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1.
Mol Phylogenet Evol ; 193: 108023, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38342159

RESUMO

The Himalaya-Hengduan Mountains (HHM), a renowned biodiversity hotspot of the world, harbors the most extensive habitats for alpine plants with extraordinary high levels of endemism. Although the general evolution pattern has been elucidated, the underlying processes driving spectacular radiations in many species-rich groups remain elusive. Corydalis DC. is widely distributed throughout the Northern Hemisphere containing more than 500 species, with high diversity in HHM and adjacent regions. Using 95 plastid genes, 3,258,640 nuclear single nucleotide polymorphisms (SNPs) and eight single-copy nuclear genes (SCNs) generated from genome skimming data, we reconstructed a robust time-calibrated phylogeny of Corydalis comprising more than 100 species that represented all subgenera and most sections. Molecular dating indicated that all main clades of Corydalis began to diverge in the Eocene, with the majority of extant species in HHM emerged from a diversification burst after the middle Miocene. Global pattern of mean divergence times indicated that species distributed in HHM were considerably younger than those in other regions, particularly for the two most species-rich clades (V and VI) of Corydalis. The early divergence and the recent diversification of Corydalis were most likely promoted by the continuous orogenesis and climate change associated with the uplift of the Qinghai-Tibetan Plateau (QTP). Our study demonstrates the effectivity of phylogenomic analyses with genome skimming data on the phylogeny of species-rich taxa, and sheds lights on how the uplift of QTP has triggered the evolutionary radiations of large plant genera in HHM and adjacent regions.


Assuntos
Corydalis , Filogenia , Himalaia , Biodiversidade , Ecossistema , Plantas
2.
J Am Chem Soc ; 145(3): 1936-1944, 2023 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-36637030

RESUMO

Piezoelectric materials that enable electromechanical conversion have great application value in actuators, transducers, sensors, and energy harvesters. Large piezoelectric (d33) and piezoelectric voltage (g33) coefficients are highly desired and critical to their practical applications. However, obtaining a material with simultaneously large d33 and g33 has long been a huge challenge. Here, we reported a hybrid perovskite ferroelectric [Me3NCH2Cl]CdBrCl2 to mitigate and roughly address this issue by heavy halogen substitution. The introduction of a large-size halide element softens the metal-halide bonds and reduces the polarization switching barrier, resulting in excellent piezoelectric response with a large d33 (∼440 pC/N), which realizes a significant optimization compared with that of previously reported [Me3NCH2Cl]CdCl3 (You et al. Science2017, 357, 306-309). More strikingly, [Me3NCH2Cl]CdBrCl2 simultaneously shows a giant g33 of 6215 × 10-3 V m/N, far exceeding those of polymers and conventional piezoelectric ceramics. Combined with simple solution preparation, easy processing of thin films, and a high Curie temperature of 373 K, these attributes make [Me3NCH2Cl]CdBrCl2 promising for high-performance piezoelectric sensors in flexible, wearable, and biomechanical devices.

3.
Angew Chem Int Ed Engl ; 62(31): e202306732, 2023 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-37272456

RESUMO

Chiral ferroelectric crystals with intriguing features have attracted great interest and many with point or axial chirality based on the stereocarbon have been successively developed in recent years. However, ferroelectric crystals with stereogenic heteroatomic chirality have never been documented so far. Here, we discover and report a pair of enantiomeric stereogenic sulfur-chiral single-component organic ferroelectric crystals, Rs -tert-butanesulfinamide (Rs -tBuSA) and Ss -tert-butanesulfinamide (Ss -tBuSA) through the deep understanding of the chemical design of molecular ferroelectric crystals. Both enantiomers adopt chiral-polar point group 2 (C2 ) and exhibit mirror-image relationships. They undergo high-temperature 432F2-type plastic ferroelectric phase transition around 348 K. The ferroelectricity has been well confirmed by ferroelectric hysteresis loops and domains. Polarized light microscopy records the evolution of the ferroelastic domains, according with the fact that the 432F2-type phase transition is both ferroelectric and ferroelastic. The very soft characteristics with low elastic modulus and hardness reveals their excellent mechanical flexibility. This finding indicates the first stereosulfur chiral molecular ferroelectric crystals, opening up new fertile ground for exploring molecular ferroelectric crystals with great application prospects.

