Interfacial-Assembly-Induced In Situ Transformation from Aligned 1D Nanowires to Quasi-2D Nanofilms.

As the dimensionality of materials generally affects their characteristics, thin films composed of low-dimensional nanomaterials, such as nanowires (NWs) or nanoplates, are of great importance in modern engineering. Among various bottom-up film fabrication strategies, interfacial assembly of nanoscale building blocks holds great promise in constructing large-scale aligned thin films, leading to emergent or enhanced collective properties compared to individual building blocks. As for 1D nanostructures, the interfacial self-assembly causes the morphology orientation, effectively achieving anisotropic electrical, thermal, and optical conduction. However, issues such as defects between each nanoscale building block, crystal orientation, and homogeneity constrain the application of ordered films. The precise control of transdimensional synthesis and the formation mechanism from 1D to 2D are rarely reported. To meet this gap, we introduce an interfacial-assembly-induced interfacial synthesis strategy and successfully synthesize quasi-2D nanofilms via the oriented attachment of 1D NWs on the liquid interface. Theoretical sampling and simulation show that NWs on the liquid interface maintain their lowest interaction energy for the ordered crystal plane (110) orientation and then rearrange and attach to the quasi-2D nanofilm. This quasi-2D nanofilm shows enhanced electric conductivity and unique optical properties compared with its corresponding 1D geometry materials. Uncovering these growth pathways of the 1D-to-2D transition provides opportunities for future material design and synthesis at the interface.

Structural Design of Intelligent Reversible Two-Way Structural Color Films.

Structural color always shows a reversible switch between reflection and transmission states when viewed from different angles, attracting increasing attention in display applications. However, this switching between reflection and transmission states of structural color suffers from the inherent lack of autonomous regulation, which is unmanageable in the case of different application scenarios. Here, we design an intelligent two-way structural color film which can reversibly change its color when applied with an extra stimulation such as voltage, heat signal, or light. A special structural feature contains a traditional photonic crystal film of polystyrene (PS) microspheres assembled by smart windows. Remarkably, our structural color film shows a prominent polarization sensitivity, and the angle dependence of the structural color broadens the gamut of display color demonstrated by both finite element theoretical analysis and experimental observation. Prospectively, this hierarchically designed film provides a promising pathway toward next-generation multicolor displays and smart windows.

Two-Dimensional Nonbenzenoid Heteroacene Crystals Synthesized via In-Situ Embedding of Ladder Bipyrazinylenes on Au(111).

Precisely introducing topological defects is an important strategy in nanographene crystal engineering because defects can tune π-electronic structures and control molecular assemblies. The synergistic control of the synthesis and assembly of nanographenes by embedding the topological defects to afford two-dimensional (2D) crystals on surfaces is still a great challenge. By in-situ embedding ladder bipyrazinylene (LBPy) into acene, the narrowest nanographene with zigzag edges, we have achieved the precise preparation of 2D nonbenzenoid heteroacene crystals on Au(111). Through intramolecular electrocyclization of o-diisocyanides and Au adatom-directed [2+2] cycloaddition, the nonbenzenoid heteroacene products are produced with high chemoselectivity, and lead to the molecular 2D assembly via LBPy-derived interlocking hydrogen bonds. Using bond-resolved scanning tunneling microscopy, we determined the atomic structures of the nonbenzenoid heteroacene product and diverse organometallic intermediates. The tunneling spectroscopy measurements revealed the electronic structure of the nonbenzenoid heteroacene, which is supported by density functional theory (DFT) calculations. The observed distinct organometallic intermediates during progression annealing combined with DFT calculations demonstrated that LBPy formation proceeds via electrocyclization of o-diisocyanides, trapping of heteroarynes by Au adatoms, and stepwise elimination of Au adatoms.

Two-Dimensional Crystal Transition from Radialene to Cumulene on Ag(111) via Retro-[2 + 1] Cycloaddition.

