Pincer

钳子
  • 文章类型: Journal Article
    凸轮和钳形畸形的动态相互作用可导致股骨髋臼撞击(FAI)综合征的病理性接触力。在髋臼骨折重建过程中发现了类似的畸形。我们假设髋臼骨折患者的FAI畸形患病率高于对照组。
    这项回顾性影像学研究比较了定义FAI畸形的参数,该参数是连续入院的100例髋臼骨折患者和100例没有髋臼损伤的骨盆外侧压缩性骨折患者的对照组。两者均接受了相同的临床影像学检查。中心边缘角(CEA)和α角被用来定义患者的钳,凸轮,或混合FAI畸形。
    髋臼骨折组FAI畸形患者明显多于对照组(71%vs.18%,p<0.0001)。在患有“钳形”窝的患者中,涉及髋臼前柱和后柱的骨折要多得多(p=0.02,OR=2.95,95%CI,1.12-7.78)。
    髋臼骨折患者中凸轮和钳形畸形的患病率很高,特别是双柱骨折。
    UNASSIGNED: Dynamic interaction of cam and pincer deformities can result in pathological contact forces in femoroacetabular impingement (FAI) syndrome. Similar deformities were noted during acetabular fracture reconstruction. We hypothesise that the prevalence of FAI deformity is higher in patients sustaining acetabular fractures than in a control group.
    UNASSIGNED: This retrospective radiographic study compared the parameters that define FAI deformity in 100 patients consecutively admitted to a trauma unit with an acetabular fracture and a control group of 100 patients with lateral compression pelvic fracture without acetabular injury. Both underwent identical clinical imaging. Centre-edge angles (CEA) and alpha angles were used to define patients with pincer, cam, or mixed FAI deformity.
    UNASSIGNED: There were significantly more patients with FAI deformity in the acetabular fracture group than in the control group (71% vs. 18%, p < 0.0001). There were considerably more fractures involving both anterior and posterior acetabular columns in patients with \'pincer\' sockets (p = 0.02, OR = 2.95, 95% CI, 1.12-7.78).
    UNASSIGNED: There is a high prevalence of cam and pincer deformities in patients with acetabular fractures, particularly bi-column fractures.
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  • 文章类型: Journal Article
    夹式配合物[NiIIBr(CNC)]Br(4),[CrIIIBr3(CNC)](5a)和[CrIIIBr2.3Cl0.7(CNC)](5b),其中CNC=3,3'-(吡啶-2,6-二基)双(1-均三基-3,4,5,6-四氢嘧啶-2-亚基),是从新型配体CNC获得的,通过氨解从前体(CHNCH)Br2和[NiIIBr2(PPh3)2]或从[CrII{N(SiMe3)2}2(THF)2]和(CHNCH)Br2原位生成,分别。四面体扭曲的正方形平面(τ4^0.30)几何形状和4中Ni的单重态基态归因于CNC骨架的空间约束。计算方法强调了配位几何形状和单线态-三重态能量差对四氢嘧啶翼尖的N-取代基的大小的依赖性,并将其与5元咪唑啉-2-亚基钳类似物的情况进行了对比。5a和5b中的八面体CrIII金属中心大概是在CH2Cl2的一个电子氧化之后形成的。4/MAO和5a/MAO是乙烯低聚和聚合的中等活性催化剂,分别。类似的(CH^N^CH)Br2前体,其中(CH^N^CH)=3,3'-(吡啶-2,6-二基双(亚甲基))双(1-均三甲基-3,4,5,6-四氢嘧啶-1-铵),也准备好了,然而,由于所得游离C^N^C配体的固有不稳定性,其配位化学没有研究。
    The pincer complexes [NiIIBr(CNC)]Br (4), [CrIIIBr3(CNC)] (5 a) and [CrIIIBr2.3Cl0.7(CNC)] (5 b), where CNC=3,3\'-(pyridine-2,6-diyl)bis(1-mesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene), were obtained from the novel ligand CNC, generated in situ from the precursor (CHNCH)Br2 and [NiIIBr2(PPh3)2] or from [CrII{N(SiMe3)2}2(THF)2] and (CHNCH)Br2 by aminolysis, respectively. The tetrahedrally distorted square planar (τ4≅0.30) geometry and the singlet ground state of Ni in 4 were attributed to steric constraints of the CNC backbone. Computational methods highlighted the dependence of the coordination geometry and the singlet-triplet energy difference on the size of the N-substituent of the tetrahydropyrimidine wingtips and contrasted it to the situation in 5-membered imidazolin-2-ylidene pincer analogues. The octahedral CrIII metal center in 5 a and 5 b is presumably formed after one electron oxidation from CH2Cl2. 4/MAO and 5 a/MAO were catalysts of moderate activity for the oligomerization and polymerization of ethylene, respectively. The analogous (CH^N^CH)Br2 precursor, where (CH^N^CH)=3,3\'-(pyridine-2,6-diylbis(methylene))bis(1-mesityl-3,4,5,6-tetrahydropyrimidin-1-ium), was also prepared, however its coordination chemistry was not studied due to the inherent instability of the resulting free C^N^C ligand.
