Substituent Positioning Effects on the Magnetic Properties of Sandwich-Type Erbium(III) Complexes with Bis(trimethylsilyl)-Substituted Cyclooctatetraenyl Ligands.

Lanthanide complexes with judiciously designed ligands have been extensively studied for their potential applications as single-molecule magnets. With the influence of ligands on their magnetic properties generally established, recent research has unearthed certain effects inherent to site differentiation due to the different types and varying numbers of substituents on the same ligand platform. Using two new sandwich-type Er(III) complexes with cyclooctatetraenyl (COT) ligands featuring two differently positioned trimethylsilyl (TMS) substituents, namely, [Li(DME)Er(COT1,5-TMS2)2]n (Er1) and [Na(DME)3][Er(COT1,3-TMS2)2] (Er2) [COT1,3-TMS2 and COT1,5-TMS2 donate 1,3- and 1,5-bis(trimethylsilyl)-substituted cyclooctatetraenyl ligands, respectively; DME = 1,2-dimethoxyethane], and with reference to previously reported [Li(DME)3][Er(COT1,4-TMS2)2] (A) and [K(DME)2][Er(COT1,4-TMS2)2] (B), any possible substituent position effects have been explored for the first time. The rearrangement of the TMS substituents from the starting COT1,4-TMS2 to COT1,3-TMS2 and COT1,5-TMS2, by way of formal migration of the TMS group, was thermally induced in the case of Er1, while for the formation of Er2, the use of Na+ in the placement of its Li+ and K+ congeners is essential. Both Er1 and Er2 display single-molecule magnetic behaviors with energy barriers of 170(3) and 172(6) K, respectively. Magnetic hysteresis loops, butterfly-shaped for Er1 and wide open for Er2, were observed up to 12 K for Er1 and 13 K for Er2. Studies of magnetic dynamics reveal the different pathways for relaxation of magnetization below 10 K, mainly by the Raman process for Er1 and by quantum tunneling of magnetization for Er2, leading to the order of magnitude difference in magnetic relaxation times and sharply different magnetic hysteresis loops.

Two-Electron Oxidations at a Single Cerium Center.

Two-electron oxidations are ubiquitous and play a key role in the synthesis and catalysis. For transition metals and actinides, two-electron oxidation often takes place at a single-metal site. However, redox reactions at rare-earth metals have been limited to one-electron processes due to the lack of accessible oxidation states. Despite recent advancements in nontraditional oxidation state chemistry, the low stability of low-valent compounds and large disparity among different oxidation states prevented the implementation of two-electron processes at a single rare-earth metal center. Here we report two-electron oxidations at a cerium(II) center to yield cerium(IV) terminal oxo and imido complexes. A series of cerium(II-IV) complexes supported by a tripodal tris(amido)arene ligand were synthesized and characterized. Experimental and theoretical studies revealed that the cerium(II) complex is best described as a 4f2 ion stabilized by δ-backdonation to the anchoring arene, while the cerium(IV) oxo and imido complexes exhibit multiple bonding characters. The accomplishment of two-electron oxidations at a single cerium center brings a new facet to molecular rare-earth metal chemistry.

NtMYB305a binds to the jasmonate-responsive GAG region of NtPMT1a promoter to regulate nicotine biosynthesis.

MYB transcription factors play essential roles in regulating plant secondary metabolism and jasmonate (JA) signaling. Putrescine N-methyltransferase is a key JA-regulated step in the biosynthesis of nicotine, an alkaloidal compound highly accumulated in Nicotiana spp. Here we report the identification of NtMYB305a in tobacco (Nicotiana tabacum) as a regulatory component of nicotine biosynthesis and demonstrate that it binds to the JA-responsive GAG region, which comprises a G-box, an AT-rich motif, and a GCC-box-like element, in the NtPMT1a promoter. Yeast one-hybrid analysis, electrophoretic mobility shift assay and chromatin immunoprecipitation assays showed that NtMYB305a binds to the GAG region in vitro and in vivo. Binding specifically occurs at the ∼30-bp AT-rich motif in a G/C-base-independent manner, thus defining the AT-rich motif as previously unknown MYB-binding element. NtMYB305a localized in the nucleus of tobacco cells where it is capable of activating the expression of a 4×GAG-driven GUS reporter in an AT-rich motif-dependent manner. NtMYB305a positively regulates nicotine biosynthesis and the expression of NtPMT and other nicotine pathway genes. NtMYB305a acts synergistically with NtMYC2a to regulate nicotine biosynthesis, but no interaction between these two proteins was detected. This identification of NtMYB305a provides insights into the regulation of nicotine biosynthesis and extends the roles played by MYB transcription factors in plant secondary metabolism.

