Characterization of the MIKCC-type MADS-box gene family in blueberry and its possible mechanism for regulating flowering in response to the chilling requirement.

MAIN CONCLUSION: The expression peak of VcAP1.4, VcAP1.6, VcAP3.1, VcAP3.2, VcAG3, VcFLC2, and VcSVP9 coincided with the endo-dormancy release of flower buds. Additionally, GA4+7 not only increased the expression of these genes but also promoted flower bud endo-dormancy release. The MIKCC-type MADS-box gene family is involved in the regulation of flower development. A total of 109 members of the MIKCC-type MADS-box gene family were identified in blueberry. According to the phylogenetic tree, these 109 MIKCC-type MADS-box proteins were divided into 13 subfamilies, which were distributed across 40 Scaffolds. The results of the conserved motif analysis showed that among 20 motifs, motifs 1, 3, and 9 formed the MADS-box structural domain, while motifs 2, 4, and 6 formed the K-box structural domain. The presence of 66 pairs of fragment duplication events in blueberry suggested that gene duplication events contributed to gene expansion and functional differentiation. Additionally, the presence of cis-acting elements revealed that VcFLC2, VcAG3, and VcSVP9 might have significant roles in the endo-dormancy release of flower buds. Meanwhile, under chilling conditions, VcAP3.1 and VcAG7 might facilitate flower bud dormancy release. VcSEP11 might promote flowering following the release of endo-dormancy, while the elevated expression of VcAP1.7 (DAM) could impede the endo-dormancy release of flower buds. The effect of gibberellin (GA4+7) treatment on the expression pattern of MIKCC-type MADS-box genes revealed that VcAP1.4, VcAP1.6, VcAP3.1, VcAG3, and VcFLC2 might promote flower bud endo-dormancy release, while VcAP3.2, VcSEP11, and VcSVP9 might inhibit its endo-dormancy release. These results indicated that VcAP1.4, VcAP1.6, VcAP1.7 (DAM), VcAP3.1, VcAG3, VcAG7, VcFLC2, and VcSVP9 could be selected as key regulatory promoting genes for controlling the endo-dormancy of blueberry flower buds.

Inhibiting collective cation migration in Li-rich cathode materials as a strategy to mitigate voltage hysteresis.

Lithium-rich cathodes are promising energy storage materials due to their high energy densities. However, voltage hysteresis, which is generally associated with transition metal migration, limits their energy efficiency and implementation in practical devices. Here we reveal that voltage hysteresis is related to the collective migration of metal ions, and that isolating the migration events from each other by creating partial disorder can create high-capacity reversible cathode materials, even when migrating transition metal ions are present. We demonstrate this on a layered Li-rich chromium manganese oxide that in its fully ordered state displays a substantial voltage hysteresis (>2.5 V) associated with collective transition metal migration into Li layers, but can be made to achieve high capacity (>360 mAh g-1) and energy density (>1,100 Wh kg-1) when the collective migration is perturbed by partial disorder. This study demonstrates that partially cation-disordered cathode materials can accommodate a high level of transition metal migration, which broadens our options for redox couples to those of mobile cations.

Bioinformatics characteristics and expression analysis of IL-8 and IL-10 in largemouth bass (Micropterus salmoides) upon Nocardia seriolae infection.

IL-8 and IL-10 are crucial inflammatory cytokines that participate in defending host cells against infections. To demonstrate the function of the two interleukin genes in largemouth bass (Micropterus salmoides), we initially cloned and identified the cDNA sequences of il-8 and il-10 in largemouth bass, referred to as Msil-8 and Msil-10, respectively. The open reading frame (ORF) of Msil-8 was 324 bp in length, encoding 107 amino acids, while the ORF of Msil-10 consisted of 726 bp and encoded 241 amino acids. Furthermore, the functional domains of the SCY domain in MsIL-8 and the IL-10 family signature motif in MsIL-10 were highly conserved across vertebrates. Additionally, both MsIL-8 and MsIL-10 showed close relationships with M. dolomieu. Constitutive expression of Msil-8 and Msil-10 was observed in various tissues, with the highest level found in the head kidney. Subsequently, largemouth bass were infected with Nocardia seriolae via intraperitoneal injection to gain a further understanding of the function of these two genes. Bacterial loads were initially detected in the foregut, followed by the midgut, hindgut, and liver. The mRNA expression of Msil-8 was significantly down-regulated after infection, especially at 2 days post-infection (DPI), with a similar expression to Msil-10. In contrast, the expression of Msil-8 and Msil-10 was significantly upregulated in the foregut at 14 DPI. Taken together, these results reveal that the function of IL-8 and IL-10 was likely hindered by N. seriolae, which promoted bacterial proliferation and intercellular diffusion.