4.
Chem Soc Rev ; 50(14): 8248-8278, 2021 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-34081064

RESUMO

With prosperity, decay, and another spring, molecular ferroelectrics have passed a hundred years since Valasek first discovered ferroelectricity in the molecular compound Rochelle salt. Recently, the proposal of ferroelectrochemistry has injected new vigor into this century-old research field. It should be highlighted that piezoresponse force microscopy (PFM) technique, as a non-destructive imaging and manipulation method for ferroelectric domains at the nanoscale, can significantly speed up the design rate of molecular ferroelectrics as well as enhance the ferroelectric and piezoelectric performances relying on domain engineering. Herein, we provide a brief review of the contribution of the PFM technique toward assisting the design and performance optimization of molecular ferroelectrics. Relying on the relationship between ferroelectric domains and crystallography, together with other physical characteristics such as domain switching and piezoelectricity, we believe that the PFM technique can be effectively applied to assist the design of high-performance molecular ferroelectrics equipped with multifunctionality, and thereby facilitate their practical utilization in optics, electronics, magnetics, thermotics, and mechanics among others.

5.
Sensors (Basel) ; 22(23)2022 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-36501941

RESUMO

We demonstrate a narrow-linewidth, high side-mode suppression ratio (SMSR) semiconductor laser based on the external optical feedback injection locking technology of a femtosecond-apodized (Fs-apodized) fiber Bragg grating (FBG). A single frequency output is achieved by coupling and integrating a wide-gain quantum dot (QD) gain chip with a Fs-apodized FBG in a 1-µm band. We propose this low-cost and high-integration scheme for the preparation of a series of single-frequency seed sources in this wavelength range by characterizing the performance of 1030 nm and 1080 nm lasers. The lasers have a maximum SMSR of 66.3 dB and maximum output power of 134.6 mW. Additionally, the lasers have minimum Lorentzian linewidths that are measured to be 260.5 kHz; however, a minimum integral linewidth less than 180.4 kHz is observed by testing and analyzing the power spectra of the frequency noise values of the lasers.

6.
Angew Chem Int Ed Engl ; 61(42): e202204584, 2022 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-35853827

RESUMO

Glucose and lactate play important roles for tumor growth. How to simultaneously deprive tumors of glucose and lactate is a big challenge. We have developed a cascade catalytic system (denoted as FPGLC) based on fluorinated polymer (FP) with co-loading of glucose oxidase (GOx), lactate oxidase (LOx), and catalase (CAT). GOx and LOx deprive glucose and lactate, respectively, resulting in abundant hydrogen peroxide (H2 O2 ) generation. Meanwhile, CAT catalyzes H2 O2 into O2 , which not only promotes catalytic reactions of GOx and LOx for consuming more glucose and lactate, but also alleviates tumor hypoxia. Benefiting from the excellent cross-membrane and transmucosal penetration capacities of FP, FPGLC rapidly accumulated in tumors and subsequently mediated enhanced cascade catalytic therapy under the guidance of photoacoustic imaging. These results demonstrate that the dual depletion of glucose and lactate with O2 supply is a promising strategy for efficient antitumor starvation therapy.


Assuntos
Nanopartículas , Neoplasias , Catalase , Linhagem Celular Tumoral , Polímeros de Fluorcarboneto , Glucose , Glucose Oxidase , Humanos , Peróxido de Hidrogênio , Lactatos , Neoplasias/patologia
7.
J Am Chem Soc ; 143(51): 21685-21693, 2021 12 29.
Artigo em Inglês | MEDLINE | ID: mdl-34928580

