Self-assembled soft alloy with Frank-Kasper phases beyond metals.

Soft building blocks, such as micelles, cells or soap bubbles, tend to adopt near-spherical geometry when densely packed together. As a result, their packing structures do not extend beyond those discovered in metallic glasses, quasicrystals and crystals. Here we report the emergence of two Frank-Kasper phases from the self-assembly of five-fold symmetric molecular pentagons. The µ phase, an important intermediate in superalloys, is indexed in soft matter, whereas the ϕ phase exhibits a structure distinct from known Frank-Kasper phases in metallic systems. We find a broad size and shape distribution of self-assembled mesoatoms formed by molecular pentagons while approaching equilibrium that contribute to the unique packing structures. This work provides insight into the manipulation of soft building blocks that deviate from the typical spherical geometry and opens avenues for the fabrication of 'soft alloy' structures that were previously unattainable in metal alloys.

Taking Olefin Metathesis to the Limit: Stereocontrolled Synthesis of Trisubstituted Alkenes.

ConspectusIn this Account, we share the story of the development of catalytic olefin metathesis processes that efficiently deliver a wide range of acyclic and macrocyclic E- or Z-trisubstituted alkenes. The tale starts with us unveiling, in collaboration with Richard Schrock and his team, the blueprint in 2009 for the design of kinetically controlled Z-selective olefin metathesis reactions. This paved the way for the development of Mo-, W-, and Ru-based catalysts and strategies for synthesizing countless linear and macrocyclic Z-olefins. Six years later, in 2015, we found that abundant Z-alkene feedstocks, such as oleic acid, can be directly transformed to high-value and more difficult-to-access alkenes through a cross-metathesis reaction promoted by a Ru-catechothiolate complex that we had developed; the approach, later coined stereoretentive olefin metathesis, was extended to the synthesis of E-alkenes.It was all about disubstituted alkenes until when in 2017 we addressed the challenge of accessing stereodefined Z- and E-trisubstituted alkenes, key to medicine and materials research. These transformations can be most effectively catalyzed by Mo monoaryloxides pyrrolide (MAP) and chloride (MAC) complexes. A central aspect of the advance is the merging of olefin metathesis, which delivered trisubstituted alkenyl fluorides, chlorides, and bromides with cross-coupling. These catalytic and stereoretentive transformations can be used in various combinations, thereby enabling access to assorted Z- or E-trisubstituted alkene. Ensuing work led to the emergence of other transformations involving substrates that can be purchased with high stereoisomeric purity, notably E- and Z-trihalo alkenes. Trisubstituted olefins, Z or E, bearing a chemoselectively and stereoretentively alterable F,Cl-terminus or B(pin),Cl-terminus may, thus, be easily and reliably synthesized. Methods for stereoretentive preparation of other alkenyl bromide regioisomers and α,ß-unsaturated carboxylic and thiol esters, nitriles, and acid fluorides followed, along with stereoretentive ring-closing metathesis reactions that afford macrocyclic trisubstituted olefins. Z- and E-Macrocyclic trisubstituted olefins, including those that contain little or no entropic support for cyclization (minimally functionalized) and/or are disfavored under substrate-controlled conditions, can now be synthesized. The utility of this latest chapter in the history of olefin metathesis has been highlighted by applications to the synthesis of several biologically active compounds, as well as their analogues, such as those marked by one or more site-specifically incorporated fluorine atoms or more active but higher energy and otherwise unobtainable conformers.The investigations discussed here, which represent every stereoretentive method that has been reported thus far for preparing a trisubstituted olefin, underscore the inimitable power of Mo-based catalysts. This Account also showcases a variety of mechanistic attributes─some for the first time, and each instrumental in solving a problem. Extensive knowledge of mechanistic nuances will be needed if we are to address successfully the next challenging problem, namely, the development of catalysts and strategies that may be used to synthesize a wide range of tetrasubstituted alkenes, especially those that are readily modifiable, with high stereoisomeric purity.

Multimode interference methane sensor based on a ZIF-8/PDMS composite film.

