Cleavage and reassembly of C-C bonds is a fascinating and challenging strategy to forge complex high-value molecules in an atom-and step-efficient manner.Herein,we disclose a photoredox-catalyzed four-atom skeletal ed...Cleavage and reassembly of C-C bonds is a fascinating and challenging strategy to forge complex high-value molecules in an atom-and step-efficient manner.Herein,we disclose a photoredox-catalyzed four-atom skeletal editing strategy,enabling highly selective reassembly of 1,3-diketones into architecturally distinct acylated 1,5-ketoalcohols with excellent atom,step,and redox economy.Notably,this propoxy insertion unit(i.e.,three sp3-hybridized carbons and one oxygen atom)is derived from the other two simple and readily available starting materials(i.e.,alkene and aldehyde).Experimental studies have elucidated the key intermediate(lactol)and reaction mechanism(radical-radical crossover cyclizationearrangement),which are distinct from classical De Mayo reaction.More importantly,the rapid construction of high-value-added product γ,δ-unsaturated ketones and dihydropyrans is also achieved via photocatalytic synthesis of acylated 1,5-ketoalcohols/Lewis acid-promoted Wagner-Meerwein rearrangement cascade and photocatalytic formal[2+2+2]annulation/MsCl-promoted elimination cascade,respectively.展开更多
Common artifacts existing in anisotropic elastic reverse time migration(ERTM)image are mainly crosstalk artifacts,false images and low-frequency noise.To address these problems,we propose a new elastic wave decomposit...Common artifacts existing in anisotropic elastic reverse time migration(ERTM)image are mainly crosstalk artifacts,false images and low-frequency noise.To address these problems,we propose a new elastic wave decomposition approach in vertical transversely isotropic(VTI)media,which decompose original elastic wavefield into up-/down-going P-wave and S-wave components for ameliorating imaging artifacts in ERTM.We first apply a space-domain VTI P/S wave-mode decomposition operator,reducing the cross-talk artifacts of ERTM image.Then,we derive the dispersion relation formulation of P-wave and S-wave which are used to construct Hilbert transformed operators in VTI media.For adapting to complex model,the first-order Taylor expansion around anisotropic parameter is applied to these derived P/S wave Hilbert transformed operators.We therefore present an up/down wavefield separation operator for VTI media that requires solving the wave equation only once,computing both the original wavefield and its Hilbert transform.This up/down going separated operator can be used to suppress false images and low-frequency noise of ERTM images.Finally we embed proposed up/down going wave separation into P/S wave-mode decomposition and develop a new elastic wave decomposing approach,which can efficiently improve the image quality in VTI ERTM.Simple and complex synthetic models demonstrate the effectiveness of our method.展开更多
The amide moiety plays an important role as a powerful bioactive backbone,and as the synthetic chemistry community moves toward more sp3-rich scaffolds,alkyl halides have become the feedstock of choice for obtainin...The amide moiety plays an important role as a powerful bioactive backbone,and as the synthetic chemistry community moves toward more sp3-rich scaffolds,alkyl halides have become the feedstock of choice for obtaining carbonylation products.With the development of photoredox catalysis,several aminocarbonylation systems for alkyl halides were developed which usually require transition metal catalysis.Considering the demands for green sustainable chemical synthesis,here we report a metal-free,exogenous catalyst-free aminocarbonylation reaction of alkyl iodides under atmospheric pressure of carbon monoxide.Through a combination of EDA and XAT strategies,the reaction occurs efficiently under only light irradiation at room temperature.展开更多
Herein,we present a copper-catalyzed carbonylative cross-coupling of unactivated alkyl bromides with aryl boronates under CO atmosphere which enabling the efficient synthesis of C(sp3)-C(sp2)ketones with extensive fun...Herein,we present a copper-catalyzed carbonylative cross-coupling of unactivated alkyl bromides with aryl boronates under CO atmosphere which enabling the efficient synthesis of C(sp3)-C(sp2)ketones with extensive functional group compatibility.This strategy represents a significant advance in copper-catalyzed carbonylation involving alkyl bromides and C(sp2)-nucleophiles.The protocol addresses key challenges commonly encountered in the coupling of C(sp3)-alkyl halides with aryl boron reagents,such as sluggish oxidative addition of alkyl halides,competing Suzuki-Miyaura cross-coupling,undesired dehalogenation and so on.Distinguished by its broad substrate scope and high functional group tolerance,this approach offers a robust and versatile platform for the streamlined synthesis of alkyl aryl ketones.展开更多
Carboxylic acid derivatives withα-quaternary carbon center are one of the most ubiquitous moieties in synthetic and medicinal chemistry.Hence,novel and efficient synthetic methods towards carboxylic acid derivatives ...Carboxylic acid derivatives withα-quaternary carbon center are one of the most ubiquitous moieties in synthetic and medicinal chemistry.Hence,novel and efficient synthetic methods towards carboxylic acid derivatives withα-quaternary carbon remain in high demand.However,most of the precursors of these complex compounds are not easy to prepare.Reported herein is a carbonylative five-component synthesis of amides and esters withα-quaternary carbon center enabled by palladium catalysis from abundant acrylonitrile,carbon monoxide,fluoroalkyl halides,and nucleophiles.Diverse amides and esters withα-quaternary carbon which contain difluoromethyl or perfluoroalkyl moiety were prepared in good to excellent yields,providing an efficient synthetic platform for sequential transformations.展开更多
