d-Orbital Reconstructions Forced by Double Bow-Shaped Deformations and Second Coordination Sphere Effects of Cu(II) Heme Analogs in HER.

Both geometric architecture and electronic configurations of heme proteins contribute to its activity. In this work we designed and synthesized a series of four copper(II) porphyrin complexes (4-, 3-, 2- and 1-Cu) where the molecular conformations are modulated by a pair of stepwise shortened straps on the same porphyrin side (cis-ortho) to give double bow-shaped skeletons. Single crystal structures demonstrate that the straps gradually increase the saddle deformation and the deviation of the metal centers, which is in accordance with two, unusual d-orbital reconstructions of two different ground states, as revealed by 4 K EPR and DFT calculations. In the study of the electrocatalytic hydrogen evolution reaction (HER), 1-Cu, with the shortest straps, showed the most apparent improvement of activity. Second coordination sphere (SCS) effects created by the double bow-shaped architecture and the strong saddle porphyrin core in 1-Cu are found to play key roles in proton trapping during the catalytic process. The work contributes a novel strategy to improve the catalytic performance of heme analogs through ligand geometric modulation.

Electronic Configurations and the Effect of Peripheral Substituents of (Nitrosyl)iron Corroles.

There have been debates on the electronic configurations of (nitrosyl)iron corroles for decades. In this work, pentacoordinate [Fe(TPC)(NO)], [Fe(TTC)(NO)], and [Fe(TpFC)(NO)] with different para-substituted phenyl groups (TPC, TTC, and TpFC = tris(phenyl, 4-tolyl, or 4-fluorophenyl)corrole, respectively) have been isolated and investigated by various techniques including single-crystal X-ray diffraction, UV-vis spectroscopy, cyclic voltammetry, Fourier transform infrared, NMR, and absorption fine structure spectroscopy. Multitemperature and high-magnetic-field (3, 6, and 9 T) Mössbauer spectroscopy was also applied on all three complexes, which determined the S = 0 diamagnetic states, consistent with the magnetic susceptibility and electron paramagnetic resonance measurements. Density functional theory predictions by different functionals were compared, and the new calculation strategy, which gave remarkable agreement of the experimental Mössbauer parameters (ΔEQ and δ), allowed further assignment on the electronic configuration of {FeNO}6-(corrole3-) with antiferromagnetically coupled (S = 1/2, FeIII) and (S = 1/2, NO). Correlated sequences between the electronic donating/withdrawing capability of para substituents and the reduction/oxidation potentials, metal out-of-plane displacements (Δ4 and Δ23), and Mössbauer parameters (Vzz and ΔEQ) were also established, which suggests the strong effects of peripheral substituents.

Snake Venom Identification via Fluorescent Discrimination.

The identification and discrimination of snake venom are highly desired for timely clinical treatment. However, the complex components in snake venom make it a great challenge to achieve rapid and accurate identification. Inspired by the organism's taste sensing system, a fluorescent sensor array that could differentiate snake venoms was fabricated. The interaction of snake venoms with different fluorescent dyes in the sensor array gave rich information, based on which efficient detection of complex snake venom was achieved. The main six proteins of snake venom in the same concentration, different concentrations, and their mixtures were identified with 100% accuracy. Furthermore, seven snake venoms belonging to different snake families were discriminated in PBS buffer and human plasma. Interferents of bovine serum albumin (BSA), thrombin, and transferrin (TRF) demonstrated the practicability of the fluorescent sensor array. This strategy of a multiresponse sensor array provides an effective method for accurate and rapid venom toxicology analysis, benefiting early and timely clinical diagnosis and treatment.

Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect.

Several H-H bond forming pathways have been proposed for the hydrogen evolution reaction (HER). Revealing these HER mechanisms is of fundamental importance for the rational design of catalysts and is also extremely challenging. Now, an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported. Three nickel(II) porphyrins were designed and synthesized with distinct steric effects by introducing bulky amido moieties to ortho- or para-positions of the meso-phenyl groups. These porphyrins exhibited different catalytic HER behaviors. For these Ni porphyrins, although their 1e-reduced forms are active to reduce trifluoroacetic acid, the resulting Ni hydrides (depending on the steric effects of porphyrin rings) have different pathways to make H2 . Understanding HER processes, especially controllable switching between homolytic and heterolytic H-H bond formation pathways through molecular engineering, is unprecedented in electrocatalysis.

