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A multifaceted approach towards understanding the peculiar behavior of(α)-hydroxyiminophosphonates

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Organic Chemistry Frontiers 2022年第1期9卷 173-182页

作者： thomas Toupy Christopher Kune Kristof van Hecke Loïc Quinton Jean-Christophe M.Monbaliu Center for Integrated Technology and Organic Synthesis MolSys Research UnitUniversity of LiègeB-4000 Liège(Sart Tilman)Belgium Mass Spectrometry Laboratory MolSys Research UnitUniversity of LiègeB-4000 Liège(Sart Tilman)Belgium XStruct Department of ChemistryGhent UniversityKrijgslaan 281-S3B-9000 GhentBelgium

The peculiar isomer-selective reduction of(α)-hydroxyiminophosphonates(oxime isomers)into(α)-hydroxyaminophosphonate(hydroxylamine)derivatives is presented.A library of 16(α)-hydroxyiminophosphonates is prepared and studied via a unique multifaceted approach involving the interplay of NMR,XRD,MS,IM-MS and computational chemistry *** combination of NMR,XRD and HPLC enables the seamless separation,identification and quantification of the oxime isomers(E/Z).Tandem MS(MS/MS)enables the determination of the fragmentation patterns for both *** energy breakdown curves highlight the order of apparition of the fragments as well as their related energy of fragmentation,demonstrating that the strength of the C–P bond in the Z isomers is much weaker than in the E *** chemistry demonstrates that favorable protonation site is isomer-dependent with the phosphonate moiety being the favorable protonation site for the E isomers,while protonation occurs preferentially on the amino moiety for Z isomers regardless of the phosphite *** combination of these various methods led an unprecedented level of characterization of oxime isomers,providing a better uderstanding of the isomer-dependent behavior of(α)-hydroxyiminophosphonates.

关键词： isomers phosphonate moiety

The CRAFITY score can identify patients with hepatocellular carcinoma showing poor response to treatment with atezolizumab and bevacizumab

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Hepatobiliary Surgery and Nutrition 2023年第1期12卷 148-150页

作者： Sabine Lieb Sebastian Ebel Daniel Seehofer thomas Berg Florian van Bommel Division of Hepatology Department of Medicine IILeipzig University Medical CenterLeipzigGermany Department of Diagnostic and Interventional Radiology Leipzig University Medical CenterLeipzigGermany Department of Visceral VascularThoracic and Transplant SurgeryLeipzig University Medical CenterLeipzigGermany

With great interest we have read the comment of *** on the recently published CRAFITY score for the prediction of response to anti-programmed death(ligand)1[PD-(L)1]-based immunotherapy in patients with unresectable h... 详细信息

关键词： patients hepatocellular carcinoma

A conceptual framework and an empirical test of complementarity and facilitation with respect to phosphorus uptake by plant species mixtures

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Pedosphere 2022年第2期32卷 317-329页

作者： Chunjie LI thomas W.KUYPER Wopke van DER WERF Junling ZHANG Haigang LI Fusuo ZHANG Ellis HOFFLAND College of Resources and Environmental Science National Academy of Agriculture Green DevelopmentChina Agricultural UniversityBeijing 100193China Wageningen University Soil Biology GroupP.O.Box 476700 AA WageningenThe Netherlands Wageningen University Centre for Crop Systems AnalysisP.O.Box 4306700 AK WageningenThe Netherlands Inner Mongolia Key Laboratory of Soil Quality and Nutrient Resources Key Laboratory of Grassland Resource(IMAU)Ministry of EducationCollege of GrasslandResources and EnvironmentInner Mongolia Agricultural UniversityHohhot 010018China

Plant species have different traits for mobilizing sparingly soluble phosphorus (P) resources,which could potentially lead to overyielding in P uptake by plant species mixtures compared to monocultures due to higher P uptake as a result of resource (P) partitioning and ***,there is circumstantial evidence at best for overyielding as a result of these *** (the outcome) is easily confused with underlying mechanisms because of unclear *** aimed to define a conceptual framework to separate outcome from underlying mechanisms and test it for facilitation and complementarity with respect to P acquisition by three plant species combinations grown on four *** conceptual framework describes both mechanisms of complementarity and facilitation and outcomes (overyielding of mixtures or no overyielding) depending on the competitive ability of the species to uptake the mobilized ***/chickpea mixtures were grown in pots on two calcareous soils mixed with calcium-bound P (CaP) and phytate P (PhyP).Cabbage/faba bean mixtures were grown on both acid and neutral soils mixed with P-coated iron (hydr)oxide (FeP) and ***/maize mixtures were grown on all four *** carboxylate concentration and acid phosphatase activity (mechanisms) as well as plant P uptake and biomass (outcome) were determined for monocultures rhizosphere and species *** of P uptake occurred in millet/chickpea mixtures on one calcareous *** found no indications for P acquisition from different P sources,neither in millet/chickpea,nor in cabbage/faba bean *** and faba bean on the neutral soil differed in rhizosphere acid phosphatase activity and carboxylate concentration,but showed no *** and maize,with similar root exudates,showed overyielding (the observed P uptake being 22%higher than the expected P uptake) on one calcareous *** concluded that although differences in plant physiological tr