The impact of rolling temperature and the crystallographic orientation ofα-colonies on the globularization behavior of lamellarα+βmicrostructure in Ti-6Al-4V alloy was investigated.Firstly,the lamellar structure wa...The impact of rolling temperature and the crystallographic orientation ofα-colonies on the globularization behavior of lamellarα+βmicrostructure in Ti-6Al-4V alloy was investigated.Firstly,the lamellar structure was heavily rolled at 600,700,800 and 900°C,respectively.Heavy rolling from temperatures of 600 to 900°C resulted in an increased volume fraction and thickness ofβlamellae,while the corresponding parameters forαlamellae decreased.Then,these rolledα+βlamellar microstructures were spheroidized into equiaxed grains upon subsequent annealing.The results demonstrate that the globularization fraction of the lamellar structures diminishes as the rolling temperature increases.Additionally,the globularization fraction forα-colonies with hard crystallographic orientations,such as//ND and//TD,is considerably lower compared to those with softer orientations,positioned at certain angles to ND,RD,and TD during annealing process.This results in heterogeneous globularization ofαlamellae,leading to the development of pronounced sharp micro-texture.Furthermore,the slipping deformations ofα-colonies with varying crystallographic orientations during rolling were meticulously analyzed.展开更多
1-deoxynojirimycin (1-DNJ) contents in the silkworm,Bombyx mori,at different developmental stages and tissues were investigated by using reverse-phase high-performance liquid chromatography. The 1-DNJ contents of silk...1-deoxynojirimycin (1-DNJ) contents in the silkworm,Bombyx mori,at different developmental stages and tissues were investigated by using reverse-phase high-performance liquid chromatography. The 1-DNJ contents of silkworm larvae change significantly with their developmental stages. The male larvae showed higher accumulation efficiency of 1-DNJ than the females and also a significant variation was observed among the silkworm strains. The present results show that tissue distribution of 1-DNJ was significantly higher in blood,digestive juice,and alimentary canal,but no 1-DNJ was observed in the silkgland. Moreover,1-DNJ was not found in silkworms fed with artificial diet that does not contain mulberry leaf powder. This proves that silkworms obtain 1-DNJ from mulberry leaves; they could not synthesize 1-DNJ by themselves. The accumulation and excretion of 1-DNJ change periodically during the larval stage. There was no 1-DNJ in the newly-hatched larvae and 1-DNJ was mainly accumulated during the early and middle stages of every instar,while excreted at later stages of larval development. Further,it is possible to extract 1-DNJ from the larval feces and it is optimal to develop the 1-DNJ related products for diabetic auxiliary therapy.展开更多
BACKGROUND In clinical practice,the diagnosis is sometimes difficult with contrast-enhanced ultrasound(CEUS)when the case has an atypical perfusion pattern.Color parametric imaging(CPI)is an analysis software for CEUS...BACKGROUND In clinical practice,the diagnosis is sometimes difficult with contrast-enhanced ultrasound(CEUS)when the case has an atypical perfusion pattern.Color parametric imaging(CPI)is an analysis software for CEUS with better detection of temporal differences in CEUS imaging using arbitrary colors.It measures the differences in arrival time of the contrast agent in lesions so that the perfusion features of atypical hemangioma and colorectal cancer(CRC)liver metastasis can be distinguished.AIM To evaluate the role of a novel type of CPI of CEUS in the differential diagnosis of atypical hemangioma from liver metastases in patients with a history of CRC.METHODS From January 2016 to July 2018,42 patients including 20 cases of atypical hemangioma and 22 cases of liver metastases from CRC were enrolled.These patients had a mean age of 60.5±9.3 years(range:39-75 years).All patients received ultrasound,CEUS and CPI examinations.Resident and staff radiologists independently and retrospectively reviewed CEUS and CPI images.Two sets of criteria were assigned:(1)Routine CEUS alone;and(2)CEUS and CPI.The diagnostic sensitivity,specificity,accuracy and receiver operating characteristic(ROC)curve of resident and staff radiologists were analyzed.RESULTS The following CPI features were significantly different between liver hemangioma and liver metastases analyzed by staff and resident radiologists:Peripheral nodular enhancement(65%-70.0%vs 4.5%-13.6%,P<0.001,P=0.001),mosaic/chaotic enhancement(5%-10%vs 68.2%-63.6%,P<0.001,P<0.001)and feeding artery(20%vs 59.1%-54.5%,P=0.010,P=0.021).CPI imaging offered significant improvements in detection rates compared with routine CEUS in both resident and staff groups.By resident radiologists,the specificity and accuracy of CEUS+CPI were significantly increased compared with that of CEUS(77.3%vs 45.5%,P=0.030;78.6%vs 50.0%,P=0.006).In addition,the area under the curve(AUC)of CEUS+CPI was significantly higher than that of CEUS(0.803 vs 0.757,P=0.036).By staff radiologists,accuracy was improved in CEUS+CPI(81.0%vs 54.8%,P=0.010),whereas no significant differences in specificity and sensitivity were found(P=0.144,P=0.112).The AUC of CEUS+CPI was significantly higher than that of CEUS(0.890 vs 0.825,P=0.013)by staff radiologists.CONCLUSION Compared with routine CEUS,CPI could provide specific information on the hemodynamic features of liver lesions and help to differentiate atypical hemangioma from liver metastases in patients with CRC,even for senior radiologists.展开更多
