Overall, the resulting paradigm comprises a system wherein the extent of band bending induced by metal ion binding is the primary driver of photoelectrochemical (PEC)-HER benefits, while the kinetic (catalytic) effects of the PNP-Ni(II) are minimal. This suggests that dipole and band-edge engineering must be a primary design consideration (not secondary to catalyst) in semiconductor|catalyst hybrids for PEC-HER.Highly stable superprotonic conductivity (>10-2 S cm-1) has been achieved through the unprecedented solvent-free-coordinative urea insertion in MOF-74 [M2(dobdc), M = Ni2+, Mg2+; dobdc = 2,5-dioxido-1,4-benzenedicarboxylate] without an acidic moiety. The urea is bound to open metal sites and alters the void volume and surface functionality, which triggers a significant change in proton conductivity and diffusion mechanism. Solid-state 2H NMR revealed that the high conductivity was attributed to the strengthening of the hydrogen bonds between guest H2O induced by hydrogen bonds in the interface between H2O and the polarized coordinated urea.Ganglioside GM3 is a sialylated membrane-based glycosphingolipid that regulates insulin receptor signaling via direct association with the receptor. The level of expression of GM3 synthase (GM3S) and GM3 is increased in tissues of patients with diabetes and murine models of diabetes, and obesity-induced insulin resistance is attenuated in GM3S-deficient mice. Therefore, GM3S has been considered a therapeutic target for type II diabetes; however, no GM3S inhibitors have been reported to date. In this study, we established a high-throughput scintillation proximity assay that can detect GM3S activity to screen GM3S inhibitors from our original chemical library. We also established methods for detecting the activity of GM3S and another sialyltransferase, ST3Gal3, through direct measurement of the enzyme products using an automatic rapid solid-phase extraction system directly coupled to a mass spectrometer. Consequently, we successfully identified two different chemotypes of GM3S-selective inhibitors with a mixed mode of inhibition. We believe that these compounds can be further developed into drugs to treat or prevent diabetes as well as contribute to the development of the ganglioside research field.Because of the permission of the manipulations of modular construction on the atomic level, covalent organic frameworks (COFs) have attracted extensive attention in the electrocatalytic field. Owing to the lack of metal sites in pristine COFs constructed only by metal-free organic building units, it generally exhibits extremely low electrocatalytic activity. Thereby, linking metal sites on the backbone of pyrolysis-free COFs but not loading them on the surface to enhance the electrocatalytic activity is highly desirable but still remains a huge challenge. To this end, herein, we report an efficient and general cation-exchange strategy to synthesize Ni/Fe metal-ion-incorporated COFs (NixFe1-x@COF-SO3) for the oxygen evolution reaction (OER) based on the fundamental structure design of COFs. Impressively, the turnover frequency (TOF) value in Ni0.5Fe0.5@COF-SO3 reaches 0.14 s-1 at the overpotential of 300 mV, which outperforms most recently reported OER electrocatalysts, indicative of ultrahigh metal-atom utilization efficiency.Natural enzyme complex with the subunits cooperating with each other could catalyze cascade reactions in biological system but, just like the limitation of free-floating natural enzymes, usually suffer from deactivation in harsh environment such as high temperature. In this study, a purpose-driven design of amphiphilic aerogel working as the enzymes-immobilization substrate to form the multienzyme complex (MEC) was demonstrated. The aerogel was synthesized only by a single polymer poly(vinyl alcohol) (PVA) as well as a surface modulator maleic acid (MA), the incorporation of which tunes the surface wettability. The usage of the amphiphilic aerogel may do favor for multienzyme immobilization, conserving the enzyme conformation as well as stabilizing the enzymes in high temperature. As a typical example, glucose oxidase and hemin were firmly coimmobilized in the aerogel matrix and actively catalyze the cascade reactions of (i) glucose to gluconic acid and (ii) 3,3,5,5-tetramethylbenzidine (TMB) to its oxidized state. The enzymes could resist the degradation under high temperature (70-100 °C) which is witnessed by the rate of decrease in activity was progressively slackened. Taking the advantage of the chromogenic reaction of TMB, a glucose sensor based on aerogel-enzyme composite for glucose detection in whole blood and sweat was established, exhibiting reliable results and satisfactory recovery. The modified aerogel could also withstand multiple physical deformation meantime maintaining good adsorption capacity as well as catalytic performance. The enzymes-loading aerogel model may hopefully contribute to composing sensors based on other analytes.The problem of controlling cells endowed with a genetic toggle switch has been recently highlighted as a benchmark problem in synthetic biology. It has been shown that a carefully selected periodic forcing can balance a population of such cells in an undifferentiated state. The effectiveness of these control strategies, however, can be hindered by the presence of stochastic perturbations and uncertainties typically observed in biological systems and is therefore not robust. Here, we propose the use of feedback control strategies to enhance robustness and performance of the balancing action by selecting in real-time both the amplitude and the duty-cycle