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Four novel isostructural heterometallic dysprosium–hexacyanometallate frameworks, namely {[Dy4(L)4(H2O)4(CH3OH)4M(CN)6]·Cl·8H2O}n and {[Dy4(L)4(H2O)4(CH3OH)4M(CN)6]·Br·4CH3OH}n (M = Fe for 1 and 3, Co for 2 and 4; H2L = N′-(2-hydroxybenzylidene)picolinohydrazide) have been successfully assembled by a feasible approach employing a superparamagnetic dimeric unit as the building block and hexacyanometallates [M(CN)6]3− as bridges. Within these frameworks, hexacyanometallates serve as 4-way nodes and connect the adjacent dimeric building blocks to form a three-dimensional diamond-like structure with a Schlafli symbol of 6^6. Magnetic measurements indicate the ferromagnetic nature of intradimer Dy3+–Dy3+ interactions, the antiferromagnetic coupling between Dy3+ ions and adjacent [Fe(CN)6]3− units, as well as the dynamic magnetic behaviour under zero dc field with the effective energy barriers of 111(2), 283(8), 108(2), and 280(15) K for 1–4, respectively. Ab initio calculations and in-depth magneto-structural studies demonstrate that the magnetic anisotropy of Dy3+ ions and the intradimer ferromagnetic coupling are positive factors for slowing down the quantum tunnelling of magnetization (QTM), resulting in the highest effective energy barrier and the largest coercive field for 2 among all compounds, while the antiferromagnetic interaction between Dy3+ ions and [Fe(CN)6]3− units can accelerate the QTM and thus shut off the magnetic memory effect of 1 and 3 at low temperature.

Zirconium-based metal-organic frameworks (Zr-MOFs) have shown tremendous prospects as highly efficient adsorbents against toxic chemicals under ambient conditions. Here, we report for the first time the enhanced toxic chemical adsorption and mass transfer properties of hierarchically porous Zr-MOF nanoarchitectures. A general and scalable sol-gel-based strategy combined with facile ambient pressure drying (APD) was utilized to construct MOF-808, MOF-808-NH2, and UiO-66-NH2 xerogel monoliths, denoted as G808, G808-NH2, and G66-NH2, respectively. The resulting Zr-MOF xerogels demonstrated 3D porous networks assembled by nanocrystal aggregates, with substantially higher mesoporosities than the precipitate analogues. Microbreakthrough tests on powders and tube breakthrough experiments on engineered granules were conducted at different relative humidities to comprehensively evaluate the NO2 adsorption capabilities. The Zr-MOF xerogels showed considerably better NO2 removal abilities than the precipitates, whether intrinsically or under simulated respirator canister/protection filter environment conditions. Multiple physicochemical characterizations were conducted to illuminate the NO2 filtration mechanisms. Analysis on adsorption kinetics and mass transfer patterns in Zr-MOF xerogels was further performed to visualize the underlying structure-activity relationship using the gravimetric uptake and zero length column methods with cyclohexane and acetaldehyde as probes. The results revealed that the synergy of hierarchical porosities and nanosized crystals could effectively expedite the intracrystalline diffusion for the G66-NH2 xerogel as well as alleviate the surface resistance for the G808-NH2 xerogel, which led to accelerated overall adsorption uptake and thus enhanced performance toward toxic chemical removal.