Two-dimensional (2D) crystal-to-crystal transition is an important method in crystal engineering because of its ability to directly create diverse crystal materials from one crystal. However, steering a 2D single-layer crystal-to-crystal transition on surfaces with high chemo- and stereoselectivity under ultra-high vacuum conditions is a great challenge because the transition is a complex dynamic process. Here, we report a highly chemoselective 2D crystal transition from radialene to cumulene with retention of stereoselectivity on Ag(111) via retro-[2 + 1] cycloaddition of three-membered carbon rings and directly visualize the transition process involving a stepwise epitaxial growth mechanism by the combination of scanning tunneling microscopy and non-contact atomic force microscopy. Using progression annealing, we found that isocyanides on Ag(111) at a low annealing temperature underwent sequential [1 + 1 + 1] cycloaddition and enantioselective molecular recognition based on C-H···Cl hydrogen bonding interactions to form 2D triaza[3]radialene crystals. In contrast, a higher annealing temperature induced the transformation of triaza[3]radialenes to generate trans-diaza[3]cumulenes, which were further assembled into 2D cumulene-based crystals through twofold N-Ag-N coordination and C-H···Cl hydrogen bonding interactions. By combining the observed distinct transient intermediates and density functional theory calculations, we demonstrate that the retro-[2 + 1] cycloaddition reaction proceeds via the ring opening of a three-membered carbon ring, sequential dechlorination/hydrogen passivation, and deisocyanation. Our findings provide new insights into the growth mechanism and dynamics of 2D crystals and have implications for controllable crystal engineering.

Self-Assembly of Nanowires: From Dynamic Monitoring to Precision Control.

Natural biomaterials often show ordered nanowire structures (ONWS) which display unique structural color or superior mechanical performance. Meanwhile, plenty of modern nanodevices with ONWS have flourished with activities focused on both basic and applied research. Manipulating synthetic nanowire (NW) from a disordered state to a hierarchically ordered structure via various assembly strategies brings about intriguing and exotic chemical/physical properties. In the past decades, many methods have been developed to assemble NWs and fabricate organized architectures, such as Langmuir-Blodgett interfacial assembly, spin-coating assembly, fluid-flow-induced assembly, and ice-template assembly. Nevertheless, for practical applications, large-scale and high-efficiency assembly strategies toward precise controlled architectures are largely limited by the lack understanding of assembly mechanisms. Especially, the manipulation principles and driving forces behind the state-of-art assembly strategies are still unclear. Besides, the lesser research attention on dynamic kinetics also impedes the revelation of the NW self-assembly mechanism. With the emergence of advanced in situ techniques, such as synchrotron-based X-ray techniques and in situ transmission electron microscopy (TEM), the dynamic monitoring of NW behavior in many practical environments becomes possible. In addition, the alignment direction and the stacking manner of NW film are of significance to the final performance. There is a lack of connection between the properties of one-dimensional nanoscale building blocks and the functionalities of the macro-assembly structures. To this end, dynamic monitoring is highly desired, which enables the precision modulation of NW assembly structure, leading to the discovery or prediction of new structures, novel properties, and performance optimization.In this Account, we aim to uncover the underlying kinetics of NW assembly or local reaction and mass transportation processes, as well as to build a solid connection from individual NWs to NW assembly structures with enhanced properties and eventually to macroscopic materials application. We first review the recent progress in state-of-art NW assembly strategies for diverse aligned structures according to the manipulation principle and the driving forces. To systematically review the NW self-assembly strategies, we categorize these strategies into three states: NWs on the liquid interface via surface tension, NW assembly in liquid via solution-shearing flow field, and NW assembly at the solid interval via physical repulsive force. Then, we introduce the existing advanced characterization techniques, including synchrotron-based X-ray scattering and in situ TEM, to dynamically monitor the intermediate states of the NW assembly and transport processes. The comprehensive understanding of this thermodynamic and kinetic mechanism facilitates the rational design, large scale, and high-efficiency fabrication of NW assemblies, thus promoting their applications in tailored optical-electrical electronics, smart electrochromic devices, electrocatalysis, structural materials, and chiral photonic crystals.

Manipulating Nanowire Structures for an Enhanced Broad-Band Flexible Photothermoelectric Photodetector.

The photothermoelectric effect, directly converting light energy into electrical energy, shows promising prospects in self-powered broad-band optical detection, which can extend to various applications, such as sensing, optoelectronic communications, and wide-temperature-range measurements. However, the low photosensitivity, narrow-band response, and rapid performance degeneration under continuous illumination restrict its broad application. Herein, we propose a simple bottom-up strategy to manipulate nanowires (NWs) into a well-defined multilayer Te-Ag2Te-Ag NW film, resulting in a high-performance photothermoelectric photodetector with a broad-band responsivity (4.1 V/W), large detectivity (944 MHz1/2 W-1), and fast response speed (0.4-0.7 s from 365 to 1200 nm). In addition, the ultrathin structure endows this device with slow and weak transverse heat conduction, enabling a stable voltage without an obvious degeneration over 1500 s. The highly anisotropic arrangement of NWs gives this device a prominent polarization sensitivity. Prospectively, this hierarchically designed nanowire film provides a promising pathway toward engineering photodetectors with high performance.