The microstructure and dry sliding wear behav- ior of cast Al-18 wt% MgaSi in-situ metal matrix com- posite modified by Nd were investigated. Experimental results show that, after introducing a proper amount of Nd, bo...The microstructure and dry sliding wear behav- ior of cast Al-18 wt% MgaSi in-situ metal matrix com- posite modified by Nd were investigated. Experimental results show that, after introducing a proper amount of Nd, both primary and eutectic Mg2Si in the Al-18 wt% Mg2Si composite are well modified. The morphology of primary Mg2Si is changed from irregular or dendritic to polyhedral shape, and its average particle size is signifi- cantly decreased. Moreover, the morphology of the eutectic MgzSi phase is altered from flake-like to very short fibrous or dot-like. The wear rates and friction coefficient of the composites with Nd are lower than those without Nd. Furthermore, the addition of 0.5 wt% Nd changes the wear mechanism of the composite from the combination of abrasive, adhesive, and delamination wear without Nd into a single mild abrasion wear with 0.5 wt% Nd.展开更多
In the late phase of Bombyx mori nucleopolyhedrovirus(BmNPV)infection,a large amount of polyhedra appear in the infected cell nucleolus,these polyhedra being dense protein crystals protecting the incorporated virions ...In the late phase of Bombyx mori nucleopolyhedrovirus(BmNPV)infection,a large amount of polyhedra appear in the infected cell nucleolus,these polyhedra being dense protein crystals protecting the incorporated virions from the harsh environment.To investigate whether the foreign protein could be immobilized into the polyhedra of BmNPV,two recombinant baculoviruses were generated by a novel BmNPV polyhedrin-plus(polh +)Bac-to-Bac system,designated as vBmBac(polh +)-enhanced green fluorescent protein(EGFP)and vBmBac(polh +)-LacZ,which can express the polyhedrin and foreign protein simultaneously.Light microscopy analysis showed that all viruses produced polyhedra of normal appearance.Green fluorescence can be apparently detected on the surface of the vBmBac(polh +)-EGFP polyhedra,but not the BmNPV polyhedra.Fluorescence analysis and anti-desiccation testing confirmed that EGFP was embedded in the polyhedra.As expected,the vBmBac(polh +)-LacZ polyhedra contained an amount of LacZ and had a higherβ-galactosidase activity.Sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE)and Western blotting were also performed to verify if the foreign proteins were immobilized into polyhedra.This study provides a new inspiration for efficient preservation of useful proteins and development of new pesticides with toxic proteins.展开更多
BACKGROUND The immunosuppressive capacity of mesenchymal stem cells(MSCs)is dependent on the“license”of several proinflammatory factors to express immunosuppressive factors such as programmed cell death 1 ligand 1(P...BACKGROUND The immunosuppressive capacity of mesenchymal stem cells(MSCs)is dependent on the“license”of several proinflammatory factors to express immunosuppressive factors such as programmed cell death 1 ligand 1(PD-L1),which determines the clinical therapeutic efficacy of MSCs for inflammatory or immune diseases.In MSCs,interferon-gamma(IFN-γ)is a key inducer of PD-L1 expression,which is synergistically enhanced by tumor necrosis factor-alpha(TNF-α);however,the underlying mechanism is unclear.AIM To reveal the mechanism of pretreated MSCs express high PD-L1 and explore the application of pretreated MSCs in ulcerative colitis.METHODS We assessed PD-L1 expression in human umbilical-cord-derived MSCs(hUC-MSCs)induced by IFN-γand TNF-α,alone or in combination.Additionally,we performed signal pathway inhibitor experiments as well as RNA interference experiments to elucidate the molecular mechanism by which IFN-γalone or in combination with TNF-αinduces PD-L1 expression.Moreover,we used luciferase reporter gene experiments to verify the binding sites of the transcription factors of each signal transduction pathway to the targeted gene promoters.Finally,we evaluated the immunosuppressive capacity of hUC-MSCs treated with IFN-γand TNF-αin both an in vitro mixed lymphocyte culture assay,and in vivo in mice with dextran sulfate sodium-induced acute colitis.RESULTS Our results suggest that IFN-γinduction alone upregulates PD-L1 expression in hUC-MSCs while TNF-αalone does not,and that the co-induction of IFN-γand TNF-αpromotes higher expression of PD-L1.IFN-γinduces hUCMSCs to express PD-L1,in which IFN-γactivates the JAK/STAT1 signaling pathway,up-regulates the expression of the interferon regulatory factor 1(IRF1)transcription factor,promotes the binding of IRF1 and the PD-L1 gene promoter,and finally promotes PD-L1 mRNA.Although TNF-αalone did not induce PD-L1 expression in hUCMSCs,the addition of TNF-αsignificantly enhanced IFN-γ-induced JAK/STAT1/IRF1 activation.TNF-αupregulated IFN-γreceptor expression through activation of the nuclear factor kappa-B signaling pathway,which significantly enhanced IFN-γsignaling.Finally,co-induced hUC-MSCs have a stronger inhibitory effect on lymphocyte proliferation,and significantly ameliorate weight loss,mucosal damage,inflammatory cell infiltration,and up-regulation of inflammatory factors in colitis mice.CONCLUSION Overall,our results suggest that IFN-γand TNF-αenhance both the immunosuppressive ability of hUC-MSCs and their efficacy in ulcerative colitis by synergistically inducing high expression of PD-L1.展开更多