RESUMO

A ferroelectric/ferroelastic is a material whose spontaneous polarization/strain can be switched by applying an external electric field/mechanical stress. However, the optical control of spontaneous polarization/strain remains relatively unexplored in crystalline materials, although photoirradiation stands out as a nondestructive, noncontact, and remote-controlled stimulus beyond stress or electric field. Here, we present two new organic single-component homochiral photochromic multiferroics, (R)- and (S)-N-3,5-di-tert-butylsalicylidene-1-4-bromophenylethylamine (SA-Ph-Br(R) and SA-Ph-Br(S)), which show a full ferroelectric/ferroelastic phase transition of 222F2 type at 336 K. Under photoirradiation, their spontaneous polarization/strain can be switched quickly within seconds and reversibly between two ferroelectric/ferroelastic phases with the respective enol and trans-keto forms triggered by structural photoisomerizations. In addition, they possess a superior acoustic impedance characteristic with a value of ∼2.42 × 106 kg·s-1·m-2, lower than that of polyvinylidene fluoride (PVDF, (3.69-4.25) × 106 kg·s-1·m-2), which can better match human tissues. This work realizes for the first time that multiple ferroic orders in single-component organic crystals with ultralow acoustic impedance can be simultaneously controlled and coupled by three physical channels (electric, stress, light fields), suggesting their great potential in multichannel data storage, optoelectronics, and related applications compatible with all-organic electronics and human tissues.

8.
J Am Chem Soc ; 143(34): 13816-13823, 2021 09 01.
Artigo em Inglês | MEDLINE | ID: mdl-34425050

RESUMO

The optical control of polarization switching is attracting tremendous interest because photoirradiation stands out as a nondestructive, noncontact, and remote-control means beyond an electric or strain field. The current research mainly uses various photoexcited electronic effects to achieve the photocontrol polarization, such as a light-driven flexoelectric effect and a photovoltaic effect. However, since photochromism was discovered in 1867, the structural phase transition caused by photoisomerization has never been associated with ferroelectricity. Here, we successfully synthesized an organic photochromic ferroelectric with polar space group Pna21, 3,4,5-trifluoro-N-(3,5-di-tert-butylsalicylidene)aniline, whose color can change between yellow and orange via laser illumination. Its dielectric permittivity and spontaneous polarization can be switched reversibly with a photoinduced phase transition triggered by structural photoisomerization between the enol form and the trans-keto form. To our knowledge, this is the first photoswitchable ferroelectric crystal to achieve polarization switching through a structural phase transition triggered by photoisomerization. This finding paves the way toward photocontrol of smart materials and biomechanical applications in the future.

9.
FASEB J ; 34(12): 16552-16566, 2020 12.
Artigo em Inglês | MEDLINE | ID: mdl-33118211

RESUMO

Human osteoarthritis cartilage contains chondrocytes (OAC) and mesenchymal stromal cells (OA-MSC). Here, we found that TGF-ß had different effects on OA-MSC and OAC, and revealed its lateral signaling mechanism in OA. RNAseq analysis indicated that OA-MSC expressed the same level of Bone Morphogenetic Protein (BMP) Receptor-1A as OAC but only 1/12 of Transforming Growth Factor beta (TGF-ß) Receptor-1. While TGF-ß specifically activated SMAD2 in OAC, it also activated BMP signaling-associated SMAD1 in OA-MSC. While TGF-ß stimulated chondrogenesis in OAC, it induced hypertrophy, mineralization, and MMP-13 in OA-MSC. Inhibiting TGF-ßR1 suppressed MMP-13 in OA-MSC but stimulated it in OAC. In contrast, by specifically targeting BMPR1A/ACVR1 in both cell types, LDN193189 inhibits cartilage degeneration through suppressing hypertrophy and MMP-13 in a mouse osteoarthritis model. Thus, LDN193189, a drug under development to inhibit constitutive BMP signaling during heterotopic ossification, may be re-purposed for OA treatment.


Assuntos
Cartilagem Articular/metabolismo , Células-Tronco Mesenquimais/metabolismo , Osteoartrite/metabolismo , Transdução de Sinais/fisiologia , Fator de Crescimento Transformador beta/metabolismo , Animais , Células Cultivadas , Condrócitos/metabolismo , Condrogênese/fisiologia , Humanos , Hipertrofia/metabolismo , Masculino , Camundongos , Camundongos Endogâmicos C57BL , Receptor do Fator de Crescimento Transformador beta Tipo I/metabolismo , Proteína Smad2/metabolismo
10.
Angew Chem Int Ed Engl ; 60(30): 16668-16673, 2021 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-33982370