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  • 文章类型: Journal Article
    背景:随着最近对髋骨关系的兴趣,股骨髋臼撞击(FAI)与腰椎-骨盆-股骨复合体(LPFC)之间的联系似乎是决定性的.本研究的目的是(1)比较骨盆版本,以及(2)两个健康受试者群体之间的LPFC的所有参数,将那些有FAI放射学征象的和没有FAI放射学征象的进行比较。最后(3)根据FAI的类型对LPFC参数进行评价。
    目的:有FAI放射学征象的无症状受试者有上骨盆前倾。
    方法:这项回顾性研究基于118名自愿无症状患者的前瞻性队列研究,其中包括62名男性(52.5%),平均年龄为25.6岁±4.4(1939)。以下参数:骨盆版本(PV),骨盆发病率(PI),腰椎前凸(LL),骶骨斜坡(SS),髋关节屈曲,在参考站立位置和弓步位置使用EOSimaging™测量内在(IER)和外在(EER)伸展储备。FAI的放射学征象(凸轮,钳子,混合)在这些收购中进行鉴定,然后分为2组。第一组是呈现FAI(FAI+)的一个或多个图像的组,第二组没有FAI(FAI-)的图像。
    结果:FAI+组143髋,FAI-组93髋。有36.4%的凸轮和45%的钳子。平均值为9.08°±7.81(-11.0;27.0),平均值为12.33°±8.94(-5.0;55.0),与FAI-组相比,FAI+组的PV显著降低(p=0.022).对主要结果(PV)的事后功率分析证实了足够的功率(1-β=0.809)。与FAI-组相比,凸轮组的IER和EER显著较低(分别为p=0.014和p=0.047).FAI-组和钳子组之间的比较分析发现PI存在显着差异(p=0.001),PV(p<0.001),IER(p=0.017)和髋关节屈曲(p<0.001),弓步位置的SS(p=0.031)和EER(p=0.039)。
    结论:有FAI影像学征象的无症状受试者站立时表现为骨盆虚弱。这种骨盆过度前倾主要是在放射性钳征时发现的。
    方法:III,回顾性比较研究。
    BACKGROUND: With the recent interest in hip-spine relationship, the link between femoroacetabular impingement (FAI) and the lumbar-pelvic-femoral complex (LPFC) appears decisive. The objectives of this study were (1) to compare the pelvic version, as well as (2) all the parameters of the LPFC between two populations of healthy subjects, comparing those with radiological signs of FAI to those without and finally, (3) to evaluate the LPFC parameters according to the type of FAI.
    OBJECTIVE: Asymptomatic subjects with radiological signs of FAI had superior pelvic anteversion.