BACKGROUND Severe skeletal class II malocclusion is the indication for combined orthodontic and orthognathic treatment.CASE SUMMARY A woman with a chief complaint of a protruding chin and an inability to close her lip...BACKGROUND Severe skeletal class II malocclusion is the indication for combined orthodontic and orthognathic treatment.CASE SUMMARY A woman with a chief complaint of a protruding chin and an inability to close her lips requested orthodontic camouflage.The treatment plan consisted of extracting the right upper third molar,right lower third molar,left lower second molar,and left upper third molar and moving the maxillary dentition distally using a convenient method involving microimplant nail anchors,push springs,long arm traction hooks,and elastic traction chains.After 52 months of treatment,her overbite and overjet were normal,and her facial profile was favorable.CONCLUSION This method can be used for distal movement of the maxillary dentition and to correct severe skeletal class II malocclusion in adults.展开更多
Polyvinyl chloride (PVC) polymerizing process is a typical complicated industrial process with the characteristics of large inertia, big time delay and nonlinearity. Firstly, for the general nonlinear and discrete t...Polyvinyl chloride (PVC) polymerizing process is a typical complicated industrial process with the characteristics of large inertia, big time delay and nonlinearity. Firstly, for the general nonlinear and discrete time system, a design scheme of model-free adaptive (MFA) controller is given. Then, particle swarm optimization (PSO) algorithm is applied to optimizing and setting the key parameters for controller tuning. After that, the MFA controller is used to control the system of polymerizing temperature. Finally, simulation results are given to show that the MAC strategy based on PSO obtains a good controlling performance index.展开更多
A convenient and transition-metal free protocol for quinazolinones synthesis with o-aminobenzamides and benzyl amines as substrates has been developed. Using H;O;as the oxidant, various quinazolinones were obtained in...A convenient and transition-metal free protocol for quinazolinones synthesis with o-aminobenzamides and benzyl amines as substrates has been developed. Using H;O;as the oxidant, various quinazolinones were obtained in moderate to good yields under metal- and additive-free conditions.展开更多
A novel palladium-catalyzed carbonylative cyclization of alkene-tethered indoles with phenols or arylboronic acids is described,which provides a facile approach to access indolo[2,1-a]isoquinoline scaffolds.This metho...A novel palladium-catalyzed carbonylative cyclization of alkene-tethered indoles with phenols or arylboronic acids is described,which provides a facile approach to access indolo[2,1-a]isoquinoline scaffolds.This method employs benzene-1,3,5-triyl triformate(TFBen)as the CO surrogate for the incorporation of a carbonyl group into indolo[2,1-a]isoquinoline scaffolds,and a variety of carbonyl-containing indolo[2,1-a]isoquinoline derivatives are prepared in good yields.展开更多
Chronic non-healing wounds,such as diabetic foot ulcers,represent a clinical challenge with an increasing incidence.1 A deeper understanding of the molecular mechanisms underlying wound healing is of great significanc...Chronic non-healing wounds,such as diabetic foot ulcers,represent a clinical challenge with an increasing incidence.1 A deeper understanding of the molecular mechanisms underlying wound healing is of great significance.RNA m6A modification is a widespread and important epigenetic regulatory mechanism,2 but its role in wound healing remains unclear.In this study,we found that METTL3,an RNA m6A methyltransferase,is a positive regulator of wound healing and that its low expression is closely related to chronic diabetic wounds.展开更多
The fetal weight vs. the gestational age has great significance for fetal growth evaluation in clinic especially in the judgement of IUGR. In this paper, the quantification theory and its application for estimation of...The fetal weight vs. the gestational age has great significance for fetal growth evaluation in clinic especially in the judgement of IUGR. In this paper, the quantification theory and its application for estimation of the gestational age and fetal weight are reported.It is the first time that the theory is applied in this field. The estimation error.of gestational age is less than one week and that of fetal weight is less than 130g.展开更多
The catalytic production of chiral amides from readily available unactivated internal alkenes remains a significant challenge in synthetic chemistry.In this work,we developed a highly enantioselective hydroaminocarbon...The catalytic production of chiral amides from readily available unactivated internal alkenes remains a significant challenge in synthetic chemistry.In this work,we developed a highly enantioselective hydroaminocarbonylation procedure for nonactivated internal alkenes and a wide range ofα-chiral amides were produced effectively with exceptional enantioselectivities using copper as the catalyst.This method is compatible with both symmetric and asymmetric internal alkenes,as well as various hydroxylamine electrophiles,demonstrating wide substrate scope and broad functional group tolerance.The established catalytic system showcases remarkable enantioselective performance in the asymmetric hydroaminocarbonylation of challenging substrates,such as the methyl-ethylα-chiral amide synthesis from trans-2-butene,despite the minimal steric difference between the methyl and ethyl group.This work represents important progress in the field of asymmetric hydroaminocarbonylation and offers a useful tool for the production of valuableα-chiral amide compounds from readily available internal alkenes.展开更多