Structural Design of Nanowire Wearable Stretchable Thermoelectric Generator.

Wearable thermoelectric generators as renewable energy conversion technologies have witnessed rapid development in the past decade. Herein, we design a nanowire (NW) film wavy structure which possesses an excellent temperature gradient ratio for stretchable thermoelectric generators. Taking advantage of the photothermal effect of Te NWs as the hot side and p-n NWs heterofilms (n-type Ag2Te and p-type Cu1.75Te NWs) as thermoelectric materials, a considerable output voltage can be achieved under light irradiation. Besides the electricity output, the wearable device can also make our skin warm and comfortable in cold weather. Meanwhile, we combine thermoelectric generators with passive radiative cooling technology to reduce insolation of the human body and improve the performance of the device under intense solar irradiation in hot weather. Interestingly, it can also offer continuous green energy to realize various signal perceptions, suggesting a robust strategy for electricity output and self-powered wearable electronics.

Gut Microbial Perturbation and Host Response Induce Redox Pathway Upregulation along the Gut-Liver Axis during Giardiasis in C57BL/6J Mouse Model.

Apicomplexan infections, such as giardiasis and cryptosporidiosis, negatively impact a considerable proportion of human and commercial livestock populations. Despite this, the molecular mechanisms of disease, particularly the effect on the body beyond the gastrointestinal tract, are still poorly understood. To highlight host-parasite-microbiome biochemical interactions, we utilised integrated metabolomics-16S rRNA genomics and metabolomics-proteomics approaches in a C57BL/6J mouse model of giardiasis and compared these to Cryptosporidium and uropathogenic Escherichia coli (UPEC) infections. Comprehensive samples (faeces, blood, liver, and luminal contents from duodenum, jejunum, ileum, caecum and colon) were collected 10 days post infection and subjected to proteome and metabolome analysis by liquid and gas chromatography-mass spectrometry, respectively. Microbial populations in faeces and luminal washes were examined using 16S rRNA metagenomics. Proteome-metabolome analyses indicated that 12 and 16 key pathways were significantly altered in the gut and liver, respectively, during giardiasis with respect to other infections. Energy pathways including glycolysis and supporting pathways of glyoxylate and dicarboxylate metabolism, and the redox pathway of glutathione metabolism, were upregulated in small intestinal luminal contents and the liver during giardiasis. Metabolomics-16S rRNA genetics integration indicated that populations of three bacterial families-Autopobiaceae (Up), Desulfovibrionaceae (Up), and Akkermanasiaceae (Down)-were most significantly affected across the gut during giardiasis, causing upregulated glycolysis and short-chained fatty acid (SCFA) metabolism. In particular, the perturbed Akkermanasiaceae population seemed to cause oxidative stress responses along the gut-liver axis. Overall, the systems biology approach applied in this study highlighted that the effects of host-parasite-microbiome biochemical interactions extended beyond the gut ecosystem to the gut-liver axis. These findings form the first steps in a comprehensive comparison to ascertain the major molecular and biochemical contributors of host-parasite interactions and contribute towards the development of biomarker discovery and precision health solutions for apicomplexan infections.

Utilising lipid and, arginine and proline metabolism in blood plasma to differentiate the biochemical expression in functional dyspepsia (FD) and irritable bowel syndrome (IBS).