Ethylene inhibits ABA-induced stomatal closure via regulating NtMYB184-mediated flavonol biosynthesis in tobacco.

Stomatal movement can be regulated by ABA signaling through synthesis of reactive oxygen species (ROS) in guard cells. By contrast, ethylene triggers the biosynthesis of antioxidant flavonols to suppress ROS accumulation and prevent ABA-induced stomatal closure; however, the underlying mechanism remains largely unknown. In this study, we isolated and characterized the tobacco (Nicotiana tabacum) R2R3-MYB transcription factor NtMYB184, which belongs to the flavonol-specific SG7 subgroup. RNAi suppression and CRISPR/Cas9 mutation (myb184) of NtMYB184 in tobacco caused down-regulation of flavonol biosynthetic genes and decreased the concentration of flavonols in the leaves. Yeast one-hybrid assays, transactivation assays, EMSAs, and ChIP-qPCR demonstrated that NtMYB184 specifically binds to the promoters of flavonol biosynthetic genes via MYBPLANT motifs. NtMYB184 regulated flavonol biosynthesis in guard cells to modulate ROS homeostasis and stomatal aperture. ABA-induced ROS production was accompanied by the suppression of NtMYB184 and flavonol biosynthesis, which may accelerate ABA-induced stomatal closure. Furthermore, ethylene stimulated NtMYB184 expression and flavonol biosynthesis to suppress ROS accumulation and curb ABA-induced stomatal closure. In myb184, however, neither the flavonol and ROS concentrations nor the stomatal aperture varied between the ABA and ABA+ethylene treatments, indicating that NtMYB184 was indispensable for the antagonism between ethylene and ABA via regulating flavonol and ROS concentrations in the guard cells.

Piezochromism and Conductivity Modulations under High Pressure by Manipulating the Viologen Radical Concentration.

Manipulating the radical concentration to modulate the properties in solid multifunctional materials is an attractive topic in various frontier fields. Viologens have the unique redox capability to generate radical states through reversible electron transfer (ET) under external stimuli. Herein, taking the viologens as the model, two kinds of crystalline compounds with different molecule-conjugated systems were designed and synthesized. By subjecting the specific model viologens to pressure, the cross-conjugated 2-X all exhibit much higher radical concentrations, along with more sensitive piezochromic behaviors, compared to the linear-conjugated 1-X. Unexpectedly, we find that the electrical resistance (R) of 1-NO3 decreased by three orders of magnitude with the increasing pressure, while that in high-radical-concentration 2-NO3 remained almost unchanged. To date, such unusual invariant conductivity has not been documented in molecular-based materials under high pressure, breaking the conventional wisdom that the generations of radicals are beneficial to improve conductivity. We highlight that adjusting the molecular conjugation modes can be used as an effective way to regulate the radical concentrations and thus modulate properties rationally.

Tunable Chromic Properties of Viologen-Metal Polymers Modulated by Coordination Modes for Inkless Erasable Printing.

Inkless and erasable printing (IEP) based on chromic materials holds great promise to alleviate environmental and sustainable problems. Metal-organic polymers (MOPs) are bright platforms for constructing IEP materials. However, it is still challenging to design target MOPs with excellent specific functions rationally due to the intricate component-structure-property relationships. Herein, an effective strategy was proposed for the rational design IEP-MOP materials. The stimuli-responsive viologen moiety was introduced into the construction of MOPs to give it potential chromic behaviors and two different coordination models (i. e. bilateral coordination model, M1 ; unilateral coordinated model, M2 ) based on the same viologen ligand were designed. Aided by theoretical calculations, model M1 was recommended secondarily as a more suitable system for IEP materials. Along this line, two representative viologen-ZnII MOPs 1 and 2 with models M1 and M2 were synthesized successfully. Experiments exhibit that 1 does have quicker stimuli response, stronger color contrast and longer radical lifetime compared to 2. Significantly, the obtained 1-IEP media brightly inherits the excellent chromic characteristics of 1 and the flexibility of the paper at the same time, which achieves most daily printing requirements, as well as enough resolution and durability to be used in identification by smart device.