Bioinspired Synergy Sensor Chip of Photonic Crystals-Graphene Oxide for Multiamines Recognition.

Benefiting from the integrated functions of cilia and glomeruli in the olfactory system, animals can discriminate various odors even in hostile environments. Inspired by this synergetic system of response and signal processing units, a sensor chip of graphene oxide (GO) and photonic crystals (PCs) is fabricated. The GO aerogel functions like the olfactory cilia, which effectively captures the analytes and generates abundant sensing signals for recognition; and the PCs act as the olfactory glomeruli, whose periodic structure enables selective enhancement of the fluorescent signals to realize further signal processing. Ten biogenic amines and seven drug amines are effectively discriminated. The integrated sensor strategy of response and signal manipulation units will promote enormous pursuits of rapid clinical diagnosis or intractable pathology analysis.

Patterned Arrays of Functional Lateral Heterostructures via Sequential Template-Directed Printing.

The precise integration of microscale dots and lines with controllable interfacing connections is highly important for the fabrication of functional devices. To date, the solution-processible methods are used to fabricate the heterogeneous micropatterns for different materials. However, for increasingly miniaturized and multifunctional devices, it is extremely challenging to engineer the uncertain kinetics of a solution on the microstructures surfaces, resulting in uncontrollable interface connections and poor device performance. Here, a sequential template-directed printing process is demonstrated for the fabrication of arrayed microdots connected by microwires through the regulation of the Rayleigh-Taylor instability of material solution or suspension. Flexibility in the control of fluidic behaviors can realize precise interface connection between the micropatterns, including the microwires traversing, overlapping or connecting the microdots. Moreover, various morphologies such as circular, rhombic, or star-shaped microdots as well as straight, broken or curved microwires can be achieved. The lateral heterostructure printed with two different quantum dots displays bright dichromatic photoluminescence. The ammonia gas sensor printed by polyaniline and silver nanoparticles exhibits a rapid response time. This strategy can construct heterostructures in a facile manner by eliminating the uncertainty of the multimaterials interface connection, which will be promising for the development of novel lateral functional devices.

µ-Oxido-bis-[(5,10,15,20-tetra-phenyl-porphyrinato-κ4 N,N',N'',N''')manganese(III)].

In the crystal structure of the title oxido-bridged binuclear complex, [MnIII(TPP)]2O (TPP = tetra-phenyl-porphyrinate, C44H28N4) or [Mn2(C44H28N4)2O], the two penta-coordinate manganese(III) ions are bridged by a single oxido ligand, with an Mn-O distance of 1.7600 (3) Šand an Mn-O-Mn bridging angle of 176.1 (2)°. The bridging O2- ligand is located on a twofold rotation axis, resulting in point group 2 for the entire complex. The MnIII atom is displaced out of the 24-atom mean plane of the porphyrine entity by 0.52 Å. C-H⋯π and π-π inter-actions help to stabilize the mol-ecular packing within the crystal structure.

Heterogeneous Integration of Three-Primary-Color Photoluminescent Nanoparticle Arrays with Defined Interfaces.

Minimized photoluminescent devices require both high-density fluorescent arrays and minimal cross-talk between neighboring pixels on the limited area. However, the challenges to achieve the overall integration of nanomaterial-based devices hinder the development of microscale full-color displays, including micro/nanoarray density, orientation control, multimaterial interface morphology, and uniform colors. Here, we report a heterogeneous integration approach to control the orientation, combination, and density of fluorescent micro/nanoarrays on flexible substrates. By controlling the defined interface and critical shrinkage width of liquid bridges, the width of three-primary-color micro/nanolines reached 100 nm. The interval between two parallel luminous lines is down to 40 µm, and the optical cross-talk effect is remarkably reduced. This work provides a facile approach to prepare high-performance micro-photoluminescent and imaging arrays for next-generation flexible display and lighting technology.