Aminosilylalkanes are important motifs in bioactive molecules,yet methods for their direct incorporation remain limited.In particular,the efficient introduction of gem-difluoro groups–known to significantly modulate ...Aminosilylalkanes are important motifs in bioactive molecules,yet methods for their direct incorporation remain limited.In particular,the efficient introduction of gem-difluoro groups–known to significantly modulate the physical,chemical,and biological properties of organic molecules–into aminosilylalkane remains a challenge.Herein,we report a cobalt-catalyzed silyldifluoromethylamination of styrenes using TMSCF2H and nitrogen nucleophiles.By employing readily available starting materials,a series of complex,highly functionalized aminosilyldifluoroalkane derivatives were synthesized in moderate to good yields.This methodology establishes a novel strategy for constructing organosilicon compounds,complementing existing synthetic approaches.展开更多
摘要Cleavage and reassembly of C-C bonds is a fascinating and challenging strategy to forge complex high-value molecules in an atom-and step-efficient manner.Herein,we disclose a photoredox-catalyzed four-atom skeletal editing strategy,enabling highly selective reassembly of 1,3-diketones into architecturally distinct acylated 1,5-ketoalcohols with excellent atom,step,and redox economy.Notably,this propoxy insertion unit(i.e.,three sp3-hybridized carbons and one oxygen atom)is derived from the other two simple and readily available starting materials(i.e.,alkene and aldehyde).Experimental studies have elucidated the key intermediate(lactol)and reaction mechanism(radical-radical crossover cyclizationearrangement),which are distinct from classical De Mayo reaction.More importantly,the rapid construction of high-value-added product γ,δ-unsaturated ketones and dihydropyrans is also achieved via photocatalytic synthesis of acylated 1,5-ketoalcohols/Lewis acid-promoted Wagner-Meerwein rearrangement cascade and photocatalytic formal[2+2+2]annulation/MsCl-promoted elimination cascade,respectively.
基金jointly supported by BGP.Inc,CNPC under grant 2023ZZ05-05。
摘要Common artifacts existing in anisotropic elastic reverse time migration(ERTM)image are mainly crosstalk artifacts,false images and low-frequency noise.To address these problems,we propose a new elastic wave decomposition approach in vertical transversely isotropic(VTI)media,which decompose original elastic wavefield into up-/down-going P-wave and S-wave components for ameliorating imaging artifacts in ERTM.We first apply a space-domain VTI P/S wave-mode decomposition operator,reducing the cross-talk artifacts of ERTM image.Then,we derive the dispersion relation formulation of P-wave and S-wave which are used to construct Hilbert transformed operators in VTI media.For adapting to complex model,the first-order Taylor expansion around anisotropic parameter is applied to these derived P/S wave Hilbert transformed operators.We therefore present an up/down wavefield separation operator for VTI media that requires solving the wave equation only once,computing both the original wavefield and its Hilbert transform.This up/down going separated operator can be used to suppress false images and low-frequency noise of ERTM images.Finally we embed proposed up/down going wave separation into P/S wave-mode decomposition and develop a new elastic wave decomposing approach,which can efficiently improve the image quality in VTI ERTM.Simple and complex synthetic models demonstrate the effectiveness of our method.
基金supported by National Key R&D Program of China(No.2023YFA1507500)the International Partnership Program of Chinese Academy of Sciences(No.028GJHZ2023045FN)。
摘要The amide moiety plays an important role as a powerful bioactive backbone,and as the synthetic chemistry community moves toward more sp3-rich scaffolds,alkyl halides have become the feedstock of choice for obtaining carbonylation products.With the development of photoredox catalysis,several aminocarbonylation systems for alkyl halides were developed which usually require transition metal catalysis.Considering the demands for green sustainable chemical synthesis,here we report a metal-free,exogenous catalyst-free aminocarbonylation reaction of alkyl iodides under atmospheric pressure of carbon monoxide.Through a combination of EDA and XAT strategies,the reaction occurs efficiently under only light irradiation at room temperature.
摘要Herein,we present a copper-catalyzed carbonylative cross-coupling of unactivated alkyl bromides with aryl boronates under CO atmosphere which enabling the efficient synthesis of C(sp3)-C(sp2)ketones with extensive functional group compatibility.This strategy represents a significant advance in copper-catalyzed carbonylation involving alkyl bromides and C(sp2)-nucleophiles.The protocol addresses key challenges commonly encountered in the coupling of C(sp3)-alkyl halides with aryl boron reagents,such as sluggish oxidative addition of alkyl halides,competing Suzuki-Miyaura cross-coupling,undesired dehalogenation and so on.Distinguished by its broad substrate scope and high functional group tolerance,this approach offers a robust and versatile platform for the streamlined synthesis of alkyl aryl ketones.
基金the financial support from National Key R&D Program of China(No.2023YFA1507500)DICP。
摘要Carboxylic acid derivatives withα-quaternary carbon center are one of the most ubiquitous moieties in synthetic and medicinal chemistry.Hence,novel and efficient synthetic methods towards carboxylic acid derivatives withα-quaternary carbon remain in high demand.However,most of the precursors of these complex compounds are not easy to prepare.Reported herein is a carbonylative five-component synthesis of amides and esters withα-quaternary carbon center enabled by palladium catalysis from abundant acrylonitrile,carbon monoxide,fluoroalkyl halides,and nucleophiles.Diverse amides and esters withα-quaternary carbon which contain difluoromethyl or perfluoroalkyl moiety were prepared in good to excellent yields,providing an efficient synthetic platform for sequential transformations.