Solvent-Induced In(III)-MOFs with Controllable Interpenetration Degree Performing High-Efficiency Separation of CO2/N2 and CO2/CH4.

Herein, three In(III)-based metal-organic frameworks (In-MOFs) with different degrees of interpenetration (DOI), namely In-MOF-1, In-MOF-2, and In-MOF-3, constructed by In3+ and Y-shaped ligands 4,4',4″-s-triazine-2,4,6-triyltribenzoate (H3TATB), are successfully synthesized through the ionothermal/solvothermal method. Subsequently, three novel In-MOFs, including noninterpenetration polycatenation, 2-fold interpenetrated, and 4-fold interpenetrated structure, are employed as the platform for systematically investigating the separation efficiency of CO2/N2, CO2/CH4, and CO2/CH4/N2 mixture gas system. Among them, In-MOF-2 shows the highest CO2 uptake capacities at 298 K and simultaneously possesses the low adsorption enthalpy of CO2 (26.4 kJ/mol at low coverage), a feature desirable for low-energy-cost adsorbent regeneration. The CO2/N2 (v: v = 15/85) selectivity of In-MOF-2 reaches 37.6 (at 298 K and 1 bar), also revealing outstanding selective separation ability from flue gases and purifying natural gas, affording a unique robust separation material as it has moderate DOI and pore size. In-MOF-2 shows exceptional stability and feasibility to achieve reproducibility. Aperture adjustment makes In-MOF-2 a versatile platform for selectively capturing CO2 from flue gases or purifying natural gas.

Nickel-Catalyzed Enantioselective Synthesis of Dienyl Sulfoxide.

Sulfoxides are widely used in the pharmaceutical industry and as ligands in asymmetric catalysis. However, the efficient asymmetric synthesis of this structural motif remains limited. In this study, we disclosed a Ni-catalyzed enantioconvergent reaction that utilizes both racemic allenyl carbonates and ß-sulfinyl esters. Our method employs cheap and more sustainable Ni(II) as a precatalyst and successfully overcomes the challenging poisoning effect and instability of sulfenate generated in situ. This enables the synthesis of a series of dienyl sulfoxides with enantioselectivity of up to 98 % ee. The product exhibits tremendous potential in various applications, including diastereoselective Diels-Alder reactions, coordination with transition metals, and incorporation into medicinal compounds, among others. Using a combination of experimental and computational methods, we have uncovered an interesting associated outersphere mechanism that contrasts with conventional mechanisms commonly observed in asymmetric transition metal catalysis.

Molecular characterization of SPL gene family during flower morphogenesis and regulation in blueberry.

The SPL gene is a plant-specific transcription factor involved in the regulation of plant growth and development, which have been identified in woody plants. The process of floral bud differentiation affects the timing of flowering and fruit set and regulates plant growth, however, the mechanism of regulation of flower development by SPL genes is less studied. In this study, 56 VcSPL genes were identified in the tetraploid blueberry. The VcSPL gene family was classified into six subfamilies, and analysis of cis-elements showed that VcSPL genes were regulated by light, phytohormones (abscisic acid, MeJA), and low temperature. In the evolutionary analysis, segmental replication may play an important role in VcSPL gene amplification. Interestingly, we also studied diploid blueberry (Bilberry), in which 24 SPL genes were identified, and 36 homologous pairs were found, suggesting a high degree of convergence in the syntenic relationship between blueberry (Vaccinium corymbosum L) and bilberry (Vaccinium darrowii). Based on the expression profile, VcSPL genes were expressed at high levels in flowers, shoots, and roots, indicating a diversity of gene functions. Then we selected 20 differentially-expressed SPL genes to further investigate the role of VcSPL in floral induction and initiation. It showed that the genes VcSPL40, VcSPL35, VcSPL45, and VcSPL53 may play a crucial role in the blueberry floral transition phase (from vegetative growth to flower initiation). These results provided important information for understanding and exploring the role of VcSPLs in flower morphogenesis and plant growth.