Adaptability to Crystal Fields in a Series of COT/Monodentate Ligand-Based Dy and Er Single Ion Magnets.

Herein, DyIII and ErIII, the typical oblate and prolate Kramers Ln ions, were employed to synthesize a series of isostructural pairs: 2-5Ln (Ln = Dy and Er). In the [(COT)Ln(THF)4]+ cationic fragments of 2Ln, central ions were coordinated by the equatorial ligand cyclooctatetraenyl (COT) and THF solvents, while in the heteroleptic complexes 3Ln ((COT)Ln(OAr')), 4Ln ((COT)Ln(OAr″)), and 5Ln ((COT)Ln(N††)), the coordination geometries were formed by the cooperation of COT and bulky aryloxides OAr' (2,6-bis(diphenylmethyl)-4-methylphenyl), OAr″ (2,6-bis(1-adamantyl)-4-methylphenyl), and amide N†† (bis(triisopropylsilyl) amide) for 3Ln, 4Ln, and 5Ln, respectively. Among these complexes, with the combinations of varying coordination geometries and different anisotropies of f orbitals, 2Er, 3Dy, and 4Dy were found to be zero-field SIMs with effective energy barriers of 181.9, 527.7, and 622.0 K, respectively, which are consistent with the structural analyses and ab initio calculations. The blocking temperatures (TB) of 3Dy and 4Dy are 4 and 7 K, respectively, as confirmed by the hysteresis loops at varying temperatures. The structures of 5Ln exhibit an almost perfect umbrella-shaped geometry, characterized by N-Ln-Centroid (COT) angles measuring 178.9 and 179.3° for 5Dy and 5Er, respectively. Crystallographic data from these structures were utilized to investigate the impact of ligand alignment on the magnetic properties of the compounds.

Two Pairs of Homochiral Parallelogram-like Dy4 Cluster Complexes with Strong Magneto-Optical Properties.

Two pairs of homochiral Dy(III) tetranuclear cluster complexes derived from (+)/(-)-3-trifluoroacetyl camphor (D-Htfc/L-Htfc), [Dy4(OH)2(L1)4(D-tfc)2(DMF)2]·4DMF (D-1) [H2L1 = (E)-2-(2-hydroxy-3-methoxybenzylideneamino)phenol)]/[Dy4(OH)2(L1)4(L-tfc)2(DMF)2]·4DMF (L-1) and [Dy4(OH)2(L2)4(D-tfc)2(DMF)2]·2H2O·3MeCN (D-2) [H2L2 = (E)-3-(2-hydroxy-3-methoxybenzylideneamino)naphthalen-2-ol]/[Dy4(OH)2(L2)4(L-tfc)2(DMF)2]·2H2O·3MeCN (L-2), were synthesized at room temperature, which have a Dy4 parallelogram-like core. The magnetic studies revealed that D-1 exhibits single-molecule magnet (SMM) behavior under zero dc magnetic field, and its magnetic relaxation has a distinct Raman process in addition to the Orbach process, with the Ueff/k value of 57.5 K and the C value of 28.27 s-1K-2.14; while D-2 displays dual magnetic relaxation behavior at 0 Oe field, with the Ueff/k value 114.8 K for the slow relaxation process (SR) and the C value of 10.656 s-1K-5.80 for the fast relaxation process (FR), respectively. Theoretical calculations indicated that the conjugated groups (phenyl vs naphthyl) of the Schiff base bridging ligands (H2L1 and H2L2) significantly affect the intramolecular magnetic interactions between the Dy3+ ions and ultimately lead to different relaxations. Furthermore, magnetic circular dichroism (MCD) measurements showed that these two pairs of Dy4 enantiomers exhibit strong room temperature magneto-optical Faraday effects; notably, increasing the conjugated group on the Schiff base bridging ligand is beneficial to enhancing the magneto-optical Faraday effects.

A Combined Synthetic, Magnetic, and Theoretical Study on Enhancing Ligand-Field Axiality for Dy(III) Single-Molecule Magnets Supported by Ferrocene Diamide Ligands.