摘要The impact of rolling temperature and the crystallographic orientation ofα-colonies on the globularization behavior of lamellarα+βmicrostructure in Ti-6Al-4V alloy was investigated.Firstly,the lamellar structure was heavily rolled at 600,700,800 and 900°C,respectively.Heavy rolling from temperatures of 600 to 900°C resulted in an increased volume fraction and thickness ofβlamellae,while the corresponding parameters forαlamellae decreased.Then,these rolledα+βlamellar microstructures were spheroidized into equiaxed grains upon subsequent annealing.The results demonstrate that the globularization fraction of the lamellar structures diminishes as the rolling temperature increases.Additionally,the globularization fraction forα-colonies with hard crystallographic orientations,such as//ND and//TD,is considerably lower compared to those with softer orientations,positioned at certain angles to ND,RD,and TD during annealing process.This results in heterogeneous globularization ofαlamellae,leading to the development of pronounced sharp micro-texture.Furthermore,the slipping deformations ofα-colonies with varying crystallographic orientations during rolling were meticulously analyzed.
摘要1-deoxynojirimycin (1-DNJ) contents in the silkworm,Bombyx mori,at different developmental stages and tissues were investigated by using reverse-phase high-performance liquid chromatography. The 1-DNJ contents of silkworm larvae change significantly with their developmental stages. The male larvae showed higher accumulation efficiency of 1-DNJ than the females and also a significant variation was observed among the silkworm strains. The present results show that tissue distribution of 1-DNJ was significantly higher in blood,digestive juice,and alimentary canal,but no 1-DNJ was observed in the silkgland. Moreover,1-DNJ was not found in silkworms fed with artificial diet that does not contain mulberry leaf powder. This proves that silkworms obtain 1-DNJ from mulberry leaves; they could not synthesize 1-DNJ by themselves. The accumulation and excretion of 1-DNJ change periodically during the larval stage. There was no 1-DNJ in the newly-hatched larvae and 1-DNJ was mainly accumulated during the early and middle stages of every instar,while excreted at later stages of larval development. Further,it is possible to extract 1-DNJ from the larval feces and it is optimal to develop the 1-DNJ related products for diabetic auxiliary therapy.
基金Supported by Capital Medical Development Program,No.2018-2-2154National Natural Science Foundation of China,No.81773286
摘要BACKGROUND In clinical practice,the diagnosis is sometimes difficult with contrast-enhanced ultrasound(CEUS)when the case has an atypical perfusion pattern.Color parametric imaging(CPI)is an analysis software for CEUS with better detection of temporal differences in CEUS imaging using arbitrary colors.It measures the differences in arrival time of the contrast agent in lesions so that the perfusion features of atypical hemangioma and colorectal cancer(CRC)liver metastasis can be distinguished.AIM To evaluate the role of a novel type of CPI of CEUS in the differential diagnosis of atypical hemangioma from liver metastases in patients with a history of CRC.METHODS From January 2016 to July 2018,42 patients including 20 cases of atypical hemangioma and 22 cases of liver metastases from CRC were enrolled.These patients had a mean age of 60.5±9.3 years(range:39-75 years).All patients received ultrasound,CEUS and CPI examinations.Resident and staff radiologists independently and retrospectively reviewed CEUS and CPI images.Two sets of criteria were assigned:(1)Routine CEUS alone;and(2)CEUS and CPI.The diagnostic sensitivity,specificity,accuracy and receiver operating characteristic(ROC)curve of resident and staff radiologists were analyzed.RESULTS The following CPI features were significantly different between liver hemangioma and liver metastases analyzed by staff and resident radiologists:Peripheral nodular enhancement(65%-70.0%vs 4.5%-13.6%,P<0.001,P=0.001),mosaic/chaotic enhancement(5%-10%vs 68.2%-63.6%,P<0.001,P<0.001)and feeding artery(20%vs 59.1%-54.5%,P=0.010,P=0.021).CPI imaging offered significant improvements in detection rates compared with routine CEUS in both resident and staff groups.By resident radiologists,the specificity and accuracy of CEUS+CPI were significantly increased compared with that of CEUS(77.3%vs 45.5%,P=0.030;78.6%vs 50.0%,P=0.006).In addition,the area under the curve(AUC)of CEUS+CPI was significantly higher than that of CEUS(0.803 vs 0.757,P=0.036).By staff radiologists,accuracy was improved in CEUS+CPI(81.0%vs 54.8%,P=0.010),whereas no significant differences in specificity and sensitivity were found(P=0.144,P=0.112).The AUC of CEUS+CPI was significantly higher than that of CEUS(0.890 vs 0.825,P=0.013)by staff radiologists.CONCLUSION Compared with routine CEUS,CPI could provide specific information on the hemodynamic features of liver lesions and help to differentiate atypical hemangioma from liver metastases in patients with CRC,even for senior radiologists.