    METHODS: This retrospective study was based on a prospective cohort of 118 voluntary asymptomatic patients including 62 men (52.5%) with a mean age of 25.6 years±4.4 (19-39). The following parameters: pelvic version (PV), pelvic incidence (PI), lumbar lordosis (LL), sacral slope (SS), hip flexion, intrinsic (IER) and extrinsic (EER) extension reserve were measured using EOS imaging™ in the reference standing position and the lunge position. The radiological signs of FAI (cam, pincer, mixed) were identified on these acquisitions then separated into 2 groups. The first was the group presenting with one or more images of FAI (FAI+) and the second group with no images of FAI (FAI-).
    RESULTS: There were 143 hips in the FAI+ group compared to 93 hips in the FAI- group. There were 36.4% cams and 45% pincers. With an average of 9.08°±7.81 (-11.0; 27.0) versus 12.33°±8.94 (-5.0; 55.0), the PV was significantly lower (p=0.022) in the FAI+ group compared to the FAI- group. A post-hoc power analysis on the primary outcome (PV) confirmed sufficient power (1-β=0.809). Compared to the FAI- group, the cam group presented a significantly lower IER and EER (respectively p=0.014 and p=0.047). The comparative analysis between the FAI- and pincer groups found a significant difference in PI (p=0.001), PV (p<0.001), IER (p=0.017) and hip flexion (p<0.001), SS in lunge position (p=0.031) and EER (p=0.039).
    CONCLUSIONS: Asymptomatic subjects with radiographic signs of FAI present with weak pelvic version when standing. This pelvic hyper-anteversion is mainly found in the event of a radiological pincer sign.
    METHODS: III, retrospective comparative study.
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  • 文章类型: Journal Article
    对于股髋臼撞击(FAI)中的凸轮病变,股骨头上的切除量或切除起点是有争议的。
    本研究的目的是研究术后切除深度的影响,和凸轮病变的切除弧比在实现实质性临床获益(SCB)的频率上,改良Harris髋关节评分(mHHS)和髋关节预后评分日常生活活动能力(HOSADL)的患者可接受状态(PASS),术后2年。
    所有接受FAI首次髋关节镜检查并随访2年的患者均纳入本研究。患者报告的结果包括mHHS,HOSADL,疼痛视觉模拟评分(疼痛VAS)。放射学参数,如阿尔法角度传统(αT),α软骨(αC),切除弧比(%α角软骨-α角传统/360°),使用45°Dunn视图测量切除深度(\'\'D\'\'mm)和切除深度比\'D%\'(D/股骨头直径%)。
    我们确定了26例患者(27髋),随访2年。有10名女性和16名男性患者。患者的平均年龄为33±12岁。mHHS达到SCB阈值的频率较高与唇修复相关(73%vs.清创27%p=0.03),术前αT较低(64°vs.76°,p=0.04),术前mHHS较低(54vs.81,p<0.001)和更高的术前VAS评分(8vs.7,p=0.02)。
    mHHS达到PASS阈值的频率较高与较低的αC(82°vs.92°p:0.02),较低的RA(8%与11%,p=0.03),下D(2.8毫米与4.5mmp:0.03),较低的D%(4.7%与8.4%p=0.04)和更高的术后mHHS(97vs.82p<0.001)。HOSADL获得SCB的频率较高与较低的D%(5%与10.5%,p=0.04)。凸轮切除深度会影响达到临床意义评分的频率,切除深度小于股骨头直径的6%似乎适合获得最佳结果。当使用α角作为参考时,在头部软骨上切除的起始点需要<90°。
    UNASSIGNED: The amount of resection or the starting point of the resection on the femoral head for cam lesions in femoroacetabular impingement (FAI) is controversial.
    UNASSIGNED: The purpose of this study was to study the effect of postoperative resection depth, and resection arc ratio of cam lesion on the frequency of achieving substantial clinical benefit (SCB), patient acceptable state (PASS) in modified Harris Hip Score (mHHS) and Hip Outcome Score Activity of Daily Living (HOSADL), 2 years postoperatively.