Single-molecule magnets (SMMs) are expected to be promising candidates for the applications of high-density information storage materials and quantum information processing. Lanthanide SMMs have attracted considerable interest in recent years due to their excellent performance. It has always been interesting but not straightforward to study the relaxation and blocking mechanisms by embedding 3d ions into 4f SMMs. Here we report a family of air-stable 3d-4f ion-pair compounds, YFe (1), DyCr (2), DyFe (3), DyCo (4), and Dy0.04Y0.96Fe (5), composed of pentagonal bipyramidal (D5h) LnIII cations and transition metallocyanate anions. The ion-pair nature makes the dipole-dipole interactions almost the only component of the magnetic interactions that can be clarified and analytically resolved under proper approximation. Therefore, this family provides an intuitive opportunity to investigate the effects of 3d-4f and 4f-4f magnetic interactions on the behavior of site-resolved 4f SMMs. Dynamic magnetic measurements of 1 under a 4 kOe external field reveal slow magnetic relaxation originating from the isolated [FeIII]LS (S = 1/2) ions. Under zero dc field, compounds 2-5 show similar magnetic relaxation processes coming from the separated pentagonal bipyramidal (D5h) DyIII ions with high Orbach barriers of 592(5), 596(4), 595(3), and 606(4) K, respectively. Comparatively, both compounds 3 and 5 exhibit two distinct relaxation processes, respectively from the [FeIII]LS and DyIII [Ueff = 596(4) K for 3 and 610(7) K for 5] ions, under a 4 kOe dc field. The dipolar interactions between the neighboring TMIII (TM = transition metal, CrIII or [FeIII]LS) and DyIII ions were revealed to have little effect on the thermal relaxation in compounds 2, 3, and 5, or the coexistence of the two separate relaxation processes in compounds 3 and 5 under a 4 kOe dc field, but they significantly affect the quantum tunneling of magnetization and the magnetic hysteresis behavior of 2 and 3 at low temperatures compared to those of 4.

Photodynamic therapy (PDT) is a non-invasive method for cancer treatment that relies on the generation of excess reactive oxygen species (ROS), upon excitation of photosensitizer (PS), to eradicate tumor cells. However, the overexpress of endogenous antioxidants in tumor cells will eliminate the ROS and restrict the therapeutic efficacy of PDT. Herein, a novel type of PS was developed by conjugating cinnamaldehyde (CA), a kind of oxidative stress amplified agent, with porpholactam through a hydrazone bond. The new PS retains the photophysical properties of porpholactam, which displays high singlet oxygen quantum yield for the PDT function. The results of in vitro experiments performed including ROS assay and the cytotoxicity in cancer cells suggest that the rational design of the novel porpholactam-CA derivatives result in enhanced ROS generation upon irradiation, providing a possible approach to achieve enhanced therapeutic effects in PDT.

Developing efficient sensing materials with superior sensing capabilities of sensitive, fast, selective detection of volatile organic compounds (VOCs) is necessary for fields like environmental gas monitoring and non-invasive disease diagnosis. Recently, carbon nanotubes, graphene, MXene, and other carbon-based nanomaterials have been paid much attention for possible use as high-performance VOCs sensing materials due to unique physical structures and excellent electric properties. The tunability of the chemical character and surface properties of the carbon-based nanomaterials increases their potential in constructing selective sensors targeting VOCs gases. Besides, the mechanical flexibility of the carbon-based nanomaterials allows the new designs of gas sensing platforms and puts the carbon-based nanomaterials at the forefront of other sensing materials for wearable applications. In this review, we highlight the most recent progress of the carbon-based nanomaterials in the detection of VOCs gases with an emphasis on the available strategies for the construction of these VOCs gas sensors. These strategies are proved by addressing some representative paradigms, and their suitability in applications like environmental gas monitoring and non-invasive disease diagnosis is assessed. This review is intended to offer timely sources of information and provide insight for future research works on designing high-performance VOCs gas sensors by utilizing carbon-based materials.

In this study, we have established a convenient and efficient approach named Modification of DNA Regions with Metagenomic DNA Fragments (MDRMDF) for protein engineering. Degenerate primers were designed corresponding to conserved regions of the gene of interest which were used for amplification of fragments with template of the metagenomic DNA. The resulting PCR products were used to replace the corresponding regions of the gene of interest to introduce modified gene for function-based screening. Therefore, this method can make full use of the metagenomic DNA sequences with unknown metagenomic gene information for efficient protein engineering. The β-xylosidase BH3683 was used to construct a MDRMDF library which was screened with a newly designed p-NPX-M9 medium-based strategy. As a result, a mutant protein Xyl-M56 showing high activity, improved pH stability and higher tolerance to organic solvents was obtained which may have potential for industrial application. The MDRMDF method may find wide application in enzyme engineering, metabolic engineering and other fields, especially offering a new methodological option for the directed evolution of proteins.