关键词： carboxylate intercrop phosphatase phosphorus acquisition phosphorus mobilization phoshorus source rhizosphere root exudation

Therapeutic anticoagulation for splanchnic vein thrombosis in acute pancreatitis: A national survey and case-vignette study

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World Journal of Gastroenterology 2023年第21期29卷 3328-3340页

作者： Noor J Sissingh Jesse V Groen Hester C Timmerhuis Marc G Besselink Bas Boekestijn thomas L Bollen Bert A Bonsing Frederikus A Klok Hjalmar C van Santvoort Robert C Verdonk Casper H J van Eijck Jeanin E van Hooft Jan Sven D Mieog Department of Gastroenterology and Hepatology Leiden University Medical CentreLeiden 2333 ZANetherlands Department of Research and Development St.Antonius HospitalNieuwegein 3420 EMNetherlands Department of Surgery Leiden University Medical CentreLeiden 2333 ZANetherlands Department of Surgery St.Antonius HospitalNieuwegein 3420 EMNetherlands Department of Surgery Amsterdam UMCLocation University of AmsterdamAmsterdam 1081 HZNetherlands Amsterdam Gastroenterology Endocrinology Metabolism Amsterdam 1105 AZNetherlands Department of Radiology Leiden University Medical CentreLeiden 2333 ZANetherlands Department of Radiology St.Antonius HospitalNieuwegein 3420 EMNetherlands Department of Medicine-Thrombosis and Hemostasis Leiden University Medical CentreLeiden 2333 ZANetherlands Department of Surgery University Medical Centre UtrechtUtrechtUtrecht 3584 CXNetherlands Department of Gastroenterology and Hepatology St.Antonius HospitalNieuwegein 3420 EMNetherlands Department of Surgery Erasmus Medical CentreRotterdam 3015 GDNetherlands

BACKGROUND Splanchnic vein thrombosis(SVT)is a major complication of moderate and severe acute *** is no consensus on whether therapeutic anticoagulation should be started in patients with acute pancreatitis and *** To gain insight into current opinions and clinical decision making of pancreatologists regarding SVT in acute *** A total of 139 pancreatologists of the Dutch Pancreatitis Study Group and Dutch Pancreatic Cancer Group were approached to complete an online survey and case vignette *** threshold to assume group agreement was set at 75%.RESULTS The response rate was 67%(n=93).Seventy-one pancreatologists(77%)regularly prescribed therapeutic anticoagulation in case of SVT,and 12 pancreatologists(13%)for narrowing of splanchnic vein *** most common reason to treat SVT was to avoid complications(87%).Acute thrombosis was the most important factor to prescribe therapeutic anticoagulation(90%).Portal vein thrombosis was chosen as the most preferred location to initiate therapeutic anticoagulation(76%)and splenic vein thrombosis as the least preferred location(86%).The preferred initial agent was low molecular weight heparin(LMWH;87%).In the case vignettes,therapeutic anticoagulation was prescribed for acute portal vein thrombosis,with or without suspected infected necrosis(82%and 90%),and thrombus progression(88%).Agreement was lacking regarding the selection and duration of long-term anticoagulation,the indication for thrombophilia testing and upper endoscopy,and about whether risk of bleeding is a major barrier for therapeutic *** In this national survey,the pancreatologists seemed to agree on the use of therapeutic anticoagulation,using LMWH in the acute phase,for acute portal thrombosis and in the case of thrombus progression,irrespective of the presence of infected necrosis.