基金financially supported by the National Natural Youth Science Foundation of China (No. 50901038)the Key Laboratory Foundation of Liaoning Provincial Committee of Education (Nos. 20060394 and 2009S053)
摘要The microstructure and dry sliding wear behav- ior of cast Al-18 wt% MgaSi in-situ metal matrix com- posite modified by Nd were investigated. Experimental results show that, after introducing a proper amount of Nd, both primary and eutectic Mg2Si in the Al-18 wt% Mg2Si composite are well modified. The morphology of primary Mg2Si is changed from irregular or dendritic to polyhedral shape, and its average particle size is signifi- cantly decreased. Moreover, the morphology of the eutectic MgzSi phase is altered from flake-like to very short fibrous or dot-like. The wear rates and friction coefficient of the composites with Nd are lower than those without Nd. Furthermore, the addition of 0.5 wt% Nd changes the wear mechanism of the composite from the combination of abrasive, adhesive, and delamination wear without Nd into a single mild abrasion wear with 0.5 wt% Nd.
基金supported by the National Basic Research Program(973)of China(No.2012CB114600)the Zhejiang Provincial Natural Science Foundation(No.Y3110058)the Public Agricultural Program of Zhejiang Province(No.2012C32G2010076),China
摘要In the late phase of Bombyx mori nucleopolyhedrovirus(BmNPV)infection,a large amount of polyhedra appear in the infected cell nucleolus,these polyhedra being dense protein crystals protecting the incorporated virions from the harsh environment.To investigate whether the foreign protein could be immobilized into the polyhedra of BmNPV,two recombinant baculoviruses were generated by a novel BmNPV polyhedrin-plus(polh +)Bac-to-Bac system,designated as vBmBac(polh +)-enhanced green fluorescent protein(EGFP)and vBmBac(polh +)-LacZ,which can express the polyhedrin and foreign protein simultaneously.Light microscopy analysis showed that all viruses produced polyhedra of normal appearance.Green fluorescence can be apparently detected on the surface of the vBmBac(polh +)-EGFP polyhedra,but not the BmNPV polyhedra.Fluorescence analysis and anti-desiccation testing confirmed that EGFP was embedded in the polyhedra.As expected,the vBmBac(polh +)-LacZ polyhedra contained an amount of LacZ and had a higherβ-galactosidase activity.Sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE)and Western blotting were also performed to verify if the foreign proteins were immobilized into polyhedra.This study provides a new inspiration for efficient preservation of useful proteins and development of new pesticides with toxic proteins.
基金Supported by the National Natural Science Foundation of China,No.81871568,No.32100643COVID-19 Infection and Prevention Emergency Special Project of Chongqing Education Commission,No.KYYJ202009.
摘要BACKGROUND The immunosuppressive capacity of mesenchymal stem cells(MSCs)is dependent on the“license”of several proinflammatory factors to express immunosuppressive factors such as programmed cell death 1 ligand 1(PD-L1),which determines the clinical therapeutic efficacy of MSCs for inflammatory or immune diseases.In MSCs,interferon-gamma(IFN-γ)is a key inducer of PD-L1 expression,which is synergistically enhanced by tumor necrosis factor-alpha(TNF-α);however,the underlying mechanism is unclear.AIM To reveal the mechanism of pretreated MSCs express high PD-L1 and explore the application of pretreated MSCs in ulcerative colitis.METHODS We assessed PD-L1 expression in human umbilical-cord-derived MSCs(hUC-MSCs)induced by IFN-γand TNF-α,alone or in combination.Additionally,we performed signal pathway inhibitor experiments as well as RNA interference experiments to elucidate the molecular mechanism by which IFN-γalone or in combination with TNF-αinduces PD-L1 expression.Moreover,we used luciferase reporter gene experiments to verify the binding sites of the transcription factors of each signal transduction pathway to the targeted gene promoters.Finally,we evaluated the immunosuppressive capacity of hUC-MSCs treated with IFN-γand TNF-αin both an in vitro mixed lymphocyte culture assay,and in vivo in mice with dextran sulfate sodium-induced acute colitis.RESULTS Our results suggest that IFN-γinduction alone upregulates PD-L1 expression in hUC-MSCs while TNF-αalone does not,and that the co-induction of IFN-γand TNF-αpromotes higher expression of PD-L1.IFN-γinduces hUCMSCs to express PD-L1,in which IFN-γactivates the JAK/STAT1 signaling pathway,up-regulates the expression of the interferon regulatory factor 1(IRF1)transcription factor,promotes the binding of IRF1 and the PD-L1 gene promoter,and finally promotes PD-L1 mRNA.Although TNF-αalone did not induce PD-L1 expression in hUCMSCs,the addition of TNF-αsignificantly enhanced IFN-γ-induced JAK/STAT1/IRF1 activation.TNF-αupregulated IFN-γreceptor expression through activation of the nuclear factor kappa-B signaling pathway,which significantly enhanced IFN-γsignaling.Finally,co-induced hUC-MSCs have a stronger inhibitory effect on lymphocyte proliferation,and significantly ameliorate weight loss,mucosal damage,inflammatory cell infiltration,and up-regulation of inflammatory factors in colitis mice.CONCLUSION Overall,our results suggest that IFN-γand TNF-αenhance both the immunosuppressive ability of hUC-MSCs and their efficacy in ulcerative colitis by synergistically inducing high expression of PD-L1.
基金Supported by Medical Science Research Project Plan by Health Commission of the Hebei Province,No.20220063.
摘要BACKGROUND Severe skeletal class II malocclusion is the indication for combined orthodontic and orthognathic treatment.CASE SUMMARY A woman with a chief complaint of a protruding chin and an inability to close her lips requested orthodontic camouflage.The treatment plan consisted of extracting the right upper third molar,right lower third molar,left lower second molar,and left upper third molar and moving the maxillary dentition distally using a convenient method involving microimplant nail anchors,push springs,long arm traction hooks,and elastic traction chains.After 52 months of treatment,her overbite and overjet were normal,and her facial profile was favorable.CONCLUSION This method can be used for distal movement of the maxillary dentition and to correct severe skeletal class II malocclusion in adults.