Assembly of Helical Nanostructures: Solvent-Induced Morphology Transition and Its Effect on Cell Adhesion.

Being able to precisely manipulate both the morphology and chiroptical signals of supramolecular assemblies will help to better understand the natural biological self-assembly mechanism. Two simple l/d-phenylalanine-based derivatives (L/DPFM) have been designed, and their solvent-dependent morphology evolutions are illustrated. It was found that, as the content of H2 O in aqueous ethanol solutions was increased, LPFM self-assembles first into right-handed nanofibers, then flat fibrous structures, and finally inversed left-handed nanofibers. Assemblies in ethanol and H2 O exhibit opposite conformations and circular dichroism (CD) signals even though they are constructed from the same molecules. Thus, the morphology-dependent cell adhesion and proliferation behaviors are further characterized. Left-handed nanofibers are found to be more favorable for cell adhesion than right-handed nanostructures. Quantitative AFM analysis showed that the L929 cell adhesion force on left-handed LPFM fibers is much higher than that on structures with inversed handedness. Moreover, the value of cell Young's modulus is lower for left-handed nanofibrous films, which indicates better flexibility. The difference in cell-substrate interactions might lead to different effects on cell behavior.

Characteristics of preoperative atrial fibrillation in geriatric patients with hip fracture and construction of a clinical prediction model: a retrospective cohort study.

INTRODUCTION: Atrial fibrillation is the most common atrial arrhythmia in the perioperative period and is associated with prolonged hospital stay, increased costs, and increased mortality. However, there are few data on the predictors and incidence of preoperative atrial fibrillation in hip fracture patients. Our aim was to identify predictors of preoperative atrial fibrillation and to propose a valid clinical prediction model. METHODS: Predictor variables included demographic and clinical variables. LASSO regression analyzes were performed to identify predictors of preoperative atrial fibrillation, and models were constructed and presented as nomograms. Area under the curve, calibration curve, and decision curve analysis (DCA) were used to examine the discriminative power, calibration, and clinical efficacy of the predictive models. Bootstrapping was used for validation. RESULTS: A total of 1415 elderly patients with hip fractures were analyzed. Overall, 7.1% of patients had preoperative atrial fibrillation, and they were at significant risk for thromboembolic events. Patients with preoperative AF had a significantly longer delay in surgery than those without preoperative atrial fibrillation (p < 0.05). Predictors for preoperative atrial fibrillation were hypertension (OR 1.784, 95% CI 1.136-2.802, p < 0.05), C-reactive protein at admission (OR 1.329, 95% CI 1.048-1.662, p < 0.05), systemic inflammatory response index at admission (OR 2.137, 95% CI, 1.678-2.721 p < 0.05), Age-Adjusted Charlson Comorbidity Index (OR 1.542, 95% CI 1.326-1.794, p < 0.05), low potassium(OR 2.538, 95% CI 1.623-3.968, p < 0.05), anemia(OR 1.542, 95% CI 1.326-1.794, p < 0.05). Good discrimination and calibration effect of the model was showed. Interval validation could still achieve the C-index value of 0.799. DCA demonstrated this nomogram has good clinical utility. CONCLUSION: This model has a good predictive effect on preoperative atrial fibrillation in elderly patients with hip fractures, which can help to better plan clinical evaluation.

Using nitrification inhibitors and deep placement to tackle the trade-offs between NH3 and N2 O emissions in global croplands.