The hydrogenation and co-hydrogenation behaviors of Hami coal and Tahe residue were investigated in an autoclave, and the feasible technical route for co-hydrogenation was explored. The experimental results showed that Hami coal had good hydroliquefaction performance and the suitable reaction temperature was 445°C. At 445°C and 9 MPa, the coal conversion rate reached 98.74%, and the oil yield reached 68.54%. The hydrogenation tests of Tahe residue showed obvious coking tendency at the lower temperature, and it was difficult to achieve lightening. At 430°C, the conversion rate of Tahe residue was only 66.38%, the light oil yield was only 50.01%, and its coking rate was as high as 9.45%. The coking rate increased with the reaction temperature. When the mixtures of Hami coal and Tahe residue were co-hydrogenated directly, the conversion rate of the raw materials was lower, and the coke phenomenon was obvious. At the coal/oil ratio was 40/60, the conversion rate was 97.79%, and oil yield was 73.36%. Adding hydrogen solvents into the co-hydrogenation system could effectively inhibit coke formation, increase the conversion rate, and lighten co-hydrogenation products. When the amount of coal was 45% and Tahe residue was 20%, the conversion rate of raw materials was 98.38% and the oil yield was 74.82%.

Multiferroic materials have attracted great interest because of their underlying new science and promising applications in data storage and mutual control devices. However, they are still very rare and highly imperative to be developed. Here, we report an organic–inorganic hybrid perovskite trimethylchloromethylammonium chromium chloride (TMCM–CrCl3), showing the coexistence of magnetic and electric orderings. It displays a paraelectric–ferroelectric phase transition at 397 K with an Aizu notation of 6/mFm, and spin-canted antiferromagnetic ordering with a Néel temperature of 4.8 K. The ferroelectricity originates from the orientational ordering of TMCM cations, and the magnetism is from the [CrCl3]− framework. Remarkably, TMCM–CrCl3 is the first experimentally confirmed divalent Cr2+-based multiferroic material as far as we know. A new category of hybrid multiferroic materials is pointed out in this work, and more Cr2+-based multiferroic materials will be expectedly developed in the future., An organic–inorganic hybrid perovskite Trimethylchloromethylammonium chromium(ii) chloride (TMCM–CrCl3) can simultaneously show excellent ferroelectricity and antiferromagnetism, which is the first experimentally confirmed Cr2+-based multiferroic material.

Background FOLFIRINOX and gemcitabine plus albumin-bound paclitaxel (AG) regimens are recommended as first-line therapy for both locally advanced and metastatic pancreatic cancer. However, there were no specific markers to conduct personalized regimen choice. The research is to assess delta Housfield unit (delta HU), which is the difference in CT attenuation value (in HU) between enhanced and nonenhanced phase of region of interest, as a marker for predicting chemotherapy response of unresectable pancreatic cancer. Methods A total of 179 unresectable pancreatic cancer patients were enrolled in the study. Kaplan-Meier analysis and COX regression analysis were performed for progression-free survival (PFS) and overall survival. The differences of clinical characteristics were analyzed by χ 2test. Microvessel density (MVD) was calculated by immunochemistry staining of CD34. Results Delta HU was an independent risk factor for unresectable pancreatic cancer (P = 0.017, HR 0.672, 95%CI 0.485–0.930). Patients with higher delta HU were associated with better PFS (P = 0.004). For modified FOLFIRINOX (mFOLFIRINOX) group, delta HU was an independent risk factor (P = 0.045, HR 0.571), but not for AG group (P = 0.473, HR 0.855). Delta HU was correlated with stroma MVD (P = 0.000, R = 0.483), not with parenchyma MVD (P = 0.074, R = 0.199). Conclusions Delta HU was a marker predicting chemotherapy response for unresectable pancreatic cancer. Higher delta HU was associated with better survival for patients receiving mFOLFIRINOX rather than AG. The delta HU was positively correlated with stroma MVD, explaining the relationship between delta HU and prognosis.