A multimode interference methane sensor based on a ZIF-8/PDMS composite film is proposed. The sensing principle is that the refractive index of the ZIF-8/PDMS composite film changes when it adsorbs methane, leading to a measurable optical path difference during the coupling of the cladding higher-order modes and the fundamental mode in the multimode interference fiber (MMI). The environmental methane concentration is then detectable by detecting the wavelength shifts of the interference peaks in the resulted spectrum. Through simulations and experiments aimed at enhancing sensor sensitivity, we optimized three parameters within the sensor structure: the length of the Tapered Single-Mode Fiber (TSMF), the composite film thickness, and the TSMF taper diameter. The experimental results indicate that the sensor's sensitivity reaches a maximum of 0.231 nm%-1. Additionally, the sensor exhibits excellent structural stability and measurement repeatability. The response time is as short as 40 s, and the recovery time ranges between 3 and 5 min. The proposed multimode interferometric methane sensor based on the ZIF-8/PDMS composite film has great potential to support highly sensitive methane concentration detection in many applications.

Low-disturbance automatic bias point control for optical IQ modulator using digital chaotic waveform as dither signals.

A low-disturbance automatic bias point control (ABC) method for optical in-phase and quadrature modulators (IQM) is proposed using digital chaotic waveform as dither signals. Two distinct chaotic signals, each with unique initial values, are introduced to the direct current (DC) port of IQM in conjunction with a DC voltage. Due to the robust autocorrelation performance and exceptionally low cross-correlation of chaotic signals, the proposed scheme is capable of mitigating the impact of low-frequency interference, signal-signal beat interference, and high-power RF-induced noise on transmitted signals. In addition, due to the broadwidth of chaotic signals, their power is distributed across a broad frequency range, resulting in a significant reduction in power spectral density (PSD). Compared to the conventional single-tone dither-based ABC method, the proposed scheme exhibits a reduction in peak power of the output chaotic signal by over 24.1 dB, thereby minimizing disturbance to the transmitted signal while maintaining superior accuracy and stability for ABC. The performance of ABC methods, based on single-tone and chaotic signal dithering, are experimentally evaluated in both 40Gbaud 16QAM and 20Gbaud 64QAM transmission systems. The results indicate that the utilization of chaotic dither signals leads to a reduction in measured bit error rate (BER) for 40Gbaud 16QAM and 20Gbaud 64QAM signals, with respective decreases from 2.48% to 1.26% and from 5.31% to 3.35% when the received optical power is -27dBm.

A Thiol-Michael Approach Towards Versatile Functionalized Cyclic Titanium-Oxo Clusters.

In expanding our research activities of superlattice engineering, designing new giant molecules is the necessary first step. One attempt is to use inorganic transition metal clusters as building blocks. Efficient functionalization of chemically precise transition metal clusters, however, remains a great challenge to material scientists. Herein, we report an efficient thiol-Michael addition approach for the modifications of cyclic titanium-oxo cluster (CTOC). Several advantages, including high efficiency, mild reaction condition, capability of complete addition, high atom economy, as well as high functional group tolerance were demonstrated. This approach can afford high yields of fully functionalized CTOCs, which provides a powerful platform for achieving versatile functionalization of precise transition metal clusters and further applications.

Patterns of salt transport and factors affecting typical shrub in desert-oases transition areas.

Soil salinization and water deficits are considered the primary factors limiting economic development and environmental improvement in arid areas. However, there remains limited knowledge of the adaptability of typical shrubs to salinization of desert areas in arid zones. This study was conducted in a desert oasis transition zone (Tarim River, China), aiming to investigate: i) the spatial-temporal changes in soil salinity; ii) the interactions between the pedoenvironment vs typical shrub (Calligonum mongolicum). The van Genuchten soil salinity retention ensemble model (TVGSSREM-3D) was developed to simulate variations in soil water-salt transport in the desert-oasis zone and to accurately explain the main factors influencing Calligonum mongolicum desert-oases transition areas. The results showed that monthly average salinity ranged from 2.0 to 8.0 g kg-1, with a peak in August (9.17 g kg-1). The presence of human activities (Salt Drainage Canal) and the distribution of Calligonum mongolicum resulted in a clear spatial salinity zonation. Moreover, analysis of environmental indicators using the TVGSSREM-3D model revealed strong correlations between the distribution of salinity in Calligonum mongolicum desert-oases transition areas and groundwater depth (GD), minimum relative humidity (MRH), and water vapor pressure (WVP). These findings provide a scientific basis for stabilizing, restoring, and reconstructing the ecosystem of the oasis-desert transition zone.

