ligand properties and the oxo binding energy. This energy pertains to the binding of an oxygen atom to the Fe center, a fundamental step in ORR. Through the design of 33 ligands and 5 molecular complexes that accommodate the Fe-N4 moiety, we screened a total of 278 oxo binding energies across an array of ligands and host complexes. Harnessing the power of ML models, we achieved an accurate prediction of these oxo binding energies using features collected from DFT simulations. Notably, the predominant features contributing to the oxo binding energy prediction primarily derived from complexes with attached ligands, rather than isolated ligand properties. We formulated an approach that leverages these critical features and identified the isolated ligand properties capable of effectively predicting these features. This methodology can potentially be applied to investigate other ORR intermediates and a comprehensive understanding of the ligand effect for the ORR activity in SACs can be achieved.

Synthesis and isolation of a cyclic bis-vinyl germylene via a diazoolefin adduct of germylene dichloride.

Since the successful isolation of various stable diazoolefins, an array of complexes containing these promising ligands have been synthesized. We herein report the synthesis, characterization, and structures of neutral group 14 diazoolefin complexes and the subsequent transformation into a new cyclic bis-vinyl germylene.

Construction of a highly efficient DNA nanotube sensor with peroxide-like activity.

The G-quadruplex/heme complexes are special DNA-based artificial metalloenzymes with peroxidase-like activity and are widely used in biosensing and biocatalysis. However, their peroxidase-like activity is not satisfactory. Due to the high programmability and good stability of DNA, DNA as a scaffold material is promising for enhancing the activity of artificial metalloenzymes. In this work, an effective DNA nanotube-based peroxidase was constructed using a self-assembly strategy. To improve the activity of G-quadruplex/heme complexes, a new method for the construction of G-quadruplex/heme complex arrays was proposed in a simple and inexpensive way. By designing the toes of DNA nanotubes as G-quadruplexes, G-quadruplex arrays could be formed on pure DNA nanotubes, and then the G-quadruplex arrays bind to heme to form a nanotube-supported DNAzyme termed as DNTzyme. Agarose gel electrophoresis, circular dichroism, and fluorescence microscopy were used to characterize DNTzyme. What is more, because the loading of DNAzyme on DNA nanotubes can increase their biological stability, a hydrogen peroxide detection sensor was constructed using the enhanced enzymatic activity and excellent stability of DNTzyme. The sensor could accurately and efficiently detect peroxide and show enhanced fluorescence with a detection limit of 49 nM for H2O2 and 1.4 μM for TBHP, and a color development time of about 5 min. This sensor is expected to have applications in bio-detection, biocatalysis, and drug delivery.

Murburn concept in cellular function and bioenergetics, Part 1: Understanding murzymes at the molecular level

Bioenergetics is the study of how life-activities are powered within the cell. This also deals with the interactive exchange of matter/radiation between cellular components and their environment, and the accompanying changes thereof. The acclaimed bioenergetics paradigm has relied on “electron transport chains” and selective/stoichiometric electrogenic “ion-pumping” mediated by vectorial protein-embedded membranes. Therein, an electrochemical gradient was deemed to be the driving force for chemical reactions leading to ATP production, physical thermogenesis by uncoupling proteins, and complex electromechanical processes like information relay along the axon. On one hand, this vitally deterministic perception requires the membrane proteins to “intelligently” manipulate ion-fluxes and generate/harness an electrochemical gradient by a gambit-type logic. At the other hand, it also seeks that the same gradient should cyclically control the membrane-proteins’ activity. Our recent pursuits have questioned such traditional perspectives and advocated the alternate explanation of murburn concept, leading to a revamping of the macroscopic treatments of overall thermodynamic, kinetic, mechanistic, and evolutionary (probability) considerations. The current review aims to consolidate the murburn paradigm of bioenergetics, wherein murzymes initiate redox processes by effective charge separation and diffusible reactive species formation, enabling cells to work as simple chemical engines. Herein, we discuss the reaction chemistry of some simple enzyme systems and also delve into protein complex arrays mediated powering routines like mitochondrial respiration-thermogenesis and chloroplast-centered photosynthesis. Furthermore, we remark that the “water–ion–molecules” phase continuum is actually discretized into dynamically fluctuating coacervates and express concern over the marginalization of sound chemico-physical ideas by the bioenergetics community.

Femtosecond laser printing patterned nanoparticles on flexible substrate by tuning plasmon resonances via polarization modulation

Nanoparticles patterned on stretchable films for broad applications lack efficient fabrication methods. In this study, femtosecond laser-induced transfer was employed to assemble nanoparticles into a well-defined array on a flexible substrate while mitigating the inevitable plasmon resonances. The metal islands patterned on the substrate are regularly transferred as spherical nanoparticles onto the polymer, with a small deposition deviation and large embedded depth after laser irradiation. However, inhomogeneous laser absorption in the patterned array severely amplifies the printing deviation and narrows the process window, particularly for smaller patterns and complex arrangements. Plasmon resonance excited by an incident laser causes a localized optical field distribution, which accounts for absorption enhancement or suppression. The field distribution from the numerical simulation exhibited periodicity related to the laser parameters and array geometry. A theoretical model was established to clarify the propagation of plasmon resonance waves. The field distribution was modulated by adjusting the polarization direction, guided by theoretical and simulation analyses. Finally, regular and complex nanoparticle arrays were successfully fabricated after tuning the plasmon resonances. This study provides an effective method for fabricating programmable nanoparticle arrays on flexible films.