Salmonella, being one of the most widespread foodborne pathogens, is a compulsory test item required by national food safety standard of China and many other countries. More sensitive and specific Salmonella detection method is still needed since traditional methods are time consuming and highly dependent on enormous manpower and material resources. In this research, a bacteria detection method based on CRISPR-Cas13a system (where CRISPR is Clustered Regularly Interspaced Short Palindromic Repeats) was proposed. The target DNA was amplified by PCR and transcribed into RNA by T7 transcriptase, which can activate the RNase activity of the Cas13a protein. The self-folding quenched fluorescent probe can be cleaved by the activated Cas13a protein to generate fluorescent signal. We named this method as PCF detection (PCR-CRISPR-Fluorescence based nucleic acid detection). In this study, PCF detection showed excellent sensitivity, which can detect Salmonella genomic DNA with a minimum of 101 aM or 10° CFU/ml Salmonella bacteria in 2 hr. It also showed good specificity with no cross-reaction with other common foodborne bacteria. PRACTICAL APPLICATION: The PCF detection method proposed in this article can detect Salmonella sensitively and specifically, providing a novel strategy for the detection of foodborne pathogens in food and has great application potential in other microbial detection fields.

The study of lanthanide (Ln)-transition-metal (TM) heterometallic clusters which play key roles in various high-tech applications is a rapid growing field of research. Despite the achievement of numerous Ln-TM cluster compounds comprising one Ln atom, the synthesis of Ln-TM clusters containing multiple Ln atoms remains challenging. Here, we present the preparation and self-assembly of a series of Au-bridged heterometallic clusters containing multiple cerium (Ce) atoms via on-surface coordination. By employing different pyridine and nitrile ligands, the ordered coordination assemblies of clusters containing 2, 3 and 4 Ce atoms bridged by Au adatoms are achieved on Au(111) and Au(100), as revealed by scanning tunneling microscopy. Density functional theory calculations uncover the indispensable role of the bridging Au adatoms in constructing the multi-Ce-containing clusters by connecting the Ce atoms via unsupported Ce-Au bonds. These findings demonstrate on-surface coordination as an efficient strategy for preparation and organization of the multi-Ln-containing heterometallic clusters., The preparation of lanthanide-transition metal clusters containing multiple lanthanide atoms remains challenging. Here, the authors present the controlled on-surface formation of ligand-stabilized heterometallic Ce/Au clusters containing two, three and four Ce atoms bridged by Au adatoms.

Homoleptic tris(6,6′-dimethyl-2,2′-bipyridine) rare earth metal complexes M(κ2-dmbp)3 (M = Y, Tb, Dy, Ho, Er; dmbp = 6,6′-dimethyl-2,2′-bipyridine) were synthesized by in situ reduction of 3 equiv. of dmbp with excess KC8 in the presence of 1 equiv. of rare earth metal trihalides. All compounds were characterized by X-ray crystallography, UV-Vis-NIR spectroscopy, infrared (IR) spectroscopy, elemental analysis, and magnetic measurements. While the structural parameters and spectroscopic data confirmed the existence of the trivalent rare earth metal cation and three dmbp radical anions, the electron paramagnetic resonance (EPR) spectrum and the measured magnetic moment of Y(κ2-dmbp)3 indicated that two parallel dmbp radical anions were antiferromagnetically coupled. For paramagnetic rare earth metal ions, room temperature magnetic susceptibility values indicated a weak ferromagnetic interaction between the metal ion and the remaining dmbp radical. Density functional theory (DFT) calculations were performed on Y(κ2-dmbp)3 to gain insight into the electronic structures of these homoleptic metal complexes. The computational results were consistent with the structural, spectroscopic, and magnetic data for a S = 1/2 ground state and spin densities mostly residing on one dmbp radical anion, while the spins on the other two parallel dmbp radical anions being antiferromagnetically coupled.