    UNASSIGNED: All patients who underwent first-time hip arthroscopy for FAI with a 2-year follow-up were included in this study. Patient-reported outcomes included the mHHS, HOSADL, and visual analogue scale for pain (Pain VAS). Radiological parameters such as alpha angletraditional (αT), alpha anglecartilage (αC), resection arc ratio (% alpha anglecartilage-alpha angletraditional/360°), resection depth (\'\'D\'\'mm) and resection depth ratio \'D%\' (D/femoral head diameter %) were measured using the 45° Dunn view.
    UNASSIGNED: We identified 26 patients (27 hips) with 2-year follow-up. There were 10 female and 16 male patients. The mean age of the patients was 33 ± 12 years.Higher frequency of achieving SCB threshold for mHHS was related to labrum repair (73% vs. debridement \'27%\' p = 0.03), lower preoperative αT (64° vs. 76°, p = 0.04), lower preoperative mHHS (54 vs. 81, p < 0.001) and higher preoperative VAS scores (8 vs. 7, p = 0.02). Higher frequency of reaching PASS threshold for mHHS was associated with lower αC (82°vs. 92° p:0.02), lower RA (8% vs. 11%, p = 0.03), lower D (2.8 mm vs. 4.5 mm p:0.03), lower D% (4.7% vs. 8.4% p = 0.04) and higher postoperative mHHS (97 vs. 82 p < 0.001).
    UNASSIGNED: A higher frequency of achieving SCB for HOSADL was related to lower D% (5% vs. 10.5%, p = 0.04).Cam resection depth affects the frequency of achieving clinically meaningful scores and resection depth less than 6% of the femoral head diameter seems to be appropriate for optimal results. The starting point of resection on head cartilage needs to be <90° when alpha angle is used for reference.
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  • 文章类型: Journal Article
    辅因子是许多酶的重要组成部分,因此它们的结构表征,生物物理,生化方法对于理解由此产生的催化和调节机制至关重要。在这一章中,我们提供了一个最近发现的辅因子的案例研究,镍夹式核苷酸(NPN),通过证明我们如何鉴定和彻底表征这种前所未有的含镍辅酶,该辅酶与植物乳杆菌的乳糖酶消旋酶相连。此外,我们描述了如何通过lar操纵子中编码的一组蛋白质生物合成NPN辅因子,并描述了这些新型酶的特性。对含NPN的乳酸消旋酶(LarA)和羧化酶/水解酶(LarB)进行功能和机理研究的综合方案,硫转移酶(LarE),和用于NPN生物合成的金属插入酶(LarC)被提供用于表征相同或同源家族中的酶的潜在应用。
    Cofactors are essential components of numerous enzymes, therefore their characterization by structural, biophysical, and biochemical approaches is crucial for understanding the resulting catalytic and regulatory mechanisms. In this chapter, we present a case study of a recently discovered cofactor, the nickel-pincer nucleotide (NPN), by demonstrating how we identified and thoroughly characterized this unprecedented nickel-containing coenzyme that is tethered to lactase racemase from Lactiplantibacillus plantarum. In addition, we describe how the NPN cofactor is biosynthesized by a panel of proteins encoded in the lar operon and describe the properties of these novel enzymes. Comprehensive protocols for conducting functional and mechanistic studies of NPN-containing lactate racemase (LarA) and the carboxylase/hydrolase (LarB), sulfur transferase (LarE), and metal insertase (LarC) used for NPN biosynthesis are provided for potential applications towards characterizing enzymes in the same or homologous families.