基金supported by University of Science and Technology Liaoning,National Financial Security and System Equipment Engineering Research Center(No.USTLKFGJ201502)
摘要Polyvinyl chloride (PVC) polymerizing process is a typical complicated industrial process with the characteristics of large inertia, big time delay and nonlinearity. Firstly, for the general nonlinear and discrete time system, a design scheme of model-free adaptive (MFA) controller is given. Then, particle swarm optimization (PSO) algorithm is applied to optimizing and setting the key parameters for controller tuning. After that, the MFA controller is used to control the system of polymerizing temperature. Finally, simulation results are given to show that the MAC strategy based on PSO obtains a good controlling performance index.
基金the financial supports from NSFC (No. 21472174)Education Department of Zhejiang Province (No. Y201432060)Zhejiang Sci-Tech University (Nos. 1206838-Y and 14062015-Y)
摘要A convenient and transition-metal free protocol for quinazolinones synthesis with o-aminobenzamides and benzyl amines as substrates has been developed. Using H;O;as the oxidant, various quinazolinones were obtained in moderate to good yields under metal- and additive-free conditions.
基金the financial supports from the Joint Funds of the Zhejiang Provincial Natural Science Foundation of China(No.LTY21B020001)the Fundamental Research Funds of Zhejiang Sci-Tech University(No.2021Q052)。
摘要A novel palladium-catalyzed carbonylative cyclization of alkene-tethered indoles with phenols or arylboronic acids is described,which provides a facile approach to access indolo[2,1-a]isoquinoline scaffolds.This method employs benzene-1,3,5-triyl triformate(TFBen)as the CO surrogate for the incorporation of a carbonyl group into indolo[2,1-a]isoquinoline scaffolds,and a variety of carbonyl-containing indolo[2,1-a]isoquinoline derivatives are prepared in good yields.
基金funded by the China Postdoctoral Science Foundation(No.2024M754253)the National Natural Science Foundation of China(No.82372529)+3 种基金the Chongqing Postdoctoral Science Foundation(No.CSTB2023NSCQBHX0015)the Science and Technology Innovation Enhancement Project of the Army Medical University(China)(No.2022XQN45)Postdoctoral Foundation of Daping Hospital(China)(No.ZXBSH004)Chongqing Key Laboratory of Precision Diagnosis and Treatment for Kidney Diseases(China).
摘要Chronic non-healing wounds,such as diabetic foot ulcers,represent a clinical challenge with an increasing incidence.1 A deeper understanding of the molecular mechanisms underlying wound healing is of great significance.RNA m6A modification is a widespread and important epigenetic regulatory mechanism,2 but its role in wound healing remains unclear.In this study,we found that METTL3,an RNA m6A methyltransferase,is a positive regulator of wound healing and that its low expression is closely related to chronic diabetic wounds.
摘要The fetal weight vs. the gestational age has great significance for fetal growth evaluation in clinic especially in the judgement of IUGR. In this paper, the quantification theory and its application for estimation of the gestational age and fetal weight are reported.It is the first time that the theory is applied in this field. The estimation error.of gestational age is less than one week and that of fetal weight is less than 130g.
基金support provided by the National Key R&D Program of China(grant no.2023YFA1507500)the National Natural Science Foundation of China(grant no.22302198)the International Partnership Program of Chinese Academy of Sciences(grant no.028GJHZ2023045FN).
摘要The catalytic production of chiral amides from readily available unactivated internal alkenes remains a significant challenge in synthetic chemistry.In this work,we developed a highly enantioselective hydroaminocarbonylation procedure for nonactivated internal alkenes and a wide range ofα-chiral amides were produced effectively with exceptional enantioselectivities using copper as the catalyst.This method is compatible with both symmetric and asymmetric internal alkenes,as well as various hydroxylamine electrophiles,demonstrating wide substrate scope and broad functional group tolerance.The established catalytic system showcases remarkable enantioselective performance in the asymmetric hydroaminocarbonylation of challenging substrates,such as the methyl-ethylα-chiral amide synthesis from trans-2-butene,despite the minimal steric difference between the methyl and ethyl group.This work represents important progress in the field of asymmetric hydroaminocarbonylation and offers a useful tool for the production of valuableα-chiral amide compounds from readily available internal alkenes.
基金supported by Fundamental Research Program of Shanxi Province(No.202303021211006)Shanxi Scholarship Council of China(No.2023-032).
摘要Aminosilylalkanes are important motifs in bioactive molecules,yet methods for their direct incorporation remain limited.In particular,the efficient introduction of gem-difluoro groups–known to significantly modulate the physical,chemical,and biological properties of organic molecules–into aminosilylalkane remains a challenge.Herein,we report a cobalt-catalyzed silyldifluoromethylamination of styrenes using TMSCF2H and nitrogen nucleophiles.By employing readily available starting materials,a series of complex,highly functionalized aminosilyldifluoroalkane derivatives were synthesized in moderate to good yields.This methodology establishes a novel strategy for constructing organosilicon compounds,complementing existing synthetic approaches.