A series of mononuclear lanthanide complexes with the formula [Hex4N][Ln(DBM)4] (1Ln) (Ln = Nd and Tb), [But4N][Dy(DBM)4] (2), [Et4N][Dy(DBM)4] (3), [PhCH2N(CH3)3][Dy(DBM)4] (4) and [Hex4N][Dy(TTA)4] (5) formed by four β-diketonate ligands (i.e. DBM = dibenzoylmethane, TTA = 2-thenoyltrifluoroacetone) and four organic counter ammonium cations (i.e. Hex4N = tetrahexylammonium, But4N = tetrabutylammonium, Et4N = tetraethylammonium and PhCH2N+(CH3)3) were structurally and magnetically characterized. The organic ammonium as contactless cation pairs with [Ln(β-diketonate)4]−1 moieties, the impact of different remote organic cations and the first coordination sphere comprising distinct β-diketonates on their SMM performance were elaborately studied. This is an efficient method by virtue of the interaction of the remote organic ion pair to modulate their single-molecule magnetic (SMM) properties. More importantly, the tetrakis β-diketonate Dy(III) anion can be almost intactly grafted on functional GaN substrate through an anion exchange reaction, resulting in diminishing slow magnetic relaxation behavior, which presents potential application in future SMM devices.

Oxygen bottom-blown smelting technology (SKS) is a promising way to utilize the low-grade and complex multimetallic copper ores. To reveal the wear mechanisms of the furnace linings, a post-mortem study of the used refractories (fused-grain rebonded magnesia-chromite refractory) was carried out by chemical and microstructural analysis. The results showed that the chemical interaction at the bath-lining interface was particularly strong since thick corrosion layers (around 4.0 cm) were generated, where a continuously distributed phase of forsterite was identified. This was mainly owing to the high injection pressure and the presence of Cu-CuxO melts in the slag, which greatly accelerated the slag infiltration and periclase dissolution. In this case, fused grains with a high content of intergranular spinel were found more difficult to be corroded by the slag. The significant loss of direct bonds and the softening of refractory are considered as the main degradation mechanisms for the SKS furnace linings. The interaction between FexO in slag and chromite spinel was evident, but it only occurred in the areas near the hot face, showing limited effect on the corrosion behavior.

Transition metal nitrides (TMNs) are predicted to be highly promising electrocatalysts for the nitrogen reduction reaction (NRR) by theoretical calculations. TMNs follow a special Mars-van Krevelen (MvK) mechanism during the NRR, involving surface lattice nitrogen exchange and regeneration. It is hence essential to identify the source of nitrogen, especially taking the stability of lattice nitrogen into consideration. Herein, we investigated the deactivation process of a benchmark CrN nanoparticle catalyst (CrN NPs) with a phase-pure cubic rocksalt (RS) structure for the electrochemical NRR. The current work identifies two possible deactivation pathways for CrN: (i) potential-induced structural collapse of the catalyst including both lattice N leaching and metal dissolution and (ii) ammonia poisoning due to the accumulation and strong chemical bonding of the produced ammonia on the CrN surface. This work provides new perspectives for understanding the structural evolution of nitrogen-containing electrocatalysts for NRR research.

BACKGROUND: Multiple myeloma remains a virtually incurable hematologic malignancy, which is featured with the aberrant growth of malignant plasma cells. AIMS: To elucidate the functions of miR-19a-3p in multiple myeloma. STUDY DESIGN: Cell study. METHODS: Cell counting kit-8 assay was performed to detect cell viability, and flow cytometry was conducted to detect cell apoptosis. Bioinformatics analysis predicted miR-19a-3p-associated biological function, pathway, core regulatory network, and target genes. Luciferase reporter assay verified the target sequence of miR-19a-3p regulating FBXO32. RESULTS: miR-19a-3p is upregulated in multiple myeloma cells (p