Molecular design is crucial for improving the performance of single-molecule magnets (SMMs). For dysprosium(III) SMMs, enhancing ligand-field axiality is a well-suited strategy to achieve high-performance SMMs. We synthesized a series of dysprosium(III) complexes, (NNTIPS)DyBr(THF)2 (1, NNTIPS = fc(NSiiPr3)2; fc = 1,1'-ferrocenediyl, THF = tetrahydrofuran), [(NNTIPS)Dy(THF)3][BPh4] (2), (NNTIPS)DyI(THF)2 (3), and [(NNTBS)Dy(THF)3][BPh4] (4, NNTBS = fc(NSitBuMe2)2), supported by ferrocene diamide ligands. X-ray crystallography shows that the rigid ferrocene backbone enforces a nearly axial ligand field with weakly coordinating equatorial ligands. Dysprosium(III) complexes 1-4 all exhibit slow magnetic relaxation under zero fields and possess high effective barriers (Ueff) around 1000 K, comparable to previously reported (NNTBS)DyI(THF)2 (5). We probed the influences of structural variations on SMM behaviors by theoretical calculations and found that the distribution of negative charges defined by rq, i.e., the ratio of the charges on the axial ligands to the charges on the equatorial ligands, plays a decisive role. Moreover, theoretical calculations on a series of model complexes 1'-5' without equatorial ligands unveil that the axial crystal-field parameters B20 are directly proportional to the N-Dy-N angles and support the hypothesis that enhancing the ligand-field axiality could improve SMM performance.

A phase III randomized, double-blind, placebo-controlled trial of the denosumab biosimilar QL1206 in postmenopausal Chinese women with osteoporosis and high fracture risk.

The current study evaluated the efficacy and safety of a denosumab biosimilar, QL1206 (60 mg), compared to placebo in postmenopausal Chinese women with osteoporosis and high fracture risk. At 31 study centers in China, a total of 455 postmenopausal women with osteoporosis and high fracture risk were randomly assigned to receive QL1206 (60 mg subcutaneously every 6 months) or placebo. From baseline to the 12-month follow-up, the participants who received QL1206 showed significantly increased bone mineral density (BMD) values (mean difference and 95% CI) in the lumbar spine: 4.780% (3.880%, 5.681%), total hip :3.930% (3.136%, 4.725%), femoral neck 2.733% (1.877%, 3.589%) and trochanter: 4.058% (2.791%, 5.325%) compared with the participants who received the placebo. In addition, QL1206 injection significantly decreased the serum levels of C-terminal crosslinked telopeptides of type 1 collagen (CTX): -77.352% (-87.080%, -66.844%), and N-terminal procollagen of type l collagen (P1NP): -50.867% (-57.184%, -45.217%) compared with the placebo over the period from baseline to 12 months. No new or unexpected adverse events were observed. We concluded that compared with placebo, QL1206 effectively increased the BMD of the lumbar spine, total hip, femoral neck and trochanter in postmenopausal Chinese women with osteoporosis and rapidly decreased bone turnover markers. This study demonstrated that QL1206 has beneficial effects on postmenopausal Chinese women with osteoporosis and high fracture risk.

The Value of Intraoperative Computed Tomography in the Treatment of Zygomatic Complex Fractures.

BACKGROUND: Due to the complex anatomical morphology and lack of anatomic markers on the surface of zygomatic complex (ZMC), the treatment results of ZMC fractures are often suboptimal. PURPOSE: The study aimed to evaluate the effectiveness of intraoperative computed tomography (ICT) in the treatment of unilateral ZMC fractures, and further study the feasibility of ICT to replace early postoperative Computed Tomography (CT). STUDY DESIGN, SETTING, AND SAMPLE: The investigators designed a retrospective cohort study. Adult patients who underwent surgery with unilateral ZMC fractures were enrolled. PREDICTOR VARIABLE: According to whether intraoperative CT was used, the subjects were divided into the ICT group and the control group (without ICT). MAIN OUTCOME VARIABLES: Five distances and 3 angles representing bilateral ZMC symmetry were main outcome variables. The differences of outcome variables were compared between the 2 groups and the indices of ICT group were further compared with their postoperative indices. COVARIATES: Demographics (eg age), etiology (eg traffic injury), dysfunction (eg diplopia), and surgical approach (eg vestibular incision) were collected as covariates while we conducted clinical investigation, examination, and implementation. ANALYSES: The data were analyzed using independent-samples t test, paired-samples t test, Mann-Whitney U test, and χ2 test. P value < .05 was considered statistically significant. RESULTS: A total of 60 patients (18 to 59 years) were enrolled in this study. All median values of the measurements in the ICT group were smaller than those in the control group, and the differences of horizontal displacement distance (0.56 vs 1.02 mm), anteroposterior displacement distance (1.69 vs 2.34 mm, 0.90 vs 2.35 mm), horizontal angle of bilateral zygomatic arch (2.31 vs 4.19°), and horizontal angle of bilateral zygomatic process (1.77 vs 2.94°) were significantly different between the 2 groups with P value < .05. Moreover, there was no statistically significant difference in all indices between the intraoperatively and postoperatively injured sides in the ICT group. CONCLUSIONS: ICT can improve the treatment outcomes of ZMC fractures by evaluating the fracture reduction adequacy during surgery. Moreover, ICT can replace early postoperative CT.