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  • 文章类型: Journal Article
    聚乙烯亚胺在洗涤剂等产品中发现了许多应用,粘合剂,化妆品,对于组织培养等过程,基因治疗,和二氧化碳捕获。目前生产支化聚乙烯亚胺的最先进技术涉及氮丙啶原料,挥发性和诱变的化学物质,对人类健康和环境引起了重大关注。我们在这里报道了一种从乙二醇和乙二胺合成支化聚乙烯亚胺衍生物的新方法,环境友好,市售和潜在的可再生原料。聚合反应由地球上丰富的金属的配合物催化,锰和释放H2O作为唯一的副产品。我们使用DFT计算和实验相结合的机理研究表明,反应通过亚胺中间体的形成和随后的氢化进行。
    Polyethyleneimines find many applications in products such as detergents, adhesives, cosmetics, and for processes such as tissue culture, gene therapy, and CO2 capture. The current state-of-the-art technology for the production of the branched polyethyleneimines involves aziridine feedstock which is a highly toxic, volatile and mutagenic chemical and raises significant concern to human health and environment. We report here a novel method for the synthesis of branched polyethyleneimine derivative from ethylene glycol and ethylenediamine which are much safer, environmentally benign, commercially available and potentially renewable feedstock. The polymerisation reaction is catalysed by a complex of an earth-abundant metal, manganese and liberates H2 O as the only by-product. Our mechanistic studies using a combination of DFT computation and experiment suggest that the reaction proceeds by the formation and subsequent hydrogenation of imine intermediates.
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  • 文章类型: Journal Article
    背景:影像学研究在诊断股骨髋臼撞击(FAI)中起着至关重要的作用,包括平片和磁共振成像(MRI)。FAI是骨异常的综合病理,唇和唇软骨糜烂。此类病例的手术治疗已变得更加成熟,术前成像是包括评估唇和关节软骨的路线图。
    方法:在2年内,这项研究回顾性地纳入了37例临床诊断为FAI的患者,包括17名男性和20名女性,年龄27-62岁。有22个右臀部和15个左臀部。对所有患者进行MRI检查以识别骨骼细节,唇和软骨异常,并排除共存的疾病。将影像学结果与关节镜数据进行比较。
    结果:15例患者患有钳形FAI,11例患者有CAM,11例患者合并Cam/PincerFAI。在100%的患者中检测到Labral撕裂,97%有前上唇撕裂。82%的患者有部分厚度软骨病变,8%的患者有全厚度软骨病变。与髋关节镜检查相比,MRI在检测唇撕裂方面的敏感性为100%,60%检测软骨侵蚀。
    结论:常规髋关节MRI可检测FAI的骨改变,与髋关节镜检查相比,撞击类型和相关的唇撕裂和软骨侵蚀。
    BACKGROUND: Imaging studies play a crucial role in diagnosing femoroacetabular impingement (FAI), including plain radiography and Magnetic Resonance Imaging (MRI). FAI is a combined pathology of bony abnormality, labral and labrocartilagenous erosions. Surgical treatment for such cases has become more established and preoperative imaging is the roadmap that includes the assessment of labrum and articular cartilage.
    METHODS: During a period of 2 years, thirty-seven patients with a clinical diagnosis of FAI were retrospectively enrolled in this study, including 17 men and 20 women, aged 27-62 years. There were 22 right hips and 15 left hips. MRI was done for all patients to identify bony details, labral and chondral abnormalities and to exclude coexisting disorders. The imaging findings were compared with the arthroscopic data.
    RESULTS: 15 patients had Pincer FAI, 11 patients had CAM, and 11 patients had combined Cam/Pincer FAI. Labral tear was detected in 100 % of patients, 97 % had an anterosuperior labral tear. 82 % of patients had partial thickness cartilage lesions and 8 % had full thickness cartilage lesions. MRI had a sensitivity of 100 % compared to hip arthroscopy in detecting labral tear, 60 % in detecting cartilage erosion.
    CONCLUSIONS: Conventional hip MRI detects bony changes in FAI, type of impingement and associated labral tear and cartilage erosions in comparison to the hip arthroscopy.