关键词： Acute pancreatitis Splanchnic vein thrombosis Therapeutic anticoagulation Bleeding Recanalization Outcomes

Cathepsin D overexpression in the nervous system rescues lethality and Aβ42 accumulation of cathepsin D systemic knockout in vivo

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Acta Pharmaceutica Sinica B 2023年第10期13卷 4172-4184页

作者： Xiaosen Ouyang Willayat Y.Wani Gloria A.Benavides Matthew J.Redmann Hai Vo thomas van Groen Victor M.Darley-Usmar Jianhua Zhang Department of Pathology University of Alabama at BirminghamBirminghamAL 35294USA Department of Cell Developmental and Integrative BiologyUniversity of Alabama at BirminghamBirminghamAL 35294USA Birmingham VA Medical Center University of Alabama at BirminghamBirminghamAL 35294USA

The lysosome is responsible for protein and organelle degradation and homeostasis and the cathepsins play a key role in maintaining protein quality *** D(CTSD),is one such lysosomal protease,which when deficient in humans lead to neurolipofuscinosis(NCL)and is important in removing toxic protein *** studies demonstrated that CTSD germ-line knockout-CtsdKO(CDKO)resulted in accumulation of protein aggregates,decreased proteasomal activities,and postnatal lethality on Day 26±*** of wildtype CTSD,but not cathepsin B,L or mutant CTSD,decreased a-synuclein toxicity in worms and mammalian *** this study we generated a mouse line expressing human CTSD with a floxed STOP cassette between the ubiquitous CAG promoter and the *** crossing with Nestin-cre,the STOP cassette is deleted in NESTIN+cells to allow CTSD overexpression-CTSDtg(CDtg).The CDtg mice exhibited normal behavior and similar sensitivity to subchronic 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine(MPTP)induced *** breeding CDtg mice with CDKO mice,we found that over-expression of CTSD extended the lifespan of the CDKO mice,partially rescued proteasomal deficits and the accumulation of Aβ42 in the *** new transgenic mouse provides supports for the key role of CTSD in protecting against proteotoxicity and offers a new model to study the role of CTSD enhancement in vivo.

关键词： Cathepsin D transgenic mouse Mitochondrial bioenergetics Apoptosis Cathepsin D knockout mice Dopamine Autophagy Lysosome Life expectancy Behavior

Circulating predictive and diagnostic biomarkers for hepatitis B virus-associated hepatocellular carcinoma

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World Journal of Gastroenterology 2016年第37期22卷 8271-8282页

作者： Stijn van Hees Peter Michielsen thomas vanwolleghem Department of Gastroenterology and Hepatology Antwerp University Hospital Laboratory of Experimental Medicine and Pediatrics University of Antwerp

Chronic hepatitis B virus(HBV) infected patients have an almost 100-fold increased risk to develop hepatocellular carcinoma(HCC). HCC is the fifth most common and third most deadly cancer worldwide. Up to 50% of newly diagnosed HCC cases are attributed to HBV infection. Early detection improves survival and can be achieved through regular screening. Six-monthly abdominal ultrasound, either alone or in combination with alphafetoprotein serum levels, has been widely endorsed for this purpose. Both techniques however yield limited diagnostic accuracy, which is not improved when they are combined. Alternative circulating or histological markers to predict or diagnose HCC are therefore urgently needed. Recent advances in systems biology technologies have enabled the identification of several new putative circulating biomarkers. Although results from studies assessing combinations of these biomarkers are promising, evidence for their clinical utility remains low. In addition, most of the studies conducted so far show limitations in design. Attention must be paid for instance to different ethnicities and different etiologies when studying biomarkers for hepatocellular carcinoma. This review provides an overview on the current understandings and recent progress in the field of diagnostic and predictive circulating biomarkers for hepatocellular carcinoma in chronically infected HBV patients and discusses the future prospects.

关键词： Hepatocellular carcinoma Hepatitis B virus infection Biomarkers Predictive Diagnostic Alphafetoprotein Validation Limitations MicroR NA

Comparing crystal structures with symmetry and geometry

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npj Computational Materials 2021年第1期7卷 1491-1501页

作者： John C.thomas Anirudh Raju Natarajan Anton van der Ven Materials Department University of CaliforniaSanta BarbaraCAUSA

Measuring the similarity between two arbitrary crystal structures is a common challenge in crystallography and materials *** there are an infinite number of ways to mathematically relate two crystal structures,only a few are physically *** we introduce both a geometry-based and a symmetry-adapted similarity metric to compare crystal *** crystal symmetry and combinatorial optimization we describe an algorithm to arrive at the structural relationship that minimizes these similarity metrics across all possible maps between any pair of crystal *** approach makes it possible to(i)identify pairs of crystal structures that are identical,(ii)quantitatively measure the similarity between crystal structures,and(iii)find and rank structural transformation pathways between any pair of crystal *** discuss the advantages of using the symmetryadapted cost metric over the geometric ***,we show that all known structural transformation pathways between common crystal structures are recovered with the mapping *** methodology presented in this study will be of value to efforts that seek to catalogue crystal structures,identify structural transformation pathways or prune large first-principles datasets used to parameterize on-lattice Hamiltonians.