Nonlinear optical limiting effect of porous graphene dispersions at 1064 nm.

This work presents a new, to the best of our knowledge, porous graphene dispersion in ethanol that can achieve a good nonlinear optical limiting (NOL) effect at the wavelength of 1064 nm. Using the Z-scan system, the nonlinear absorption coefficient of the porous graphene dispersion with a concentration of 0.01 mg/mL was measured as 9.69×10-9 c m/W. The NOL of the porous graphene dispersions in ethanol under three different concentrations (0.01, 0.02, and 0.03 mg/mL) were measured. Among them, the 1-cm-thick porous graphene dispersion with a concentration of 0.01 mg/mL has the best optical limiting effect, in which the linear transmittance is 76.7%, and the lowest transmittance is 24.9%. By using the pump-probe technique, we detected the formation and annihilation times of the scatter when the suspension interacts with the pump light. The analysis shows that the NOL mechanisms of the novel porous graphene dispersion are mainly nonlinear scattering and nonlinear absorption.

Doping effects on the antibonding states and carriers of two-dimensional PC6.

The absence of a bandgap in pristine graphene severely restricts its application, and there is high demand for other novel two-dimensional (2D) materials. PC6 has recently emerged as a promising 2D material with a direct band gap and ultrahigh carrier mobility. In light of the remarkable properties of an intrinsic PC6 monolayer, it would be intriguing to find out whether a doped PC6 monolayer displays properties superior to the pure system. In this study, we have performed density functional theory calculations to understand the doping effects of both P-site and C-site substitution in PC6 and, for the first time, we discovered doping-related impurity-level anomalies in this system. We successfully explained why no donor or acceptor defect states exist in the band structures of XP-PC6 (X = C, Ge, Sn, O, S, Se, or Te). In group-IV-substituted systems, these dopant states hybridize with host states near the Fermi level rather than act as acceptors, which is deemed to be a potential way to tune the mobility of PC6. In the case of group-VI substitution, the underlying mechanism relating to doping anomalies arises from excess electrons occupying antibonding states.

The effect of pressure on the structural, electronic and vibrational properties of solid carbon dioxide phases.

The structural, electronic and vibrational properties of solid carbon dioxide phases (I, II, III, and IV) under high pressure are studied using first-principles calculations. The calculated structural parameters are in good agreement with the experimental values. The third-order Birch-Murnaghan equation of state is fitted, and the corresponding parameters are obtained. We obtained the phase boundary points of each phase and plotted the phase diagram of solid carbon dioxide. The influence of pressure on the band structure and density of states is studied. The vibrational properties of the four phases of carbon dioxide were studied in detail, and the infrared and Raman spectra of the four phases were obtained. It can be seen from the calculated spectrum that the number and frequency of vibration peaks are in good agreement with the experimental values. And, we also analyze the influence of pressure on the frequency of vibration mode.

Ordered Mesoporous Silica Pyrolyzed from Single-Source Self-Assembled Organic-Inorganic Giant Surfactants.

We report the preparation of hexagonal mesoporous silica from single-source giant surfactants constructed via dihydroxyl-functionlized polyhedral oligomeric silsesquioxane (DPOSS) heads and a polystyrene (PS) tail. After thermal annealing, the obtained well-ordered hexagonal hybrid was pyrolyzed to afford well-ordered mesoporous silica. A high porosity (e.g., 581 m2/g) and a uniform and narrow pore size distribution (e.g., 3.3 nm) were achieved. Mesoporous silica in diverse shapes and morphologies were achieved by processing the precursor. When the PS tail length was increased, the pore size expanded accordingly. Moreover, such pyrolyzed, ordered mesoporous silica can help to increase both efficiency and stability of nanocatalysts.