RESUMO

Organic radical ferroics such as TEMPO have attracted widespread interest. However, the relatively low Curie temperature of 287 K and melting point of 311 K severely hinder its application potential. Despite extensive interest, high-temperature radical ferroics have not yet been found. Here, taking advantage of chemical design and supramolecular radical chemistry, we designed two high-temperature organic supramolecular radical ferroics [(NH3 -TEMPO)([18]crown-6)](ReO4 ) (1) and [(NH3 -TEMPO)([18]crown-6)](ClO4 ) (2), which can retain ferroelectricity up to 413 K and 450 K, respectively. To our knowledge, they are both the first supramolecular radical ferroics and unprecedented high-temperature radical ferroics, where the supramolecular component is vital for the stabilization of the radical and extending the working temperature window. Both also have paramagnetism, non-interacting spin moments, and excellent piezoelectric and electrostrictive behaviors comparable to that of LiNbO3 .

11.
J Am Chem Soc ; 142(46): 19698-19704, 2020 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-33156625

RESUMO

Three-dimensional (3D) organic-inorganic lead halide hybrids have become a hot academic topic because of their various functional properties. However, 3D lead halide hybrid ferroelectrics are still very rare until now. Here, we report a new 3D lead halide perovskite-related ferroelectric, (EATMP)Pb2Br6 [EATMP = (2-aminoethyl)trimethylphosphanium]. Based on nonferroelectric CH3NH3PbBr3, by replacing PbBr6 octahedra with a Pb2Br10 dimer of edge-sharing octahedra as the basic building unit, the expanded 3D lead bromide perovskite analog was formed with the large [EATMP]2+ cations occupying the voids of framework. Notably, (EATMP)Pb2Br6 displays a direct bandgap of 2.81 eV, four polarization directions, and a high Curie temperature (Tc) of 518 K (much beyond that of BaTiO3, 393 K), which is the highest among all reported 3D organic-inorganic hybrid ferroelectrics. Such a high Tc may result from the high rotational energy barrier of cations induced by a larger molecular volume and relatively low crystal symmetry. Our work provides an efficient avenue to construct new 3D organic-inorganic lead halide hybrids and would inspire the further exploration of 3D lead halide ferroelectrics.

12.
Biochem Biophys Res Commun ; 528(1): 179-185, 2020 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-32499111

RESUMO

Sirt1 involved in cellular aging and aging-related diseases, including osteoarthritis (OA). Our previous study showed Sirt1 played a role in the pathogenesis of OA, however, the underlying mechanisms are still poorly elicited. In this study, we investigated the role of Sirt1 in epigenetically regulating P53/P21 pathway in a Sirt1 loss model. Sirt1 deletion male mice (n = 10) with destabilization of the medial meniscus (DMM) were used to observe its role on OA development. Then, the relationships between SIRT1 and P53 were detected by Coimmunoprecipitation (CoIP), and the gain-off function of P53 gene was indicated by P53 activators and inhibitors in vitro. Finally, human cartilage samples from patients with OA were collected. Sirt1 deletion mice displayed a spontaneous OA development, manifesting severe chondrocytes hypertrophy markers MMP13 and ADAMTS5, highly expressed P53 and P21. Strikingly, surgery-induced meniscus injury promoted the OA pathogenesis and apoptosis in Sirt1 deficient mice. Ultimately, our CoIP data demonstrated that Sirt1 directly interacted with P53 in vitro. However inhibition of P53 alleviated OA progression. We also observed that chondrocyte apoptosis and P53 increased in osteoarthritis (OA) progression with a declining expression of Sirt1 in human cartilage. Loss of Sirt1 in cartilage led to accelerated OA pathogenesis via aberrant activation of p53/p21 mediated senescence associated secretory phenotype, hypertrophy and apoptosis.