A family of cyano-bridged 3d-4f 1D chain compounds, {RE[TM(CN)6(2-PNO)5]}·(H2O)4 {RE = YIII, TM = [FeIII]LS (1); RE = DyIII, TM = CoIII (3); RE = ErIII, TM = [FeIII]LS (4), CoIII (5); 2-PNO = 2-picoline-N-oxide} and {RE[TM(CN)6(2-PNO)5]} {RE = DyIII, TM = [FeIII]LS (2)}, were synthesized and characterized. Single-crystal X-ray diffraction studies reveal that compounds 1 and 3-5 are isostructural, while compound 2 has a similar 1D chain structure with a different chain to chain arrangement. An axially-elongated pentagonal bipyramidal (D5h) coordination geometry is formed with five 2-PNO ligands in the equatorial plane and two [TM(CN)6]3- on the apical sites around the rare earth ions in these compounds. A comparison of the magnetic relaxation behaviour in detail reveals that it is more favorable for the Er (4 and 5) than the Dy analogues (2 and 3) to exhibit SIM properties in this axially-elongated D5h coordination environment. Under zero dc field, ac susceptibility measurements show that the Dy analogues have no magnetic relaxation behaviour, while the Er analogues exhibit frequency dependence despite the strong QTM effect. Under a 1 kOe dc field, the Er analogues generally show 1-2 orders of magnitude longer relaxation time at each selected temperature and a higher relaxation energy barrier than the Dy analogues. And the RECo compounds (3 and 5) show a more suppressed QTM effect than the corresponding REFe (2 and 4) compounds, which may be ascribed to the elimination of the fluctuation field from the neighbouring [FeIII]LS ions. The ab initio calculations indicate the misplacement between the orientation of the main magnetic axis and the structural axis in the Dy analogues, and the relative consistency in the Er analogues, which should be the source of the Er analogues showing better SIM properties than the Dy analogues.

The suppression of irreversible phase change in battery-type materials during electrochemical process, leading to high-performance asymmetric supercapacitors (ASCs), remains one of the crucial challenges for the new generation of electrochemical energy storage devices. Herein, we propose a pre-activation strategy to address the corresponding problem based on an in-depth study of the failure mechanism of nickel–manganese layered double hydroxide (LDH), which is the inhibition of the exfoliation and deactivation of lattice Mn during the cycling process. The modified NiMn-LDH shows enhanced electrochemistry performance compared to pristine NiMn-LDH, with an increase in specific capacity from 855 to 1082 C g−1 and a doubling of stability after 3000 cycles. Furthermore, the assembled ASC device achieves a high specific energy density of 48.9 W h kg−1 at a power density of 810 W kg−1. The anchored, activated lattice Mn provided by hydrogen peroxide in the pre-activation strategy is proved to play a vital role in achieving high-performance ASCs. This work paves a new avenue to solve the long-standing significant challenge of battery-type materials for asymmetric supercapacitors.

Flavonoids have notable biological activities and have been widely used in the medicinal and chemical industries. However, single-copy integration of heterologous pathway genes limits the production of flavonoids. In this work, we designed and constructed single-step integration of multiple flavonoid (2S)-naringenin biosynthetic pathway genes in S. cerevisiae. The efficiency of the naringenin metabolic pathway gene integration into the rDNA site reached 93.7%. Subsequently, we used a high titer p-coumaric acid strain as a chassis, which eliminated feedback inhibition of tyrosine and downregulated the competitive pathway. The results indicated that increasing the supply of p-coumaric acid was effective for naringenin production. We additionally optimized the amount of donor DNA. The optimum strain produced 149.8 mg/L of (2S)-naringenin. The multi-copy integration of flavonoid pathway genes effectively improved (2S)-naringenin production in S. cerevisiae. We further analyzed the copy numbers and expression levels of essential genes (4CL and CHS) in the (2S)-naringenin metabolic pathway by qPCR. Higher copy numbers of the (2S)-naringenin metabolic pathway genes were associated with greater 4CL and CHS transcription, and the efficiency of naringenin production was higher. Therefore, multi-copy integration of genes in the (2S)-naringenin metabolic pathway was imperative in rewiring p-coumaric acid flux to enhance flavonoid production.