Functional gastrointestinal disorders (FGID) such as functional dyspepsia (FD) and irritable bowel syndrome (IBS) are highly prevalent and debilitating attributed to altered gut function and gut-brain interactions. FGID can be reliably diagnosed based upon the symptom pattern; but in the clinical setting FD or IBS a frequent diagnoses of exclusion after relevant structural causes of symptoms have been ruled out by appropriate testing. Thus far, there is no established biomarker for FGIDs. To address this limitation, we utilised multi-omics and chemometrics integration to characterise the blood plasma biochemistry in patients with IBS, FD, an overlap of FD/IBS, and controls using liquid chromatography-mass spectrometry (LC-MS) techniques.Cholesterol metabolism products Cholest-5,24-dien-3ß-ol, 3-O-ß-D-glucopyranoside, energy pathway metabolites, immunoglobulin-γ2 and immunoglobulin-κ, and carbonic anhydrase-1 proteins were particularly elevated in IBS. Furthermore, arginine and proline metabolisms, thyroid hormone synthesis, ferroptosis and, complementary and coagulation cascades were particularly upregulated in patients with IBS. Cer(d18:1/26:1(17Z)) and PI(14:0/22:1(11Z)) lipids were elevated in FD and FD-IBS but were depleted in IBS. Markers of central carbon metabolism and lipidome profiles allowed better discrimination and model predictability than metaproteome profile in healthy and FGID conditions.Overall, the multi-omics integration allowed the discrimination of healthy controls and FGID patients. It also effectively differentiated the biochemistry of FGID subtypes including FD, IBS and FD-IBS co-occurrence. This study points towards the possibility of multi-omics integration for rapid and high throughput analysis of plasma samples to support clinicians screen and diagnose patients with suspected FGIDs.

Inhibition of semaphorin-3a alleviates lipopolysaccharide-induced vascular injury.

Alleviating vascular injury improves the prognosis of atherosclerosis. Semaphorin-3a (Sema3A) is a special membrane-associated secreted protein with various biological properties, like pro-inflammation, anti-tumor and et al. This study aims to investigate the effects of inhibition of Sema3A on lipopolysaccharide (LPS)-induced vascular injury in mice. The mice were randomized into three groups: control, LPS, and LPS + siRNA. Mice in the combined group were given siRNA through fast tail vein injection, then LPS was injected intraperitoneally 7 days later, finally the mice were euthanized 24 h later. Vascular function and structure were assessed by vascular injury biomarkers and relevant stainings. LPS-induced vascular dysfunction and pathological injury were substantially improved by inhibition of Sema3A. Western blot and quantitative real-time polymerase chain reaction assays were used for investigating molecular pathways. The relevant proteins of vascular endothelial cells activation, intercellular adhesion molecule-1 (ICAM-1) and vascular cell adhesion molecule-1 (VCAM-1), increased after LPS stimulation, while these effects were reversed by inhibition of Sema3A. The levels of inflammatory cytokines (IL-1ß, IL-6 and NLRP3) were upregulated after LPS stimulation, however, inhibition of Sema3A reversed it through NF-κB and MAPKs signaling pathways involvement. Moreover, inhibition of Sema3A alleviated LPS-induced oxidative stress, evidenced by a decrease in total reactive oxygen species and an increase in antioxidant protein of SOD-1. The results showed that inhibition of Sema3A protects against LPS-induced vascular injury by suppressing vascular endothelial cells activation, vascular inflammation, and vascular oxidative stress, implying that inhibition of Sema3A might be used as a therapeutic strategy for septic vascular injury or atherosclerosis.

Manipulating Nanowire Assemblies toward Multicolor Transparent Electrochromic Device.

Assembling various nanowires together, enabling the assemblies with tailored optical, electrical, and multifunctional properties, represents a promising technology for next generation multifunctional electronics. Here we demonstrate a novel multicolor electrochromic device by coassembling W18O49 and V2O5 nanowires using solution-based Langmuir-Blodgett technique. The transparent W18O49 nanowire film became orange with the increasing addition of V2O5 nanowires and the film underwent a dynamic color change (orange, green, and gray) on application of different electrochemical biases of 2, 0, and -0.5 V (vs Ag/AgCl). Both the transmittance and color of the device can be easily controlled by manipulating the layers of coassembled nanowires and the ratios between the two nanowires. On the basis of this approach, different patterns can be easily fabricated with the addition of corresponding masks, and the solid electrochromic device is assembled, suggesting its significant potentials in smart windows and multicolor electrochromic displays.

Self-Powered Flexible Electrochromic Smart Window.

Electrochromic devices have attracted considerable interest for smart windows. However, current development suffers from the requirement of the external power sources and rigid ITO substrate, which not only causes additional energy consumption but also limits their applications in flexible devices. Inspired by galvanic cell, we demonstrate a self-powered flexible electrochromic device by integrating Ag/W18O49 nanowire film with the Al sheet. The Ag nanowire film first acted as the electrode to replace the ITO substrate, then coupled with the Al sheet to induce an open-circuit voltage of ∼0.83 V, which is high enough to drive the coloration of W18O49 nanowires. Remarkably, the flexible self-powered electrochromic device only expends ∼6.8 mg/cm2 of the Al sheet after 450 electrochromic switching cycles and the size can be easily expanded with an area of 20 × 20 cm2, offering significant potential applications for the next generation of flexible electrochromic smart window.