Ammonia (NH3 ) and nitrous oxide (N2 O) are two important air pollutants that have major impacts on climate change and biodiversity losses. Agriculture represents their largest source and effective mitigation measures of individual gases have been well studied. However, the interactions and trade-offs between NH3 and N2 O emissions remain uncertain. Here, we report the results of a two-year field experiment in a wheat-maize rotation in the North China Plain (NCP), a global hotspot of reactive N emissions. Our analysis is supported by a literature synthesis of global croplands, to understand the interactions between NH3 and N2 O emissions and to develop the most effective approaches to jointly mitigate NH3 and N2 O emissions. Field results indicated that deep placement of urea with nitrification inhibitors (NIs) reduced both emissions of NH3 by 67% to 90% and N2 O by 73% to 100%, respectively, in comparison with surface broadcast urea which is the common farmers' practice. But, deep placement of urea, surface broadcast urea with NIs, and application of urea with urease inhibitors probably led to trade-offs between the two gases, with a mitigation potential of -201% to 101% for NH3 and -112% to 89% for N2 O. The literature synthesis showed that deep placement of urea with NIs had an emission factor of 1.53%-4.02% for NH3 and 0.22%-0.36% for N2 O, which were much lower than other fertilization regimes and the default values recommended by IPCC guidelines. This would translate to a reduction of 3.86-5.47 Tg N yr-1 of NH3 and 0.41-0.50 Tg N yr-1 of N2 O emissions, respectively, when adopting deep placement of urea with NIs (relative to current practice) in global croplands. We conclude that the combination of NIs and deep placement of urea can successfully tackle the trade-offs between NH3 and N2 O emissions, therefore avoiding N pollution swapping in global croplands.

Application of integrated management bundle incorporating with multidisciplinary measures improved in-hospital outcomes and early survival in geriatric hip fracture patients with perioperative heart failure: a retrospective cohort study.

BACKGROUND: In elderly, hip fracture is often complicated by perioperative heart failure, related to worse prognosis. We aimed to analyze the effects of integrated management bundle incorporating with multidisciplinary measures on in-hospital outcomes and early survival in elderly hip fracture patients with perioperative heart failure. METHODS: In this retrospective cohort study, a total of 421 hip fracture patients aged 65 and over who developed perioperative heart failure were included. According to different perioperative management modes applied, patients were retrospectively divided into multidisciplinary management group (Group A), including 277 patients, and integrated management bundle group (Group B), including 144 patients. The B-type natriuretic peptide (BNP) and C-reactive protein (CRP) levels, complications, length of stay, and hospitalization costs were observed and compared between two groups. Overall survival was compared by Kaplan-Meier methods. Cox regression analysis was used to identify prognostic factors associated with overall survival. RESULTS: A total of 421 patients were enrolled for analysis, including 277 in Group A and 144 in Group B. BNP and CRP levels were significantly decreased compared with admission (P < 0.05). Furthermore, BNP and CRP in Group B decreased much more than those in Group A (P < 0.05). The reductions were observed in length of stay, hospitalization costs and incidence of pulmonary infection, hypoproteinemia, and acute cerebral infarction in Group B (all P < 0.05). The Kaplan-Meier plots showed significantly superior overall survival in Group B. Integrated management bundle was independent favorable prognostic factors. CONCLUSIONS: The integrated management bundle incorporating with multidisciplinary measures significantly improved the therapeutic effect of perioperative heart failure, reduced inflammatory response, and yielded better hospital outcomes. It brought better survival benefits for geriatric hip fracture patients with perioperative heart failure. The results of this study can play an important role in clinical work and provide a valuable theoretical basis for selection of management model in elderly hip fracture patients with perioperative heart failure.

Characteristics and perioperative complications of hip fracture in the elderly with acute ischemic stroke: a cross-sectional study.