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  • 文章类型: Journal Article
    未经授权:股骨髋臼撞击(FAI)常见于冰球,但是缺乏研究女性冰球运动员夹式撞击的数据。这项研究的目的是评估全国女子曲棍球联盟(NWHL)运动员中夹式撞击的患病率。我们的假设是,在这些运动员中,夹式撞击的患病率会增加。
    未经评估:收集了一组NWHL球员和年龄的数据,性别,同时回顾性收集与体重指数(BMI)匹配的对照.所有受试者均在18岁以上。对照组患者被排除在外,如果他们之前接受过髋关节手术,年龄大于30岁,或BMI大于35。两组的射线照片评估横向中心边缘角(LCEA),Tönnis的角度,和交叉标志。Tönnis角<0或LCEA>40度被认为是钳形形态。α角>55度被认为是凸轮形态。
    未经评估:包括37名NWHL球员和37名女性对照。根据LCEA,总共有32%的球员在任一臀部都有钳形病变,8%的Tönnis角度<0,22%的臀部有交叉征,而9%的人则有交叉征,19%,对照组为13%,分别。这些发现在各组之间没有显著差异(p>0.05)。在84%的球员中发现任一臀部的α角≥55度,但对照组没有用于α角测量的横向邓恩图像。
    未经证实:NWHL运动员的钳形形态和交叉迹象比一般人群中的报道要多,但这些发现与对照组相比没有统计学差异.凸轮型形态在这些运动员中更为普遍,并且可能与初潮时的年龄有关,这是由于在闭合前对身体的撞击。
    UNASSIGNED: Femoroacetabular impingement (FAI) appears common in ice hockey, but there is a lack of data examining pincer-type impingement in women\'s ice hockey athletes. The objective of this study was to assess the prevalence of pincer-type impingement in National Women\'s Hockey League (NWHL) athletes. Our hypothesis was that there would be an increased prevalence of pincer impingement in these athletes.
    UNASSIGNED: Data were gathered for a team of NWHL players, and age, gender, and body mass index (BMI) matched controls were also retrospectively collected. All subjects were above 18 years of age. Control patients were excluded if they had undergone prior hip surgery, were greater than age 30, or had BMI greater than 35. Radiographs of both groups were assessed for lateral center edge angle (LCEA), Tönnis angle, and crossover sign. Tönnis angle <0 or LCEA >40 degrees was considered pincer morphology. An alpha angle >55 degrees was considered cam morphology.
    UNASSIGNED: Thirty-seven NWHL players and 37 female controls were included. Overall 32% of the players had a pincer lesion in either hip based on LCEA, 8% had a Tönnis angle <0, and 22% had a crossover sign in either hip compared to 9%, 19%, and 13% for the controls, respectively. None of these findings were significantly different between the groups (p > 0.05). An alpha angle ≥55 degrees in either hip was found in 84% of players, but lateral Dunn images for alpha angle measurements were not available for the control group.
    UNASSIGNED: Pincer-type morphology and crossover signs were present in a larger portion of NWHL players than has been reported in the general population, but these findings were not statistically different than in the control group. Cam-type morphology was even more prevalent in these athletes and may be related to age at menarche due impingement at the physis prior to closure.
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  • 文章类型: Journal Article
    股骨髋臼撞击(FAI)综合征是运动医学中研究最多的疾病之一。可以提出手术或保守方法来治疗FAI,尽管最佳护理标准尚未确立。我们的目的是对FAI综合征的最佳治疗方法进行全面审查,以评估手术和非手术治疗之间的结果差异。在PubMed上进行了文献检索,EMBASE,Scopus,和PEDro数据库,使用以下关键字:\"股骨髋臼撞击\",\"FAI\",与“手术”相关,“关节镜”,“外科手术”和“保守”,“物理治疗”,\"物理治疗\",“康复”,\"练习\"。仅包括I级RCT。本文选择了四篇文章进行系统评价。我们的分析显示了不同的治疗方案,后续期,和结果;然而,4项研究中有3项纳入了有利的手术.我们的研究表明,关节镜治疗和适当的物理治疗方案都有有益的效果。然而,与仅保守治疗相比,手术方法似乎可提供更优的短期效果.需要更大样本量和更长时间随访的进一步试验来评估FAI条件的确定方法。
    Femoro-acetabular impingement (FAI) syndrome is one of the most studied conditions in sports medicine. Surgical or conservative approaches can be proposed for treating FAI, although the best standard of care is not established yet. Our aim is to provide a comprehensive review of the best treatment for FAI syndrome evaluating differences in outcomes between surgical and non-operative management. A literature search was carried out on the PubMed, EMBASE, Scopus, and PEDro databases, using the following keywords: \"femoroacetabular impingement\", \"FAI\", in association with \"surgery\", \"arthroscopy\", \"surgical\" and \"conservative\", \"physiotherapy\", \"physical therapy\", \"rehabilitation\", \"exercise\". Only Level I RCTs were included. Four articles were selected for this systematic review. Our analysis showed different therapeutic protocols, follow-up periods, and outcomes; however, three out of the four studies included favored surgery. Our study demonstrates beneficial effects for both arthroscopic treatment and a proper regimen of physical therapy, nevertheless a surgical approach seemed to offer superior short-term results when compared to conservative care only. Further trials with larger sample sizes and longer follow-ups are needed to assess the definitive approach to the FAI condition.