Assuntos
Apoptose , Condrócitos/metabolismo , Condrócitos/patologia , Inibidor de Quinase Dependente de Ciclina p21/metabolismo , Epigênese Genética , Osteoartrite/genética , Sirtuína 1/metabolismo , Proteína Supressora de Tumor p53/metabolismo , Idoso , Envelhecimento/patologia , Animais , Apoptose/genética , Cartilagem/patologia , Deleção de Genes , Humanos , Hipertrofia , Masculino , Camundongos Knockout , Pessoa de Meia-Idade , Osteoartrite/etiologia , Osteoartrite/patologia , Tíbia/patologia
13.
Front Immunol ; 15: 1356833, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38629068

RESUMO

Background: TGFB-induced factor homeobox 2 (TGIF2), a member of the Three-Amino-acid-Loop-Extension (TALE) superfamily, has been implicated in various malignant tumors. However, its prognostic significance in glioma, impact on tumor immune infiltration, and underlying mechanisms in glioma development remain elusive. Methods: The expression of TGIF2 in various human normal tissues, normal brain tissues, and gliomas was investigated using HPA, TCGA, GTEx, and GEO databases. The study employed several approaches, including Kaplan-Meier analysis, ROC analysis, logistic regression, Cox regression, GO analysis, KEGG analysis, and GSEA, to explore the relationship between TGIF2 expression and clinicopathologic features, prognostic value, and potential biological functions in glioma patients. The impact of TGIF2 on tumor immune infiltration was assessed through Estimate, ssGSEA, and Spearman analysis. Genes coexpressed with TGIF2 were identified, and the protein-protein interaction (PPI) network of these coexpressed genes were constructed using the STRING database and Cytoscape software. Hub genes were identified using CytoHubba plugin, and their clinical predictive value was explored. Furthermore, in vitro experiments were performed by knocking down and knocking out TGIF2 using siRNA and CRISPR/Cas9 gene editing, and the role of TGIF2 in glioma cell invasion and migration was analyzed using transwell assay, scratch wound-healing assay, RT-qPCR, and Western blot. Results: TGIF2 mRNA was found to be upregulated in 21 cancers, including glioma. High expression of TGIF2 was associated with malignant phenotypes and poor prognosis in glioma patients, indicating its potential as an independent prognostic factor. Furthermore, elevated TGIF2 expression positively correlated with cell cycle regulation, DNA synthesis and repair, extracellular matrix (ECM) components, immune response, and several signaling pathways that promote tumor progression. TGIF2 showed correlations with Th2 cells, macrophages, and various immunoregulatory genes. The hub genes coexpressed with TGIF2 demonstrated significant predictive value. Additionally, in vitro experiments revealed that knockdown and knockout of TGIF2 inhibited glioma cell invasion, migration and suppressed the epithelial-mesenchymal transition (EMT) phenotype. Conclusion: TGIF2 emerges as a potential biomarker for glioma, possibly linked to tumor immune infiltration and EMT.


Assuntos
Glioma , Humanos , Prognóstico , Biomarcadores , Glioma/diagnóstico , Glioma/genética , Fenótipo , Aminoácidos , Proteínas Repressoras , Proteínas de Homeodomínio/genética
14.
J Cancer ; 15(3): 809-824, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38213725

RESUMO

Background: Colorectal cancer (CRC) is one of the most common malignant tumors and has high morbidity and mortality rates. Previous studies have shown that TSPEAR mutations are involved in the development and progression of gastric cancer and liver cancer. However, the role of TSPEAR in CRC is still unclear. Methods: In The Cancer Genome Atlas (TCGA) database, 590 CRC patients with complete survival information were analyzed. We assessed TSPEAR expression in a pan-cancer dataset from the TCGA database. Cox regression analysis was performed to evaluate factors associated with prognosis. Enrichment analysis via the R package "clusterProfiler" was used to explore the potential function of TSPEAR. The single-sample GSEA (ssGSEA) method from the R package "GSVA" and the TIMER database were used to investigate the association between the immune infiltration level and TSPEAR expression in CRC. The R package "maftools" was used to explore the association between tumour mutation burden (TMB) and TSPEAR expression in CRC. CCK-8 assays and cell invasion assays were used to detect the effect of TSPEAR and TGIF2 on the biological behavior of CRC cells. Results: Pan-cancer analysis revealed that TSPEAR was upregulated in CRC tissues compared to normal tissues and that high TSPEAR expression was associated with poorer overall survival (OS) (p=0.0053). The expression of TSPEAR increased with increasing TNM stage, T stage, N stage, and M stage. The nomogram constructed with TSPEAR, age, and TNM stage showed better predictive value than TSPEAR, age, or TNM stage alone. Immune cell infiltration analysis revealed that high expression of TSPEAR was associated with lower immune cell infiltration. Tumor mutation burden (TMB) analysis indicated that high expression of TSPEAR was associated with lower TMB (p=0.005), and high TMB was associated with shorter OS (p=0.02). CCK-8 assays and cell invasion assays indicated that in vitro knockdown of TSPEAR inhibited the proliferation, migration, and invasion of CRC cells. In addition, TSPEAR expression may be regulated by the upstream transcription factor TGIF2. Conclusion: TSPEAR expression was higher in CRC tissues than in normal tissues. Its upregulation was significantly associated with a poor prognosis. Additionally, TSPEAR plays a significant role in tumor immunity and the biological behavior of CRC cells. Thus, TSPEAR may become a promising prognostic biomarker and therapeutic target for CRC patients.