Optical Gain Switching by Thermo‐Responsive Light‐Emitting Nanofibers through Moisture Sorption Swelling

AbstractThe development of intelligent photonic systems made of stimuli‐responsive materials, i.e., with features tunable and switchable by environmental signals, is gaining increasing attention. Here, the study reports on switchable optical gain based on complex arrays of nanofibers made of thermo‐responsive poly(2‐n‐propyl‐2‐oxazoline), incorporating a blue‐emitting chromophore. The fluorescent component endows the nanofibers with optical gain in addition to the moisture absorption capability of the polymer. Light amplification is found with temperature‐ and humidity‐dependent excitation threshold. The threshold value is halved close to the polymer cloud point temperature, enabling reversible switching of the emission intensity upon temperature change. Waveguiding analysis by back‐focal plane imaging on individual fibers allows the switching mechanisms to be rationalized, in terms of moisture sorption swelling‐induced morphological changes. These responsive light‐emitting nanofibers may find application in a novel class of lasers with dynamically‐controlled properties, environmentally‐switchable optoelectronics, and smart sensors.

Outsmarting Pathogens with Antibody Engineering.

There is growing interest in identifying antibodies that protect against infectious diseases, especially for high-risk individuals and pathogens for which no vaccine is yet available. However, pathogens that manifest as opportunistic or latent infections express complex arrays of virulence-associated proteins and are adept at avoiding immune responses. Some pathogens have developed strategies to selectively destroy antibodies, whereas others create decoy epitopes that trick the host immune system into generating antibodies that are at best nonprotective and at worst enhance pathogenesis. Antibody engineering strategies can thwart these efforts by accessing conserved neutralizing epitopes, generating Fc domains that resist capture or degradation and even accessing pathogens hidden inside cells. Design of pathogen-resistant antibodies can enhance protection and guide development of vaccine immunogens against these complex pathogens. Here, we discuss general strategies for design of antibodies resistant to specific pathogen defense mechanisms.

Attention-Oriented Deep Multi-Task Hash Learning

Hashing has wide applications in image retrieval at large scales due to being an efficient approach to approximate nearest neighbor calculation. It can squeeze complex high-dimensional arrays via binarization while maintaining the semantic properties of the original samples. Currently, most existing hashing methods always predetermine the stable length of hash code before training the model. It is inevitable for these methods to increase the computing time, as the code length converts, caused by the task requirements changing. A single hash code fails to reflect the semantic relevance. Toward solving these issues, we put forward an attention-oriented deep multi-task hash learning (ADMTH) method, in which multiple hash codes of varying length can be simultaneously learned. Compared with the existing methods, ADMTH is one of the first attempts to apply multi-task learning theory to the deep hashing framework to generate and explore multi-length hash codes. Meanwhile, it embeds the attention mechanism in the backbone network to further extract discriminative information. We utilize two common available large-scale datasets, proving its effectiveness. The proposed method substantially improves retrieval efficiency and assures the image characterizing quality.

Maize Terpene Synthase 8 (ZmTPS8) Contributes to a Complex Blend of Fungal-Elicited Antibiotics

In maize (Zea mays), fungal-elicited immune responses include the accumulation of terpene synthase (TPS) and cytochrome P450 monooxygenases (CYP) enzymes resulting in complex antibiotic arrays of sesquiterpenoids and diterpenoids, including α/β-selinene derivatives, zealexins, kauralexins and dolabralexins. To uncover additional antibiotic families, we conducted metabolic profiling of elicited stem tissues in mapping populations, which included B73 × M162W recombinant inbred lines and the Goodman diversity panel. Five candidate sesquiterpenoids associated with a chromosome 1 locus spanning the location of ZmTPS27 and ZmTPS8. Heterologous enzyme co-expression studies of ZmTPS27 in Nicotiana benthamiana resulted in geraniol production while ZmTPS8 yielded α-copaene, δ-cadinene and sesquiterpene alcohols consistent with epi-cubebol, cubebol, copan-3-ol and copaborneol matching the association mapping efforts. ZmTPS8 is an established multiproduct α-copaene synthase; however, ZmTPS8-derived sesquiterpene alcohols are rarely encountered in maize tissues. A genome wide association study further linked an unknown sesquiterpene acid to ZmTPS8 and combined ZmTPS8-ZmCYP71Z19 heterologous enzyme co-expression studies yielded the same product. To consider defensive roles for ZmTPS8, in vitro bioassays with cubebol demonstrated significant antifungal activity against both Fusarium graminearum and Aspergillus parasiticus. As a genetically variable biochemical trait, ZmTPS8 contributes to the cocktail of terpenoid antibiotics present following complex interactions between wounding and fungal elicitation.