Different Strategies for Designing Dual-Catalytic Enantioselective Processes: From Fully Cooperative to Non-cooperative Systems.

An emerging area of research in chemistry requires that we learn how to manage the characteristics of a pair of co-catalysts so that a transformation proceeds as we wish it to. These are processes during which one catalyst first generates a non-isolable intermediate, which then in situ undergoes a reaction that is promoted by a different catalyst. This scenario raises several design issues. Since co-catalysts often have overlapping functions, what if there is an exchange of ligands between two organometallic catalysts? How can we be certain that a co-catalyst reacts specifically with a particular intermediate? What if the less reactive co-catalyst must engage first, and the one that is more active needs to wait its turn? How might we orchestrate the proper sequence of events? While many dual-catalytic processes have been introduced and reviews are available, there are subtle yet crucial distinguishing attributes that remain unappreciated. While the terms "dual-catalysis" and "cooperative catalysis" are often used interchangeably, on many occasions the catalysts are not entirely cooperative. Here, we will discuss how chemists have been able to harmonize the opposing functions of catalysts to achieve high efficiency and/or stereoselectivity. We will show that the progress achieved thus far is likely the preamble to the future development of non-orthogonal multi-catalytic processes (i.e., transformations involving several catalysts that are not inherently cooperative) where the order with which each catalyst enters the fray will demand additional innovative strategies.

Racemic Vinylallenes in Catalytic Enantioselective Multicomponent Processes: Rapid Generation of Complexity through 1,6-Conjugate Additions.

Racemic vinylallenes are shown to be effective substrates for catalytic multicomponent diastereo- and enantioselective 1,6-conjugate addition of multifunctional allyl moieties to easily accessible α,ß,γ,δ-unsaturated diesters. Reactions may be catalyzed by 5.0 mol % of a readily accessible NHC-Cu complex at ambient temperature, and other than a vinylallene, involve B2 (pin)2 and an α,ß,γ,δ-unsaturated diester. A variety of vinylallenes were converted to products bearing a Z-trisubstituted alkenyl-B(pin) moiety, a vinyl group, a ß,γ-unsaturated diester unit, and vicinal stereogenic centers in up to 67 % yield, 87:13 Z/E ratio, >98:2 d.r., and 98:2 e.r. Chemoselective modifications involving the alkenyl-B(pin), the vinyl, or the 1,2-disubstituted olefin moieties were carried out to demonstrate versatility and utility. Stereochemical models, based on mechanistic and DFT studies, demonstrate the dynamic behavior of intermediated Cu-allyl species and account for various selectivity profiles.

Low-Temperature- and Phosphate Deficiency-Responsive Elements Control DGTT3 Expression in Chlamydomonas reinhardtii.

acyl-CoA:Diacylglycerol acyltransferases (DGAT) catalyse the final step of the triacylglycerol biosynthesis. Two major gene families have been shown to encode DGATs, DGAT1, and DGAT2. Abiotic factors such as low temperatures, nitrogen, or phosphorus deficiency was reported to play important roles in the growth and development in green algae. Whether DGATs are induced by low temperatures or phosphorus deficiency, and the corresponding promoter elements are not reported yet. In this study, we found DGTT3 to have a significant response to low temperatures, phosphorus deficiency, and other stresses, such as high concentrations of NaCl, 20 µM GA, and 20 µM abscisic acid. The promoter element of DGTT3 was then studied by deletion and scanning mutagenesis method. Results revealed that the - 319/- 247 region is essential for low-temperature and phosphate-deficiency-mediated induction of DGTT3 expression. The sequence from - 312 to - 299 of the CAATAGACTGCTGCT was the core sequence of the cold responsive element, which facilitated the promoter response to cold induction. Meanwhile, the sequence from - 319 to - 275 was critical to phosphate-deficiency regulation. Furthermore, the relationship between DNA methylation and transgenic silence in -N condition was analyzed, and results showed that the DNA methylation rate of the transformed insertion region was high. This phenomenon was responsible for the decrease in ARS gene expression in the transgenic algal strain under -N conditions.