15.
Adv Mater ; : e2400933, 2024 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-38801772

RESUMO

Photodynamic therapy (PDT) continues to encounter multifarious hurdles, stemming from the ineffectual preservation and delivery system of photosensitizers, the dearth of imaging navigation, and the antioxidant/hypoxic tumor microenvironment. Herein, a versatile cryomicroneedle patch (denoted as CMN-CCPH) is developed for traceable PDT. The therapeutic efficacy is further amplified by catalase (CAT)-induced oxygen (O2) generation and Cu2+-mediated glutathione (GSH) depletion. The CMN-CCPH is composed of cryomicroneedle (CMN) as the vehicle and CAT-biomineralized copper phosphate nanoflowers (CCP NFs) loaded with hematoporphyrin monomethyl ether (HMME) as the payload. Importantly, the bioactive function of HMME and CAT can be optimally maintained under the protection of CCPH and CMN for a duration surpassing 60 days, leading to bolstered bioavailability and notable enhancements in PDT efficacy. The in vivo visualization of HMME and oxyhemoglobin saturation (sO2) monitored by fluorescence (FL)/photoacoustic (PA) duplex real-time imaging unveils the noteworthy implications of CMN-delivered CCPH for intratumoral enrichment of HMME and O2 with reduced systemic toxicity. This versatile CMN patch demonstrates distinct effectiveness in neoplasm elimination, underscoring its promising clinical prospects.

16.
Folia Microbiol (Praha) ; 68(1): 73-86, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-35913660

RESUMO

Bacillus species as fungal antagonistic agents have been widely used in the agriculture and considered as safe products for the management of plant pathogens. In this study, we reported the whole genome sequence of strain LJBV19 isolated from grapevine rhizosphere soil. Strain LJBV19 was identified as Bacillus velezensis through morphological, physicochemical, molecular analysis and genome comparison. Bacillus velezensis LJBV19 had a significant inhibitory effect on the growth of Magnaporthe oryzae with an inhibition ratio up to 75.55% and showed broad spectrum of activity against fungal phytopathogens. The 3,973,013-bp circular chromosome with an average GC content of 46.5% consisted of 3993 open reading frames (ORFs), and 3308 ORFs were classified into 19 cluster of orthologous groups of proteins (COG) categories. Genes related to cell wall degrading enzymes were predicted by Carbohydrate-Active enZYmes (CAZy) database and validated at the metabolic level, producing 0.53 ± 0.00 U/mL cellulose, 0.14 ± 0.01 U/mL chitinase, and 0.11 ± 0.01 U/mL chitosanase. Genome comparison confirmed the taxonomic position of LJBV19, conserved genomic structure, and genetic homogeneity. Moreover, 13 gene clusters for biosynthesis of secondary metabolites in LJBV19 genome were identified and two unique clusters (clusters 2 and 12) shown to direct an unknown compound were only present in strain LJBV19. In general, our results will provide insights into the antifungal mechanisms of Bacillus velezensis LJBV19 and further application of the strain.