On-Surface Synthesis of [3]Radialenes via [1+1+1] Cycloaddition.

[3]Radialenes are the smallest carbocyclic structures with unusual topologies and cross-conjugated π-electronic structures. Here, we report a novel [1+1+1] cycloaddition reaction for the synthesis of aza[3]radialenes on the Ag(111) surface, where the steric hindrance of the chlorine substituents guides the selective and orientational assembling of the isocyanide precursors. By combining scanning tunneling microscopy, non-contact atomic force microscopy, and time-of-flight secondary ion mass spectrometry, we determined the atomic structure of the produced aza[3]radialenes. Furthermore, two reaction pathways including synergistic and stepwise are proposed based on density functional theory calculations, which reveal the role of the chlorine substituents in the activation of the isocyano groups via electrostatic interaction.

Microchemical Engineering in a 3D Ordered Channel Enhances Electrocatalysis.

The kinetics of electrode reactions including mass transfer and surface reaction is essential in electrocatalysis, as it strongly determines the apparent reaction rates, especially on nanostructured electrocatalysts. However, important challenges still remain in optimizing the kinetics of given catalysts with suitable constituents, morphology, and crystalline design to maximize the electrocatalytic performances. We propose a comprehensive kinetic model coupling mass transfer and surface reaction on the nanocatalyst-modified electrode surface to explore and shed light on the kinetic optimization in electrocatalysis. Moreover, a theory-guided microchemical engineering (MCE) strategy has been demonstrated to rationally redesign the catalysts with optimized kinetics. Experimental measurements for methanol oxidation reaction in a 3D ordered channel with tunable channel sizes confirm the calculation prediction. Under the optimized channel size, mass transfer and surface reaction in the channeled microreactor are both well regulated. This MCE strategy will bring about a significant leap forward in structured catalyst design and kinetic modulation.

A Metallic Ion-Induced Self-Assembly Enabling Nanowire-Based Aerogels.

The controlled assembly of nanowires is one of the key challenges in the development of a range of functional 3D aerogels with unique physicochemical properties for practical applications. However, the deep understanding of the dynamic assemble process for fabricating nanowire aerogels remains elusive. Herein, a facile strategy is presented for the metallic ion-induced assembly of nanowires into macroscopic aerogels via a solution-based process. This method enables the interconnecting between polymer-decorated nanowires via metallic coordination, resulting in plenty of nanowire bundles with the same orientation. Besides, the coordinated binding strength of nanowires with different metallic ions is also discussed. The assembly mechanism that the metallic ions induced dynamic behavior of nanowires is revealed via molecular dynamics theoretical evaluation. These findings benefit for constructing nanowire-based aerogels with unique structural features and multi-function, which pave new opportunities for other material systems.

Pd-Catalyzed Direct C-H Activation for the C5-Olefination of Methyleneindolinones.

The direct C-H activation without directing groups can realize the para-selectivity, which is a powerful and concise approach for functionalization of arenes. Utilizing the strategy, a C5-olefination of methyleneindolinones has been successfully developed by palladium-catalyzed direct C-H activation, which provides an expeditious access to 5-vinylindolin-2-ones with high regioselectivity. The protocol is distinguished by a mild reaction system avoiding ligand and high temperature. The kinetic isotope experiments indicate that the C-H bond cleavage is the rate-limiting step.

Radial Nanowire Assemblies under Rotating Magnetic Field Enabled Efficient Charge Separation.

Developing efficient charge separation strategies is essential to achieve high-power conversion efficiency in the fields of chemistry, biology, and material science. Herein, we develop a facile strategy for fabrication of unique wafer-scale radial nanowire assemblies by exploiting shear force in rotary solution. The assembly mechanism can be well revealed by the large-scale stochastic dynamics simulation. Free electrons can be rapidly generated to produce quantitatively tunable current output when the radial nanowire assemblies rotate under the magnetic field. Moreover, the photoconductive performance of the radial semiconductor nanowire assemblies can be remarkably enhanced as the electron-hole recombination was retrained by the efficient charge separation under the rotating magnetic field. Such large-scale unique nanowire assemblies will facilitate the design of an efficient charge separation process in biosystem, sensors, and photocatalysis.