关键词： crystal symmetry similarity

Rectifying jet breakup by electric forcing

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液滴(英文) 2023年第2期2卷 85-93页

作者： David van Assche thomas Beneyton Jean-Christophe Baret CRPP UMR5031CNRSUniversitéde BordeauxPessacFrance Institut Universitaire de France ParisFrance

The high-throughput production of monodisperse droplets is paramount in most of the applications in droplet *** a flow-focusing junction,a straightforward way to increase droplet production rate is to increase the flow ***,at a critical flow velocity,the droplet monodispersity breaks down due to a transition from the dripping to the jetting *** a result,a much more polydisperse droplet population is *** change from monodisperse to polydisperse droplet production emerges from the intrinsic properties of the instabilities of *** the jetting regime,droplet pinch-off is governed by a convective instability which amplifies random noise when traveling down the jet leading to an irregular *** show that with the use of an amplitude-modulated electric signal,we select the breakup frequency of the *** the perturbation frequency close to the natural breakup frequency of the jet,we increase the monodispersity of the droplet *** method is applicable to droplet production at a high throughput,that is,beyond the dripping to jetting threshold,including an active control since the frequency,and hence droplet sizes,are determined by the forcing frequency.

关键词： disperse regime hence

Traditional Chinese Medicine-Based Subtyping of Early-Stage Type 2 Diabetes Using Plasma Metabolomics Combined with Ultra-Weak Photon Emission

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Engineering 2019年第5期5卷 916-923页

作者： Min He Mengmeng Sun Slavik Koval Roeland van Wijk thomas Hankemeier Jan van der Greef Eduard P.A.van Wijk Mei Wang Leiden University–European Center for Chinese Medicine and Natural Compounds Institute of BiologyLeiden UniversityLeiden 2333 BEthe Netherlands Analytical BioSciences Leiden Academic Center for Drug Research(LACDR)Leiden UniversityLeiden 2333 CCthe Netherlands Changchun University of Chinese Medicine Changchun 130117China Sino-Dutch Center for Preventive and Personalized Medicine Tiel 4002 AGthe Netherlands Meluna Research Geldermalsen 4191 LCthe Netherlands SU Biomedicine Leiden 2300 AMthe Netherlands Shenzhen Huakai Traditional Chinese Medicine and Natural Medicine Research Center Shenzhen 518114China

The prevalence of type 2 diabetes mellitus(T2DM)is increasing rapidly *** of the limited success of generic interventions,the focus of the disease study has shifted toward personalized strategies,particularly in the early stages of the *** Chinese medicine(TCM)is based on a systems view combined with personalized strategies and has improved our knowledge of personalized *** a systems biology perspective,the understanding of personalized diagnostics can be improved to yield a biochemical basis for such strategies;for example,metabolomics can be used in combination with other system-based diagnostic methods such as ultra-weak photon emission(UPE).In this study,we investigated the feasibility of using plasma metabolomics obtained from 44 pre-T2DM subjects to stratify the following TCM-based subtypes:Qi-Yin deficiency,Qi-Yin deficiency with dampness,and Qi-Yin deficiency with *** studied the relationship between plasma metabolomics and UPE with respect to TCM-based subtyping in order to obtain biochemical information for further interpreting disease *** component analysis of plasma metabolites revealed differences among the TCM-based pre-T2DM *** high levels of lipids(e.g.,cholesterol esters and triglycerides)were important discriminators of two of the three subtypes and may be associated with a higher risk of cardiovascular *** metabolomics data indicate that the lipid profile is an essential component captured by UPE with respect to stratifying subtypes of *** results suggest that metabolic differences exist among different TCM-based subtypes of pre-T2DM,and profiling plasma metabolites can be used to discriminate among these *** metabolomics thus provides biochemical insights into system-based UPE measurements.

关键词： Type 2 diabetes mellitus Plasma metabolites Disease subtypes Ultra-weak photon emission Correlation networks