BACKGROUND: Patients with acute ischemic stroke (AIS) after hip fracture in the elderly have worse prognosis. We aimed to describe the characteristics and complications of hip fracture with AIS in the elderly. METHODS: This cross-sectional study selected patients with hip fracture (age ≥65 years) from January 2018 to September 2020. The collected data included age, sex, fracture types, comorbidities. In above screened patients, we further collected cerebral infarction related information of AIS patients. The least absolute shrinkage and selection operator (LASSO) logistic regression was performed to identify the strongest predictors of AIS after hip fracture. Multivariate logistic regression analysis was conducted to find independent risk factors for AIS after hip fracture. RESULTS: Sixty patients (mean age 79.7 years;female 56.7%) occurred AIS after hip fracture in 1577 cases. The most common infarction type was partial anterior circulation infarction (PACI) (70.0%). The majority of these infarction lesions were single (76.7%) and most infarction lesions(65.0%) were located in the left side. 81.7% of AIS patients had mild (Health stroke scale NIHSS <4) AIS. Older patients with AIS after hip fracture were more frequently complicated by hypertension(73.3%), prior stroke (46.7%), diabetes(35.0%) and were more likely to have hypoproteinemia(68.3%), electrolyte disorders ( 66.7%), anemia (65.0%), deep vein thrombosis (51.6%), pneumonia (46.6%),cardiac complications (45.0%). Combined with hypertension (OR 2.827, 95%CI 1.557-5.131) and male sex(OR 1.865, 95%CI 1.095-3.177) were associated with the increased risk of AIS after hip fracture. CONCLUSIONS: Older patients combined with hypertension are more likely to have AIS after hip fracture. For these patients, early preventions should be administered. AIS patients after hip fracture are prone to have multiple complications under traumatic stress, and we should enhance the management of these patients to reduce the stress and avoid occurrence of complications.

Effect of integrated management bundle on 1-year overall survival outcomes and perioperative outcomes in super elderly patients aged 90 and over with hip fracture: non-concurrent cohort study.

BACKGROUND: Due to concomitant factors like frailty and comorbidity, super elderly (≥90 years) patients with hip fracture differ from patients aged 65-89 years in perioperative complications and mortality. The integrated management bundle referred to bundled application of multiple clinical measures. The aim of this study was to analyze effect of integrated management bundle on 1-year overall survival and perioperative outcomes in super elderly patients with hip fracture, with multidisciplinary management group serving as the control group. METHODS: In this retrospective cohort study, super elderly patients with hip fracture were included from Jan 2017 to Nov 2020. Patients were retrospectively divided to multidisciplinary management group and integrated management bundle group. The primary outcome was 1- year overall survival, and the secondary outcome was perioperative outcomes. Kaplan-Meier methods was used to compare survival probability. Multivariable Cox's modeling was used to explain the effect of integrated bundle on 1-year overall survival adjusted for confounders. The perioperative outcomes including complications and in-hospital data of two groups were compared. The multivariable logistic regression was used to explain the effect of integrated bundle on the occurrence of perioperative complications adjusted for confounders. Prognostic factors related to survival was identified by multivariable Cox's regression analysis. RESULTS: Ninety-seven patients comprised multidisciplinary management group, and 83 comprised integrated management bundle group. The Kaplan-Meier plots showed that the survival probability of integrated management bundle group was significantly better than multidisciplinary management group (HR:0.435, 95%CI:0.207-0.914, P = 0.039). Multivariable analysis after adjustment for confounders showed a 42.8% lower incidence of mortality integrated management bundle group than multidisciplinary management group (HR:0.428, 95%CI:0.186-0.986, P = 0.046). Incidence of hypoproteinemia, and electrolyte disturbance in integrated management bundle group was significantly lower than multidisciplinary management group (all P < 0.05). In addition, significant reduction was observed in length of stay (P < 0.05) in integrated management bundle group. Multivariable logistic regression showed integrated management bundle was independent protective factor of hypoproteinemia, and electrolyte disturbance. mECM score ≥ 6 and ASA score > 2 were independent risk factors of overall survival (HR: 1.940, 95%CI: 1.067-3.525,P = 0.030; HR: 2.281, 95%CI: 1.113-4.678,P = 0.024). CONCLUSIONS: The integrated management bundle improved 1-year overall survival and played positive effects in improving perioperative outcomes. It might be a more suitable management modality for super elderly patients with hip fracture.

Enantioselective Reductive Divinylation of Unactivated Alkenes by Nickel-Catalyzed Cyclization Coupling Reaction.

Catalytic asymmetric dicarbofunctionalization of tethered alkenes has emerged as a promising tool for producing chiral cyclic molecules; however, it typically relies on aryl-tethered alkenes to form benzene-fused compounds. Herein, we report an enantioselective cross-electrophile divinylation reaction of nonaromatic substrates, 2-bromo-1,6-dienes. The approach thus offers a route to new chiral cyclic architectures, which are key structural motifs found in various biologically active compounds. The reaction proceeds under mild conditions, and the use of chiral t-Bu-pmrox and 3,5-difluoro-pyrox ligands resulted in the formation of divinylated products with high chemo-, regio-, and enantioselectivity. The method is applicable for the incorporation of chiral hetero- and carbocycles into complex molecules.