The Role of Intraoperative Navigation in Surgical Treatment of Unilateral Zygomatic Complex Fractures: A Systematic Review and Meta-Analysis.

PURPOSE: The application of a computer-aided navigation system (CANS) in zygomatic complex (ZMC) fractures has been extensively reported, but individual results are heterogeneous. The purpose of this systematic review was to evaluate the role of CANS in the surgical treatment of unilateral ZMC fractures. METHODS: Electronic retrieval of MEDLINE, Embase, and Cochrane Library (CENTRAL) and manual searching until November 1, 2022 were used to identify cohort studies and randomized controlled trials employing CANS in the surgical treatment of ZMC fractures. The identified reports contained at least 1 of the following outcome variables: accuracy of reduction, total treatment time, amount of bleeding, postoperative complications, satisfaction, and cost. Weighted or mean differences (MD), risk ratios, and corresponding 95% confidence intervals (CI) were calculated, where P＜.05 and I2＞50% random-effect model was adopted, and a vice versa fixed-effect model was adopted. Descriptive analysis was applied to qualitative statistics. The protocol was conducted in accordance with the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines and prospectively registered with PROSPERO (CRD42022373135). RESULTS: A total of 562 studies were identified, of which 2 cohort studies and 3 randomized controlled trials with 189 participants were included. Meta-analysis indicated that employing CANS significantly decreased the reduction error (MD = -0.86, 95% CI -1.58 to -0.14; P = .02, random-effect model) compared with conventional surgery without using CANS. The differences in total treatment time (preoperative planning time: MD = 1.44, 95% CI -3.55 to 6.43; P = .57 and operative time: MD = 3.02, 95% CI -9.21 to 15.26; P = .63, fixed-effect model) and amount of bleeding (MD = 14.86, 95% CI -8.86 to 38.58; P = .22, fixed-effect model) were not statistically significant between the two groups. Descriptive analysis suggested that postoperative complications, postoperative satisfaction, and cost were also similar with or without CANS. CONCLUSION: Within the limitations of the present review, the reduction accuracy of unilateral ZMC fractures using CANS is superior to that of conventional surgery. CANS presents limited influence on operation time, amount of bleeding, postoperative complications, postoperative satisfaction, and cost.

Delayed Doublet Emission in a Cerium(III) Complex.

Doublet emission from open-shell molecules has demonstrated its research and application value in recent years. However, understandings of the photoluminescence mechanism of open-shell molecules are far less than that of closed-shell molecules, leading to challenges in molecular design of efficient doublet emission systems. Here we report a cerium(III) 4-(9H-carbozol-9-yl)phenyl-tris(pyrazolyl)borate complex Ce(CzPhTp)3 with a new luminescence mechanism of delayed doublet emission, which also represents the first example with metal-centered delayed photoluminescence. The energy gap between the doublet and triplet excited states of Ce(CzPhTp)3 is reduced by the management of the inner and outer coordination spheres, thereby promoting efficient energy transfer between the two excited states and activating the delayed emission. The photoluminescence mechanism discovered may provide a new way for the design of efficient doublet emission and bring insights into rational molecular design and energy level regulation in open-shell molecules.

Identification of a small-molecule RPL11 mimetic that inhibits tumor growth by targeting MDM2-p53 pathway.