A general strategy for printing colloidal nanomaterials into one-dimensional micro/nanolines.

Though patterned one-dimensional (1D) micro/nanoline arrays are of great importance in the field of integrated circuits and optoelectronics, the fabrication of high-precision micro/nanolines with excellent optical and electrical performance remains a great challenge. Herein, a general strategy for printing 1D micro/nanolines is proposed by manipulating the self-assembly of functional nanoparticles as a multilayer or monolayer stack with a single-nanoparticle width. This method is universal for dispersible nanoparticles, and the silver nanoparticle was selected as a model nanoparticle due to its good conductivity, dispersibility and narrow-size distribution. The results indicate that the morphologies of printed micro/nanolines can be precisely regulated by the substrate wettability and the suspension concentration. Specifically, 1D nanoparticle-assembled architectures are printed as a monolayer stack on the substrate with a low contact angle (below 45°), while a multilayer stack is formed on the substrate with a high contact angle (above 50°) or a high concentration (more than 0.12%). The controllability of micro/nanoline morphologies can be interpreted through the influence of the three phase contact line slipping motion and the nanoparticle diffusion on diverse substrates at different concentrations. Alteration of the printing template structures enables the intervals of 1D micro/nanolines to span from 16 µm to 48 µm. These results provide an efficient methodology for fabricating micro/nano-circuits or optics and strengthening the understanding of the self-assembling process.

A General Approach for Fluid Patterning and Application in Fabricating Microdevices.

Engineering the fluid interface such as the gas-liquid interface is of great significance for solvent processing applications including functional material assembly, inkjet printing, and high-performance device fabrication. However, precisely controlling the fluid interface remains a great challenge owing to its flexibility and fluidity. Here, a general method to manipulate the fluid interface for fluid patterning using micropillars in the microchannel is reported. The principle of fluid patterning for immiscible fluid pairs including air, water, and oils is proposed. This understanding enables the preparation of programmable multiphase fluid patterns and assembly of multilayer functional materials to fabricate micro-optoelectronic devices. This general strategy of fluid patterning provides a promising platform to study the fundamental processes occurring on the fluid interface, and benefits applications in many subjects, such as microfluidics, microbiology, chemical analysis and detection, material synthesis and assembly, device fabrication, etc.

Spider-web inspired multi-resolution graphene tactile sensor.

Multi-dimensional accurate response and smooth signal transmission are critical challenges in the advancement of multi-resolution recognition and complex environment analysis. Inspired by the structure-activity relationship between discrepant microstructures of the spiral and radial threads in a spider web, we designed and printed graphene with porous and densely-packed microstructures to integrate into a multi-resolution graphene tactile sensor. The three-dimensional (3D) porous graphene structure performs multi-dimensional deformation responses. The laminar densely-packed graphene structure contributes excellent conductivity with flexible stability. The spider-web inspired printed pattern inherits orientational and locational kinesis tracking. The multi-structure construction with homo-graphene material can integrate discrepant electronic properties with remarkable flexibility, which will attract enormous attention for electronic skin, wearable devices and human-machine interactions.

Wearable Large-Scale Perovskite Solar-Power Source via Nanocellular Scaffold.

Dramatic advances in perovskite solar cells (PSCs) and the blossoming of wearable electronics have triggered tremendous demands for flexible solar-power sources. However, the fracturing of functional crystalline films and transmittance wastage from flexible substrates are critical challenges to approaching the high-performance PSCs with flexural endurance. In this work, a nanocellular scaffold is introduced to architect a mechanics buffer layer and optics resonant cavity. The nanocellular scaffold releases mechanical stresses during flexural experiences and significantly improves the crystalline quality of the perovskite films. The nanocellular optics resonant cavity optimizes light harvesting and charge transportation of devices. More importantly, these flexible PSCs, which demonstrate excellent performance and mechanical stability, are practically fabricated in modules as a wearable solar-power source. A power conversion efficiency of 12.32% for a flexible large-scale device (polyethylene terephthalate substrate, indium tin oxide-free, 1.01 cm2 ) is achieved. This ingenious flexible structure will enable a new approach for development of wearable electronics.