Phenotypic plasticity may help lizards cope with increasingly variable temperatures.

Temperature variability is predicted to increase in the coming century due to climate change. However, the biological impact of increased temperature variability on animals remains largely unexplored. Here, we experimentally exposed gravid viviparous lizards (Eremias multiocellata) to two thermal environments [constant daily maximum (CDM) versus variable daily maximum (VDM) treatment with the same average temperature] to address maternal and offspring responses to increased variability in ambient temperature. Females from the VDM treatment delayed parturition, but produced similar litter sizes and litter masses as did CDM females. Offspring from the VDM treatment selected higher body temperatures, had higher metabolic rates and higher growth rates, and grew to a similar size as those from the CDM treatment despite having a shorter growth period prior to hibernation. Therefore, phenotypic plasticity may be critical for lizards to respond effectively to climate change, and its role in responding to increasingly variable temperatures warrants further attention.

Diastereoselective carbonyl allylation with simple olefins enabled by palladium complex-catalyzed C-H oxidative borylation.

A highly diastereoselective Pd-catalyzed carbonyl allylation of aldehydes and isatins directly using simple acyclic olefins as allylating reagents is described. This transformation is actually a sequential process consisting of a Pd-catalyzed oxidative allylic C-H borylation and an allylboration of carbonyls accelerated by phosphoric acid, wherein a wide scope of olefins could be tolerated. The oxidant is revealed to play a key role in the successful realization of the allylic C-H activation-based allylation.

A pilot study on the expression of circadian clock genes in the alveolar bone of mice with periodontitis.

This study aimed to investigate the expression of circadian clock genes in mouse alveolar bone, and the possible reasons for these changes. Fifty C57 mice were orally inoculated with P. gingivalis, establishing a model of periodontitis using healthy mice as controls. The alveolar bone of both groups was taken for micro-computed tomography scanning to measure the amount of attachment loss, and the relative expression of mRNA in each clock gene and periodontitis related inflammatory factor was detected by real-time fluorescence quantitative polymerase chain reaction (qRT-PCR). After the establishment of the mouse model, the height of alveolar bone in the periodontitis group was significantly lower than that in the normal group (p < 0.05). The relative transcriptional level of Bmal1, Per2, and Cry1 mRNA was in the circadian rhythm in the normal group (p ≤ 0.05), while in the periodontitis group, its circadian rhythm disappeared and the transcriptional level characteristics were changed. Interleukin (IL)-6, tumor necrosis factor-alpha (TNF-α), and interferon (IFN-γ) mRNA transcriptional level were elevated in the periodontitis group compared to the normal group. In conclusion, the mRNA transcriptional level of Bmal1, Per2, and Cry1 in alveolar bone of normal mice has circadian rhythm, but the rhythm disappears under the condition of periodontitis, and the cause of its occurrence may be related to inflammatory cytokines.

A catalytic process enables efficient and programmable access to precisely altered indole alkaloid scaffolds.

A compound's overall contour impacts its ability to elicit biological response, rendering access to distinctly shaped molecules desirable. A natural product's framework can be modified, but only if it is abundant and contains suitably modifiable functional groups. Here we introduce a programmable strategy for concise synthesis of precisely altered scaffolds of scarce bridged polycyclic alkaloids. Central to our approach is a scalable catalytic multi-component process that delivers diastereo- and enantiomerically enriched tertiary homoallylic alcohols bearing differentiable alkenyl moieties. We used one product to launch progressively divergent syntheses of a naturally occurring alkaloid and its precisely expanded, contracted and/or distorted framework analogues (average number of steps/scaffold of seven). In vitro testing showed that a skeleton expanded by one methylene in two regions is cytotoxic against four types of cancer cell line. Mechanistic and computational studies offer an account for several unanticipated selectivity trends.

High-Performance Self-Powered Photoelectrochemical Ultraviolet Photodetectors Based on an In2O3 Nanocube Film.