BACKGROUND: Targeting ribosome biogenesis to activate p53 has recently emerged as a therapeutic strategy in human cancer. Among various ribosomal proteins, RPL11 centralizes the nucleolar stress-sensing pathway by binding MDM2, leading to MDM2 inactivation and p53 activation. Therefore, the identification of MDM2-binding RPL11-mimetics would be valuable for anti-cancer therapeutics. METHODS: Based on the crystal structure of the interface between RPL11 and MDM2, we have identified 15 potential allosteric modulators of MDM2 through the virtual screening. RESULTS: One of these compounds, named S9, directly binds MDM2 and competitively inhibits the interaction between RPL11 and MDM2, leading to p53 stabilization and activation. Moreover, S9 inhibits cancer cell proliferation in vitro and in vivo. Mechanistic study reveals that MDM2 is required for S9-induced G2 cell cycle arrest and apoptosis, whereas p53 contributes to S9-induced apoptosis. CONCLUSIONS: Putting together, S9 may serve as a lead compound for the development of an anticancer drug that specifically targets RPL11-MDM2-p53 pathway.

Observation of Biradical Spin Coupling through Hydrogen Bonds.

Investigation of intermolecular electron spin interaction is of fundamental importance in both science and technology. Here, radical pairs of all-trans retinoic acid molecules on Au(111) are created using an ultralow temperature scanning tunneling microscope. Antiferromagnetic coupling between two radicals is identified by magnetic-field-dependent spectroscopy. The measured exchange energies are from 0.1 to 1.0 meV. The biradical spin coupling is mediated through O─H⋯O hydrogen bonds, as elucidated from analysis combining density functional theory calculation and a modern version of valence bond theory.

Effects of Counterions, Coordination Anions, and Coordination Solvent Molecules on Single-Molecule Magnetic Behaviors and Nonlinear Optical Properties of Chiral Zn2Dy Schiff Base Complexes.

By changing the counterions (ClO4- and CF3SO3-) and the coordination anions (Cl- and Br-), we investigated their influences on the structures and performances of a class of Zn2Dy chiral single-molecule magnets (SMMs), which are based on a pair of chiral Schiff bases R,R-H2LSchiff and S,S-H2LSchiff {R,R-H2LSchiff = 2-((E)-((1R,2R)-2-((E)-2-hydroxy-3-methoxybenzylideneamino)cyclohexylimino)methyl)-6-methoxyphenol and S,S-H2LSchiff = 2-((E)-((1S,2S)-2-((E)-2-hydroxy-3-methoxybenzylideneamino)cyclohexylimino)methyl)-6-methoxyphenol}. Three pairs of chiral Zn2Dy Schiff base complexes were obtained by directed synthesis, which are [DyZn2(R,R-LSchiff)Cl2(H2O)](ClO4)·0.5MeOH·0.25H2O (R-1) and [DyZn2(S,S-LSchiff)Cl2(H2O)][DyZn2(S,S-LSchiff)Cl2(MeOH)](ClO4)2·MeOH·0.5H2O (S-1), [DyZn2(R,R-LSchiff)Cl2(H2O)](CF3SO3)·0.5MeOH (R-2) and [DyZn2(S,S-LSchiff)Cl2(H2O)][DyZn2(S,S-LSchiff)Cl2(MeOH)](CF3SO3)2·MeOH (S-2), and [DyZn2(R,R-LSchiff)Br2(H2O)](CF3SO3)·0.25MeOH (R-3) and [DyZn2(S,S-LSchiff)Br2(H2O)][DyZn2(S,S-LSchiff)Br2(MeOH)](CF3SO3)2 (S-3). They all exhibit good SMM behaviors, and their magnet relaxation is regulated by not only the counterions (ClO4- and CF3SO3-) but also the coordination anions (Cl- and Br-); these anions also have important effects on the second-harmonic generation (SHG) and third harmonic generation (THG) nonlinear optical properties. Interestingly, in the S-configuration complexes, the coordination solvent molecule of the Dy3+ ion on half of the molecules is the methanol molecule instead of the water molecule. This change in the coordinating solvent molecule can also significantly affect the SMM behaviors and the SHG and THG nonlinear optical properties. Moreover, ab initio calculations were applied to rationally explain the SMM properties.

Molecularly imprinted monoliths: Recent advances in the selective recognition of biomacromolecules related biomarkers.