Assuntos
Bacillus , Genoma Bacteriano , Antifúngicos/química , Genômica
17.
Chem Commun (Camb) ; 59(13): 1793-1796, 2023 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-36722410

RESUMO

Chiral organic-inorganic hybrid semiconductors (COIHSs) dominated by lead halides have recently gained tremendous interest. Here, we report a lead-free photoluminescent COIHS [R-3-hydroxylpiperidinium]2SbCl5 with a bandgap of 3.14 eV. It shows a ferroelastic phase transition at 341 K accompanied by a switchable second-harmonic generation response and presents clear ferroelastic domains, which are rarely found in lead-free COIHSs.

18.
Commun Biol ; 6(1): 39, 2023 01 13.
Artigo em Inglês | MEDLINE | ID: mdl-36639437

RESUMO

The large-scale preparation of Polyehylene terephthalate (PET) hydrolysing enzymes in low-cost is critical for the biodegradation of PET in industry. In the present study, we demonstrate that the post-translational glycosylation of Pichia pastoris makes it a remarkable host for the heterologous expression of PETase from Ideonella sakaiensis 201-F6 (IsPETase). Taking advantage of the abundant N- and O-linked glycosylation sites in IsPETase and the efficient post-translational modification in endoplasmic reticulum, IsPETase is heavily glycosylated during secretory expression with P. pastoris, which improves the specific activity and thermostability of the enzyme dramatically. Moreover, the specific activity of IsPETase increased further after the bulky N-linked polysaccharide chains were eliminated by Endo-ß-N-acetylglucosaminidase H (Endo H). Importantly, the partially deglycosylated IsPETase still maintained high thermostability because of the remaining mono- and oligo-saccharide residues on the protein molecules. Consequently, the partially deglycosylated IsPETase was able to be applied at 50 °C and depolymerized raw, untreated PET flakes completely in 2 to 3 days. This platform was also applied for the preparation of a famous variant of IsPETase, Fast-PETase, and the same result was achieved. Partially deglycosylated Fast-PETase demonstrates elevated efficiency in degrading postconsumer-PET trays under 55 °C than 50 °C, the reported optimal temperature of Fast-PETase. The present study provides a strategy to modulate thermostable IsPETase through glycosylation engineering and paves the way for promoting PET biodegradation from laboratories to factories.


Assuntos
Burkholderiales , Hidrolases , Hidrolases/química , Burkholderiales/metabolismo , Processamento de Proteína Pós-Traducional , Polissacarídeos
19.
JACS Au ; 3(4): 1196-1204, 2023 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-37124294

RESUMO

Ferroelectric materials are a special type of polar substances, including solids or liquid crystals. However, obtaining a material to be ferroelectric in both its solid crystal (SC) and liquid crystal (LC) phases is a great challenge. Moreover, although cholesteric LCs inherently possess the advantage of high fluidity, their ferroelectricity remains unknown. Here, through the reasonable H/F substitution on the fourth position of the phenyl group of the parent nonferroelectric dihydrocholesteryl benzoate, we designed ferroelectric dihydrocholesteryl 4-fluorobenzoate (4-F-BDC), which shows ferroelectricity in both SC and cholesteric LC phases. The fluorination induces a lower symmetric polar P1 space group and a new solid-to-solid phase transition in 4-F-BDC. Beneficial from fluorination, the SC and cholesteric LC phases of 4-F-BDC show clear ferroelectricity, as confirmed by well-shaped polarization-voltage hysteresis loops. The dual ferroelectricity in both SC and cholesteric LC phases of a single material was rarely found. This work offers a viable case for the exploration of the interplay between ferroelectric SC and LC phases and provides an efficient approach for designing ferroelectrics with dual ferroelectricity and cholesteric ferroelectric liquid crystals.

20.
Chem Commun (Camb) ; 59(68): 10295-10298, 2023 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-37540031

RESUMO

Bismuth(III) iodide perovskites have attracted great attention as lead-free hybrid semiconductors, but they mainly show zero- and one-dimensional structures. Herein, we report the first two-dimensional chiral perovskite-like bismuth(III) iodide hybrid [(S)-3-aminopyrrolidinium I]2Bi2/3I4 (1) with a high phase transition temperature of 408.8 K, higher than most of the reported chiral lead-free hybrid semiconductors.

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