The interplay between thermodynamics and kinetics in the solid-state synthesis of layered oxides.

In the synthesis of inorganic materials, reactions often yield non-equilibrium kinetic byproducts instead of the thermodynamic equilibrium phase. Understanding the competition between thermodynamics and kinetics is a fundamental step towards the rational synthesis of target materials. Here, we use in situ synchrotron X-ray diffraction to investigate the multistage crystallization pathways of the important two-layer (P2) sodium oxides Na0.67MO2 (M = Co, Mn). We observe a series of fast non-equilibrium phase transformations through metastable three-layer O3, O3' and P3 phases before formation of the equilibrium two-layer P2 polymorph. We present a theoretical framework to rationalize the observed phase progression, demonstrating that even though P2 is the equilibrium phase, compositionally unconstrained reactions between powder precursors favour the formation of non-equilibrium three-layered intermediates. These insights can guide the choice of precursors and parameters employed in the solid-state synthesis of ceramic materials, and constitutes a step forward in unravelling the complex interplay between thermodynamics and kinetics during materials synthesis.

Rational Fabrication of Multiple Dimensional Assemblies from Tryptophan-Based Racemate.

Fabricating structural complex assemblies from simple amino acid-based derivatives is attracting great research interests due to their easy accessibility and preparation. However, the morphological regulation of racemates (an equimolar mixture of enantiomers) were largely overlooked. In this work, through rational modulation of kinetic and thermodynamic parameters, we achieved multiple dimensional architectures employing tryptophan-based racemate (RPWM). Upon assembling, 1D bundled nanofibers, 2D lamellar nanostructure and 3D urchin-like microflowers could be obtained depending on the solvents used. The corresponding morphology evolutions were successfully illustrated by changing the enantiomeric excess (ee) value. Moreover, for RPWM, uniform 0D nanospheres were formed in H2 O under 4 °C, which could spontaneously convert into lamella under ambient temperature. Taking advantages of its temperature-responsive phase change behavior, RPWM assemblies exhibited excellent removal efficiency for organic dye RhB, and could be reused for several consecutive cycles without significant changes in its removal performance. Taken together, it's rational to envision that the engineering of racemates assembly pathways can greatly increase the robustness in a wide variety of supramolecular materials and further lead to their blooming versatile applications.

Effect of Stereochemistry on Chirality and Gelation Properties of Supramolecular Self-Assemblies.

Although chiral nanostructures have been fabricated at various structural levels, the transfer and amplification of chirality from molecules to supramolecular self-assemblies are still puzzling, especially for heterochiral molecules. Herein, four series of C2 -symmetrical dipeptide-based derivatives bearing various amino acid sequences and different chiralities are designed and synthesized. The transcription and amplification of molecular chirality to supramolecular assemblies are achieved. The results show that supramolecular chirality is only determined by the amino acid adjacent to the benzene core, irrespective of the absolute configuration of the C-terminal amino acid. In addition, molecular chirality also has a significant influence on the gelation behavior. For the diphenylalanine-based gelators, the homochiral gelators can be gelled through a conventional heating-cooling process, whereas heterochiral gelators form translucent stable gels under sonication. The racemic gels possess higher mechanical properties than those of the pure enantiomers. All of these results contribute to an increasing knowledge over control of the generation of specific chiral supramolecular structures and the development of new optimized strategies to achieve functional supramolecular organogels through heterochiral and racemic systems.

Highly Photoluminescent CsPbBr3/CsPb2Br5 NCs@TEOS Nanocomposite in Light-Emitting Diodes.