of the pulsatile inputs affecting the toggle switch behavior. We show, via in silico experiments and realistic agent-based simulations, the effectiveness of the proposed strategies even in the presence of uncertainties, stochastic effects, cell growth, and inducer diffusion. In so doing, we confirm previous observations made in the literature about coherence of the population when pulsatile forcing inputs are used, but, contrary to what was proposed in the past, we leverage feedback control techniques to endow the balancing strategy with unprecedented robustness and stability properties. We compare via in silico experiments different external control solutions and show their advantages and limitations from an in vivo implementation viewpoint.Covalent organic frameworks (COFs) with improved stability and extended π-conjugation structure are highly desirable. Here, two imine-linked COFs were converted into ultrastable and π-conjugated fused-aromatic thieno[3,2-c]pyridine-linked COFs (B-COF-2 and T-COF-2). The successful conversion was confirmed by infrared and solid-state 13C NMR spectroscopies. Furthermore, the structures of thieno[3,2-c]pyridine-linked COFs were evaluated by TEM and PXRD. It is noted that a slight difference in the structure leads to totally different photoactivity. The fully π-conjugated T-COF-2 containing triazine as the core exhibited an excellent photocatalytic NADH regeneration yield of 74% in 10 min.Optical anticounterfeiting, typically using luminescent materials to encode and unveil hidden patterns, plays an essential role in countering fraud in trademark, document security, food industry, and public safety. However, this technique is often realized through color-encoded fashion and in the visible range, preventing high-order encryption as well as visualization through scattering layers. Here, we describe a set of shortwave infrared (SWIR)-emitting lanthanide-doped nanoparticles with precisely controlled luminescence lifetime, which can be utilized as temporary codes for multilevel anticounterfeiting through opaque layers. To achieve this, we devise a core/shell/shell/shell structure of NaYF4Yb3+/Er3+ @ NaYbF4 @ NaYF4 @ NaYF4Nd3+, in which the inert NaYF4 shell acts as an energy-retarding layer to regulate energy flow from the outmost light-harvesting layer to the inner core domain to produce long-lived SWIR luminescence at 1532 nm. A precise control of the NaYF4 layer thickness enables yielding a precisely defined lifetime tunable between ∼3 and 10 ms, yet without compromising luminescence intensities. Importantly, optical patterns of these lifetime-encoded core/multishell nanoparticles are able to dynamically show a multitude of secured images in the time domain at defined time points through opaque plastic and biomimetic intralipid layers (about half a centimeter thick). Our temporal optical multiplexing results, demonstrated here in multilevel anticounterfeiting, have implications for optical data storage, biosensing, diagnostics, and nanomedicine.New ultrathin and multifunctional electromagnetic interference (EMI) shielding materials are required for protecting electronics against electromagnetic pollution in the fifth-generation networks and Internet of Things era. Micrometer-thin Ti3C2Tx MXene films have shown the best EMI shielding performance among synthetic materials so far. Yet, the effects of elemental composition, layer structure, and transition-metal arrangement on EMI shielding properties of MXenes have not been explored, despite the fact that more than 30 different MXenes have been reported, and many more are possible. Here, we report on a systematic study of EMI shielding properties of 16 different MXenes, which cover single-metal MXenes, ordered double-metal carbide MXenes, and random solid solution MXenes of M and X elements. This is the largest set of MXene compositions ever reported in a comparative study. Films with thicknesses ranging from nanometers to micrometers were produced by spin-casting, spray-coating, and vacuum-assisted filtration. All MXenes achieved effective EMI shielding (>20 dB) in micrometer-thick films. The EMI shielding effectiveness of sprayed Ti3C2Tx film with a thickness of only ∼40 nm reaches 21 dB. Adjustable EMI shielding properties were achieved in solid solution MXenes with different ratios of elements. A transfer matrix model was shown to fit EMI shielding data for highly conductive MXenes but could not describe the behavior of materials with low conductivity. This work shows that many members of the large MXene family can be used for EMI shielding, contributing to designing ultrathin, flexible, and multifunctional EMI shielding films benefiting from specific characteristics of individual MXenes.We investigated the yield and distribution of macrocyclic products formed in combinatorial libraries (CLs) obtained via double-amidation reactions of methyl diesters with α,ω-diamines. The application of the static combinatorial chemistry (SCC) approach allowed us to generate a large number of macrocyclic diamides and tetraamides in single experiments. We show that high-pressure conditions accelerate the macrocyclization process but also have a great impact on the distribution of macrocyclic products in the presented libraries, promoting the formation of macrocyclic compounds and eliminating the linear ones. The distribution of macrocyclic products was also found to be strongly dependent on the structural features of the substrates employed. Furthermore, in three- and four-substrate CLs we observed the formation of a new type of hybrid tetraamides consisting of three different components.