Biomarkers are significant indicators to assist the early diagnosis of diseases and assess the therapeutic response. However, due to the low abundance of biomarkers in complex biological fluids, it is highly desirable to explore efficient techniques to attain their selective recognition and capture before the detection. Molecularly imprinted monoliths integrate the high selectivity of imprinted polymers and the rapid convective mass transport of monoliths, and as a result, are promising candidates to achieve the specific enrichment of biomarkers from complex samples. This review summarizes the various imprinting approaches for the preparation of molecularly imprinted monoliths. The state-of-art advances as an effective platform for applications in the selective capture of biomacromolecules related biomarkers were also outlined.

Systematic Identification of Methyl Jasmonate-Responsive Long Noncoding RNAs and Their Nearby Coding Genes Unveils Their Potential Defence Roles in Tobacco BY-2 Cells.

Long noncoding RNAs (lncRNAs) are distributed in various species and play critical roles in plant growth, development, and defence against stimuli. However, the lncRNA response to methyl jasmonate (MeJA) treatment has not been well characterized in Nicotiana tabacum Bright Yellow-2 (BY-2) cells, and their roles in plant defence remain elusive. Here, 7848 reliably expressed lncRNAs were identified in BY-2 cells, of which 629 differentially expressed (DE) lncRNAs were characterized as MeJA-responsive lncRNAs. The lncRNAs in BY-2 cells had a strong genus specificity in Nicotiana. The combined analysis of the cis-regulated lncRNAs and their target genes revealed the potential up- and downregulated target genes that are responsible for different biological functions and metabolic patterns. In addition, some lncRNAs for response-associated target genes might be involved in plant defence and stress resistance via their MeJA- and defence-related cis-regulatory elements. Moreover, some MeJA-responsive lncRNA target genes were related to quinolinate phosphoribosyltransferase, lipoxygenases, and endopeptidase inhibitors, which may contribute to nicotine synthesis and disease and insect resistance, indicating that MeJA-responsive lncRNAs regulate nicotine biosynthesis and disease resistance by regulating their potential target genes in BY-2 cells. Therefore, our results provide more targets for genetically engineering the nicotine content and plant defence in tobacco plants.

Unprecedented Ferroelectricity and Ferromagnetism in a Cr2+ -Based Two-Dimensional Hybrid Perovskite.

Organic-inorganic hybrid perovskites (OIHPs) have gained tremendous interest for their rich functional properties. However, the coexistence of more than one of ferroelectricity, ferromagnetism and ferroelasticity has been rarely found in OIHPs. Herein, we report a two-dimensional Cr2+ -based OIHP, [3,3-difluorocyclobutylammonium]2 CrCl4 ([DFCBA]2 CrCl4 ), which shows both ferroelectricity and ferromagnetism. It undergoes a 4/mmmFm type ferroelectric phase transition at a temperature as high as 387 K and shows multiaxial ferroelectricity with a saturate polarization of 2.1 µC cm-2 . It acts as a soft ferromagnet with a Curie temperature of 32.6 K. This work throws light on the exploration of OIHPs with the coexistence of ferroelectricity and ferromagnetism for applications in future multifunctional smart devices.

Bioinspired Design of seco-Chlorin Photosensitizers to Overcome Phototoxic Effects in Photodynamic Therapy.

Photodynamic therapy (PDT) is a non-invasive treatment modality against a range of cancers and nonmalignant diseases, however one must be aware of the risk of causing phototoxic reactions after treatment. We herein report a bioinspired design of next-generation photosensitizers (PSs) that not only effectively produce ROS but undergo fast metabolism after treatment to overcome undesirable side effects. We constructed a series of ß-pyrrolic ring-opening seco-chlorins, termed beidaphyrin (BP), beidapholactone (BPL), and their zinc(II) derivatives (ZnBP and ZnBPL), featuring intense near-infrared absorption and effective O2 photosensitization. Irradiation of ZnBPL led to a non-cytotoxic, metabolizable beidaphodiacetamide (ZnBPD) via in situ generated O2.- but not 1 O2 , as revealed by mechanistic studies including time-resolved absorption, kinetics, and isotope labeling. Furthermore, water-soluble ZnBPL showed an effective therapeutic outcome, fast metabolism, and negligible phototoxic reactions.