The first-row transition metal compounds, [MII(L1)2](ClO4)2 (M = Ni (1); Co (2)), have been prepared by treatment of a neutral tetradentate ligand (L1 = N2,N9-dibutyl-1,10-phenanthroline-2,9-dicarboxamide) with metal perchlorate salts in MeOH. Both compounds have been structurally characterized by X-ray crystallography and it was found that the coordination numbers are 6 and 7, respectively. The reaction of 6,6′-bis(2-tbutyl-tetrazol-5-yl)-2,2′-bipyridine (L2) with hydrated FeII(ClO4)2 afforded a 8-coordinate Fe(II) compound, [FeII(L2)2](ClO4)2 (3); however its reaction with hydrated CoII(ClO4)2 resulted in 6-coordinate [CoII(L2)2](ClO4)2. It is interesting to observe field-induced slow magnetic relaxation in the 7-coordinate Co(II) compound 2 and 8-coordinate Fe(II) compound 3, which further supports the validity of designing high coordination number compounds as single-molecule magnets. Direct current magnetic studies demonstrate that 2 has a very large positive D value (56.2 cm−1) and a small E value (0.66 cm−1), indicating easy plane magnetic anisotropy. Consistent with the larger D value, an effective spin-reversal barrier of Ueff = 100 K (71.4 cm−1) is obtained, which is the highest value reported for 7-coordinate Co(II) complexes with a pentagonal bipyramidal geometry. In contrast, 8-coordinate Fe(II) compound 3 exhibits uniaxial magnetic anisotropy.

The compound (2S)-eriodictyol is an important flavonoid that can be derived from (2S)-naringenin through flavonoid 3'-hydroxylase (F3'H) catalyzation. F3'H is a cytochrome P450 enzyme that requires a cytochrome P450 reductase (CPR) to function. However, P450s have limited applications in industrial scale biosynthesis, owing to their low activity. Here, an efficient SmF3'H and a matched SmCPR were identified from Silybum marianum. To improve the efficiency of SmF3'H, we established a high-throughput detection method for (2S)-eriodictyol, in which the promoter combination of SmF3'H and SmCPR were optimized in Saccharomyces cerevisiae. The results revealed that SmF3'H/SmCPR should be expressed by using promoters with similar and strong expression levels. Furthermore, directed evolution was applied to further improve the efficiency of SmF3'H/SmCPR. With the optimized promoter and mutated combinations SmF3'HD285N/SmCPRI453V, the (2S)-eriodictyol titer was improved to 3.3 g/L, the highest titer in currently available reports. These results indicated that S. cerevisiae is an ideal platform for functional expression of flavonoid related P450 enzymes.

Irreversible consumption of sulfur aroused from shuttle reaction is the major challenge for liquid electrolyte lithium–sulfur batteries, although various sulfur-based cathodes have been designed. I...

Symmetry and axiality are thought to be guides toward the pursuit of high energy barrier and blocking temperature for the dysprosium (III) (DyIII) single-molecule magnets (SMMs). The DyIII complexe...

Epstein-Barr virus (EBV) is a γ-herpesvirus associated with the occurrence of several human malignancies. BBRF2 and BSRF1 are two EBV tegument proteins that have been suggested to form a hetero-complex and mediate viral envelopment, but the molecular basis of their interaction and the functional mechanism of this complex remains unknown. Here, we present crystal structures of BBRF2 alone and in complex with BSRF1. BBRF2 has a compact globular architecture featuring a central β-sheet that is surrounded by 10 helices, it represents a novel fold distinct from other known protein structures. The central portion of BSRF1 folds into two tightly associated antiparallel α-helices, forming a composite four-helix bundle with two α-helices from BBRF2 via a massive hydrophobic network. In vitro, a BSRF1-derived peptide binds to BBRF2 and reduces the number of viral genome copies in EBV-positive cells. Exogenous BBRF2 and BSRF1 co-localize at the Golgi apparatus. Furthermore, BBRF2 binds capsid and capsid-associated proteins, whereas BSRF1 associates with glycoproteins. These findings indicate that the BBRF2-BSRF1 complex tethers EBV nucleocapsids to the glycoprotein-enriched Golgi membrane, facilitating secondary envelopment., Epstein-Barr virus (EBV) tegument proteins BBRF2 and BSRF1 have been suggested to form a hetero-complex. Here, He et al. provide the crystal structures of BBRF2 alone and in complex with BSRF1 and suggest that the complex tethers EBV nucleocapsids to the Golgi membrane, facilitating secondary envelopment.