Ultraviolet photodetectors (UV PDs) have attracted significant attention due to their wide range of applications, such as underwater communication, biological analysis, and early fire warning systems. Indium oxide (In2O3) is a candidate for developing high-performance photoelectrochemical (PEC)-type UV PDs owing to its high UV absorption and good stability. However, the self-powered photoresponse of the previously reported In2O3-based PEC UV PDs is unsatisfactory. In this work, high-performance self-powered PEC UV PDs were constructed by using an In2O3 nanocube film (NCF) as a photoanode. In2O3 NCF photoanodes were synthesized on FTO by using hydrothermal methods with a calcining process. The influence of the electrolyte concentration, bias potential, and irradiation light on the photoresponse properties was systematically studied. In2O3 NCF PEC UV PDs exhibit outstanding self-powered photoresponses to 365 nm UV light with a high responsivity of 44.43 mA/W and fast response speed (20/30 ms) under zero bias potential, these results are superior to those of previously reported In2O3-based PEC UV PDs. The improved self-powered photoresponse is attributed to the higher photogenerated carrier separation efficiency and faster charge transport of the in-situ grown In2O3 NCF. In addition, these PDs exhibit excellent multicycle stability, maintaining the photocurrent at 98.69% of the initial value after 700 optical switching cycles. Therefore, our results prove the great promise of In2O3 in self-powered PEC UV PDs.

Investigation of the Fracture and Fragmentation of Implosively Driven Thin-Walled Cylindrical Shell: From Thermodynamic Analysis to CDEM Simulation.

The scattering of fragments is a notable characteristic of the explosive detonation of a shelled charge. This study examines the fracture and fragmentation of the shell and the process by which natural fragments form under the strains of implosion. The analysis takes into account both the explosive's energy output and the casing's dynamic response. For this purpose, utilizing a thermochemical code as an alternative to the conventionally employed cylinder test, the Jones-Wilkins-Lee equation of state (JWL EOS) was calibrated within a range of relative specific volume up to 13. The detonation of the shelled charge was subsequently analyzed using the continuum-discontinuum element method (CDEM). Following this, the formation mechanisms and scattering characteristics of natural fragments were scrutinized. The analysis found that the shell predominantly experiences shear failure with uniform evolution, displaying a "hysteresis effect" and two mutation stages in the evolution of tensile failure. Within the JWL EOS's calibrated range, the representation of fragment displacement and velocity improved by 47.97% and 5.30%, respectively. This study provides valuable guidance for designing the power field of warheads and assessing their destructive power.

Cumulative ecosystem response to Hydraulic Engineering Infrastructure Projects in an arid basin.

Hydraulic Engineering Infrastructure Projects (HEIPs) typically show profound effects on hydrological systems and ecosystems. However, data restrictions have limited the exploration of the influences of compound HEIPs on ecosystems to a few studies. This study proposes a watershed-wide ecosystem assessment framework to investigate the impact of HEIPs in the Tarim River Headwaters-Hotan River Basin on the ecosystem of the arid zone. The framework includes a deep learning-meta cellular automata algorithm (DLMCAA) based on the spatiotemporal characteristics of HEIPs and hydro-meteorological and human activities. Moreover, the spatiotemporal relationships between compound HEIPs and ecosystem variances were quantified. The framework including DLMCAA showed a good performance in simulating landcover in 2020, with a Kappa coefficient of 0.89. Therefore, the DLMCAA could be used to simulate and predict ecosystem changes under the HEIPs, which suggested that the framework is effective and practical. An analysis of the spatiotemporal distribution of each ecosystem from 1980 to 2020 showed that the low shrub ecosystems changed most significantly (26.38 %) between 1980 and 2020. Also, the use of spatially driven hydrological project data from different ABC scenarios showed that ecosystems driven by HEIPs were more stable compared to those without HEIPs under future climate change. In particular, the DLMCAA indicated that compound HEIPs had a more positive impact on ecosystem oases in arid lands compared with that of single HEIPs. The results of this study can serve as a scientific reference for assessing the impact of HEIPs, as well as for understanding ecosystem changes and facilitating sustainable water resource management in the arid regions.