All-inorganic halide perovskite (CsPb2Br5) nanocrystals (NCs) have received widespread attention owing to their unique photoelectric properties. This work reports a novel strategy to control the phase transition from CsPbBr3 to CsPb2Br5 and investigates the effects of different treatment times and treatment temperatures on perovskite NCs formation. By controlling the volume of tetraethoxysilane (TEOS) added, the formation of different phases of perovskite powder can be well controlled. In addition, a white light-emitting diode (WLED) device is designed by coupling the CsPbBr3/CsPbBr3-CsPb2Br5 NCs@TEOS nanocomposite and CaAlSiN3:Eu2+ commercial phosphor with a 460 nm InGaN blue chip, exhibiting a high luminous efficiency of 57.65 lm/W, color rendering index (CRI) of 91, and a low CCT of 5334 K. The CIE chromaticity coordinates are (0.3363, 0.3419). This work provides a new strategy for the synthesis of CsPbBr3/CsPbBr3-CsPb2Br5 NCs@TEOS nanocomposite, which can be applied to the field of WLEDs and display devices.

Solvent-Controlled Topological Evolution from Nanospheres to Superhelices.

Supramolecular assemblies with diverse morphologies are crucial in determining their biochemical or physical properties. However, the topological evolution and self-assembly intermediates as well as the mechanism remain elusive. Herein, a dynamic morphological evolution from solid nanospheres to superhelical nanofibers is revealed via self-assembly of a minimal l-tryptophan-based derivative (LPWM) with various mixed solvent combinations, including the formation of solid nanospheres, the fusion of nanospheres into pearling necklace, the disintegration of necklace into short nanofibers, the distortion of nanofibers into nanotwists, and the entanglement of nanotwists into superhelices. It is found that the breakage of intramolecular H-bonds and reconstruction of intermolecular H-bonds, as well as the variation of aromatic interactions and hydrophobic effects, are the key driving forces for topological transformation, especially the dimensional evolution. The nanospheres and nanofibers demonstrate discrepant behaviors towards mouse neural stem cell (NSC) differentiation that compared with negligible impact of nanospheres scaffold, the nanofibers scaffold is favorable for NSC differentiation into neurons. The remarkable dynamic regulation of assembly process, together with the NSC differentiation on twisted nanofibers are making this system an ideal model to interpret complex proteins fibrillation processes and investigate the structure-function relationship.

Visible Enantiomer Discrimination via Diphenylalanine-Based Chiral Supramolecular Self-Assembly on Multiple Platforms.

The development of enantioselective recognition is of great significance in medical science and pharmaceutical industry, which associates with the molecular recognition phenomenon widely observed in biological systems. In particular, the facile and straight achievement of visual enantioselective recognition has been drawing increasing consideration, but it is still a challenge. Herein, a heterochiral diphenylalanine-based gelator (LFDF) is synthesized, presenting left-handed nanofibers during self-assembly in ethanol, which accomplishes the phenylalaninol enantiomer recognition on multiple platforms. When adding l- or d-phenylalaninol into LFDF supramolecular solution followed by ultrasonic treatment, precipitate and gel are formed, respectively. Meanwhile, LFDF supramolecular gel completely collapses in a minute after dropping l-phenylalaninol, while the gel almost remains when d-type is employed. Moreover, a fluorescent supramolecular xerogel (ThT-LFDF) is fabricated by combining the LFDF gelator with thioflavine T (ThT), which could detect l-phenylalaninol accompanying with fluorescence quenching while d-type with barely decreasing. And the ThT-LFDF xerogel system shows a good sensitivity (reaches to ppm) for the detection of l-phenylalaninol. It is found that the chirality of the assembled nanofibers, as well as amino and carboxyl of phenylalaninol, plays a critical role on the discrimination process. The multiple and visible enantioselective recognition of phenylalaninol through chiral supramolecular self-assemblies shows potential applications in the fields of medical science and pharmaceutical industry.

Ni-Catalyzed Asymmetric Allylation of Secondary Phosphine Oxides.

A nickel-catalyzed asymmetric allylation of secondary phosphine oxides (SPO) for the synthesis of tertiary phosphine oxides (TPO) was realized with high enantioselectivity. The dynamic kinetic asymmetric transformation of SPO was accomplished in the presence of nickel complex. By elucidating the absolute configurations of the reacted SPO starting material and the TPO product, we confirmed that the allylation reaction proceeded through a P-stereo retention process. The protocol represents the first example of synthesizing P-stereogenic phosphine oxides by allylation reaction.