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  • 文章类型: Journal Article
    硫插入反应对于几种细胞代谢物的生物合成至关重要,包括酶辅因子。在植物乳杆菌中,含硫的镍夹式核苷酸(NPN)辅因子用作乳酸消旋酶的辅酶,拉拉.在植物乳杆菌的NPN生物合成过程中,通过LarE将硫转移到烟酸衍生的底物中,牺牲其单个半胱氨酰侧链的硫原子,形成脱氢丙氨酸残基。大多数LarE同源物包含三个保守的半胱氨酸残基,这些残基预计会在活性位点聚集;然而,该半胱氨酸簇的功能尚不清楚。在这项研究中,我们表征了Thermotogamaritima(LarETm)的LarE,并表明它使用这三个保守的半胱氨酸残基结合硫转移所需的[4Fe-4S]簇。值得注意的是,我们发现LarETm保留了所有侧链硫原子,与Larelp相反。我们还证明,当提供来自大肠杆菌(IscSEc)的L-半胱氨酸和半胱氨酸脱硫酶时,LarETm与IscSEc催化起作用,将硫烷硫原子转移到LarETm。天然质谱结果与一个模型一致,其中酶在[4Fe-4S]簇的非连接铁原子上配位硫化物,形成[4Fe-5S]物种,并将非核心硫化物转移到活化的底物上。这种提出的机理类似于在2-硫脲苷合成过程中催化硫转移的TtuA。总之,我们发现与NPN生物合成相关的LarE硫插入酶通过从蛋白质中转移牺牲硫或通过转移与[4Fe-4S]簇结合的非核心硫化物而起作用。
    Sulfur-insertion reactions are essential for the biosynthesis of several cellular metabolites, including enzyme cofactors. In Lactobacillus plantarum, a sulfur-containing nickel-pincer nucleotide (NPN) cofactor is used as a coenzyme of lactic acid racemase, LarA. During NPN biosynthesis in L. plantarum, sulfur is transferred to a nicotinic acid-derived substrate by LarE, which sacrifices the sulfur atom of its single cysteinyl side chain, forming a dehydroalanine residue. Most LarE homologs contain three conserved cysteine residues that are predicted to cluster at the active site; however, the function of this cysteine cluster is unclear. In this study, we characterized LarE from Thermotoga maritima (LarETm) and show that it uses these three conserved cysteine residues to bind a [4Fe-4S] cluster that is required for sulfur transfer. Notably, we found LarETm retains all side chain sulfur atoms, in contrast to LarELp. We also demonstrate that when provided with L-cysteine and cysteine desulfurase from Escherichia coli (IscSEc), LarETm functions catalytically with IscSEc transferring sulfane sulfur atoms to LarETm. Native mass spectrometry results are consistent with a model wherein the enzyme coordinates sulfide at the nonligated iron atom of the [4Fe-4S] cluster, forming a [4Fe-5S] species, and transferring the noncore sulfide to the activated substrate. This proposed mechanism is like that of TtuA that catalyzes sulfur transfer during 2-thiouridine synthesis. In conclusion, we found that LarE sulfur insertases associated with NPN biosynthesis function either by sacrificial sulfur transfer from the protein or by transfer of a noncore sulfide bound to a [4Fe-4S] cluster.
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