In this study, papain and alcalase were used to generate antioxidant peptides from yak bone protein. The antioxidant activities of hydrolysates in vitro were evaluated by 2,2′-azinobios-(3-ethylbenzothiazoline-6-sulphonic acid) radical scavenging activity, total reducing power, ferrous ion chelating ability and hydroxyl radical scavenging activity. The hydrolysates generated by alcalase possessed the best antioxidant activity among unhydrolyzed protein and samples treated by papain, but the antioxidant activity decreased after simulated gastrointestinal digestion in vitro. The products of simulated gastrointestinal digestion were separated by ultrafiltration and high performance liquid chromatography, and the amino acid sequences of peptides were identified by mass spectrometry. The digestion sites within peptides were predicted by a bioinformatics strategy, and ten peptides were selected for synthesis. Among 10 synthetic peptides, Gly-Phe-Hyp-Gly-Ala-Asp-Gly-Val-Ala, Gly-Gly-Pro-Gln-Gly-Pro-Arg and Gly-Ser-Gln-Gly-Ser-Gln-Gly-Pro-Ala possessed strong antioxidant activities, among which Gly-Phe-Hyp-Gly-Ala-Asp-Gly-Val-Ala had a significant cytoprotective effect in Caco-2 cells under oxidative stress induced by H2O2, which reduced the formation of reactive oxygen species and malondialdehyde, and improved the activity of antioxidant enzymes in cells. These results showed that yak bone peptides exhibited strong antioxidant activity and have a potential value as a new type of natural antioxidant.

Solidification cracking (SC) is highly related to the grain coalescence behavior during welding of aluminum alloys. In this study, the grain coalescence behavior and its effects on solidification cracking susceptibility (SCS) were investigated using the multiphase-field approach. Why SCS is high at a certain value of Cu concentration and why SC often occurs at high misorientation angles are revealed. Firstly, nominal compositions of Cu affect the morphology of microstructure during solidification. The crystals morphology is cellular at the low concentration, while the crystals are dendritic at the high concentration in the columnar grain region. The SCS of cellular grains is higher than dendrites due to the high volume fraction of solid when the grains/subgrains bridge. Under the action of tensile stress, the scarce residual liquid phase cannot backfill in time. Secondly, high misorientation angles make grain boundary energy in the solid–solid interface (σSS) is high. It is found that σSS suppresses the grain coalescence and increases the SCS of alloys. This leads the emergence of SC at high misorientation angles during welding. In this study, the coalescence behavior of grains during solidification is visually presented by simulation and the coherency point at the last-stage solidification is achieved accurately.

The thermally induced cyclodehydrofluorization of iron tetrakis(pentafluorophenyl)porphyrin proceeded highly stereoselectively to give a prochiral product on a gold surface in an ultrahigh vacuum, whereas dehydrocyclization of the respective iron tetrakisphenylporphyrin did not show such selectivity. Stereoselectivity was predominantly observed for closely packed layers, which is an indication of intermolecular cooperativity and steric constraints induced by adjacent species. Density functional theory identified intermolecular packing constraints as the origin of such selectivity during the reaction. Scanning tunneling microscopy revealed the formation of an enantiomerically pure two-dimensional self-assembly as a conglomerate of mirror domains. On-surface two-dimensional topochemistry, as reported herein, may open new routes for stereoselective synthesis.