Real-Time Visualization of Solid-Phase Ion Migration Kinetics on Nanowire Monolayer.

Ion migration has been recognized as a critical step in determining the performance of numerous devices in chemistry, biology, and material science. However, direct visualization and quantitative investigation of solid-phase ion migration among anisotropic nanostructures have been a challenging task. Here, we report an in-situ ChemTEM method to quantitatively investigate the solid-phase ion migration process among coassembled nanowires (NWs). This complicated process was tracked within a NW and between NWs with an obvious nanogap, which was revealed by both phase field simulation and ab initio modeling theoretical evaluation. A migration "bridge" between neighboring NWs was observed. Furthermore, these new observations could be applied to migration of other metal ions on semiconductor NWs. These findings provide critical insights into the solid-phase ion migration kinetics occurring in nanoscale systems with generality and offer an efficient tool to explore other ion migration processes, which will facilitate fabrication of customized and new heteronanostructures in the future.

Pathogenic New World Relapsing Fever Borrelia in a Myotis Bat, Eastern China, 2015.

We identified Candidatus Borrelia fainii, a human pathogenic bacterium causing New World relapsing fever in a Myotis bat in eastern China. This finding expands knowledge about the geographic distribution of Borrelia spp. and the potential for infection with New World relapsing fever in China.

Oxidative Catabolism of (+)-Pinoresinol Is Initiated by an Unusual Flavocytochrome Encoded by Translationally Coupled Genes within a Cluster of (+)-Pinoresinol-Coinduced Genes in Pseudomonas sp. Strain SG-MS2.

Burkholderia sp. strain SG-MS1 and Pseudomonas sp. strain SG-MS2 have previously been found to mineralize (+)-pinoresinol through a common catabolic pathway. Here, we used comparative genomics, proteomics, protein semipurification, and heterologous expression to identify a flavoprotein from the vanillyl alcohol oxidase/p-cresol methyl hydroxylase (VAO/PCMH) enzyme family in SG-MS2 that carries out the initial hydroxylation of (+)-pinoresinol at the benzylic carbon. The cognate gene is translationally coupled with a downstream cytochrome gene, and the cytochrome is required for activity. The flavoprotein has a unique combination of cofactor binding and cytochrome requirements for the VAO/PCMH family. The heterologously expressed enzyme has a Km of 1.17 µM for (+)-pinoresinol. The enzyme is overexpressed in strain SG-MS2 upon exposure to (+)-pinoresinol, along with 45 other proteins, 22 of which were found to be encoded by genes in an approximately 35.1-kb cluster also containing the flavoprotein and cytochrome genes. Homologs of 18 of these 22 genes, plus the flavoprotein and cytochrome genes, were also found in a 38.7-kb cluster in SG-MS1. The amino acid identities of four of the other proteins within the SG-MS2 cluster suggest they catalyze conversion of hydroxylated pinoresinol to protocatechuate and 2-methoxyhydroquinone. Nine other proteins upregulated in SG-MS2 on exposure to (+)-pinoresinol appear to be homologs of proteins known to comprise the protocatechuate and 2-methoxyhydroquinone catabolic pathways, but only three of the cognate genes lie within the cluster containing the flavoprotein and cytochrome genes.IMPORTANCE (+)-Pinoresinol is an important plant defense compound, a major food lignan for humans and some other animals, and the model compound used to study degradation of the ß-ß' linkages in lignin. We report a gene cluster, in one strain each of Pseudomonas and Burkholderia, that is involved in the oxidative catabolism of (+)-pinoresinol. The flavoprotein component of the α-hydroxylase which heads the pathway belongs to the 4-phenol oxidizing (4PO) subgroup of the vanillyl alcohol oxidase/p-cresol methyl hydroxylase (VAO/PCMH) enzyme family but constitutes a novel combination of cofactor and electron acceptor properties for the family. It is translationally coupled with a cytochrome gene whose product is also required for activity. The work casts new light on the biology of (+)-pinoresinol and its transformation to other bioactive molecules. Potential applications of the findings include new options for deconstructing lignin into useful chemicals and the generation of new phytoestrogenic enterolactones from lignans.