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1.
Unwinding of the C‐Terminal Residues of Neuropeptide Y is critical for Y2 Receptor Binding and Activation
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Anette Kaiser Paul Müller Tristan Zellmann Dr. Holger A. Scheidt Dr. Lars Thomas Mathias Bosse Dr. Rene Meier Prof. Dr. Jens Meiler Prof. Dr. Daniel Huster Prof. Dr. Annette G. Beck‐Sickinger Dr. Peter Schmidt 《Angewandte Chemie (International ed. in English)》2015,54(25):7446-7449
Despite recent breakthroughs in the structural characterization of G‐protein‐coupled receptors (GPCRs), there is only sparse data on how GPCRs recognize larger peptide ligands. NMR spectroscopy, molecular modeling, and double‐cycle mutagenesis studies were integrated to obtain a structural model of the peptide hormone neuropeptide Y (NPY) bound to its human G‐protein‐coupled Y2 receptor (Y2R). Solid‐state NMR measurements of specific isotope‐labeled NPY in complex with in vitro folded Y2R reconstituted into phospholipid bicelles provided the bioactive structure of the peptide. Guided by solution NMR experiments, it could be shown that the ligand is tethered to the second extracellular loop by hydrophobic contacts. The C‐terminal α‐helix of NPY, which is formed in a membrane environment in the absence of the receptor, is unwound starting at T32 to provide optimal contacts in a deep binding pocket within the transmembrane bundle of the Y2R. 相似文献
2.
PEG修饰是改善蛋白质及肽类药物药代动力学特性的有效途径。然而与蛋白质相比,肽类化合物的分子较小,PEG的分子体积较大,其长链很可能会遮蔽肽的活性位点。因此,肽类化合物PEG修饰的位置和数量对于保持肽的生物活性至关重要。为阐明PEG修饰的位置与肽生物活性之间的关系,对肽类药物日达仙(胸腺素α1,Tα1)进行了定点修饰。Tα1具有α-螺旋、β-转角和无规卷曲的结构区域。分别在这些区域选择不同的位点进行PEG修饰。PEG的定点修饰是通过引入Cys,利用其-SH与mPEG-MAL的特异性反应而实现的。Con A刺激下的脾细胞产生IFN-γ试验的初步结果表明,PEG修饰对活性的影响与修饰的位置有一定的关系,大多数情况下,PEG修饰能保持Tα1的免疫活性。PEG修饰的位点对于保持肽的生物活性是很重要的。 相似文献
3.
The reaction of (1R,2R)‐(–)‐1,2‐diaminocyclohexane ( 1 ) [DACH] with the aldehyde (1R)‐(–)‐myrtenal ( 2 ) in MeOH afforded the bidentate diimine ligand, (1R,2R)‐(–)‐N1,N2‐bis{(1R)‐(–)myrtenylidene}‐1,2‐diaminocyclohexane ( 3 ) in a high yield. Reduction of 3 using LiAlH4 led to the formation of the desired ligand ( 4 ) (1R,2R)‐(–)‐N1,N2‐bis{(1R)‐(–)myrtenyl}‐1,2‐diaminocyclohexane. Treatment of compound 4 with K2PtCl4 or K2PdCl4 yielded the corresponding platinum(II) and palladium(II) complexes, Pt‐5 and Pd‐6 , respectively. The reaction of compound 3 with K2PtCl4 gave the diimine complex Pt‐7 . The cytotoxic activity of the complexes Pt‐5 , Pd‐6 and Pt‐7 was tested and compared to the approved drugs, cisplatin ( Cis ‐Pt ) and oxaliplatin ( Ox‐Pt ). The complexes ( Pt‐5 , Pd‐6 and Pt‐7 ) inhibit L1210 cell line proliferation with an IC50 of 0.6, 4.2, and 0.7 μL, respectively as evidenced by measuring thymidine incorporation. 相似文献
4.
Glenna So‐Ming Tong Dr. Chi‐Ming Che Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(29):7225-7237
We herein report a theoretical analysis based on a density functional theory/time‐dependent density functional theory (DFT/TDDFT) approach to understand the different phosphorescence efficiencies of a family of cyclometalated platinum(II) complexes: [Pt(NCN)Cl] ( 1 ; NCN=1,3‐bis(2‐pyridyl)phenyl?), [Pt(CNN)Cl] ( 2 ; CNN=6‐phenyl‐2,2′‐bipyridyl?), [Pt(CNC)(CNPh)] ( 3 ; CNC=2,6‐diphenylpyridyl2?), [Pt(R‐CNN)Cl] ( 4 ; R‐CNN=3‐(6′‐(2′′‐naphthyl)‐2′‐pyridyl)isoquinolinyl?), and [Pt(R‐CNC)(CNPh)] ( 5 ; R‐CNC=2,6‐bis(2′‐naphthyl)pyridyl2?). By considering both the spin–orbit coupling (SOC) and the electronic structures of these complexes at their respective optimized singlet ground (S0) and first triplet ( ) excited states, we were able to rationalize the experimental findings that 1) 1 is a strong emitter while its isomer 2 is only weakly emissive in CH2Cl2 solution at room temperature; 2) although the cyclometalated ligand of 3 has a higher ligand‐field strength than that of 1 , 3 is nonemissive in CH2Cl2 solution at 298 K; and 3) extension of π conjugation at the lateral aryl rings of the cyclometalated ligands of 2 and 3 to give 4 and 5 , respectively, leads to increased emission quantum yields under the same conditions. We found that Jahn–Teller and pseudo‐Jahn–Teller effects are operative in complexes 2 and 3 , respectively, on going from the optimized S0 ground state to the optimized excited state, and thus lead to large excited‐state structural distortions and hence fast nonradiative decay. Furthermore, a strong‐field ligand may push the two different occupied d orbitals so far apart that the SOC effect is small and the radiative decay rate is slow. This work is an example of electronic‐structure‐driven tuning of the phosphorescence efficiency, and the DFT/TDDFT approach is demonstrated to be a versatile tool for the design of phosphorescent materials with target characteristics. 相似文献
5.
Dr. Shuguang Yuan Dr. H. C. Stephen Chan Prof. Horst Vogel Prof. Slawomir Filipek Prof. Raymond C. Stevens Prof. Krzysztof Palczewski 《Angewandte Chemie (International ed. in English)》2016,55(35):10331-10335
Human purinergic G protein‐coupled receptor P2Y1 (P2Y1R) is activated by adenosine 5′‐diphosphate (ADP) to induce platelet activation and thereby serves as an important antithrombotic drug target. Crystal structures of P2Y1R revealed that one ligand (MRS2500) binds to the extracellular vestibule of this GPCR, whereas another (BPTU) occupies the surface between transmembrane (TM) helices TM2 and TM3. We introduced a total of 20 μs all‐atom long‐timescale molecular dynamic (MD) simulations to inquire why two molecules in completely different locations both serve as antagonists while ADP activates the receptor. Our results indicate that BPTU acts as an antagonist by stabilizing extracellular helix bundles leading to an increase of the lipid order, whereas MRS2500 blocks signaling by occupying the ligand binding site. Both antagonists stabilize an ionic lock within the receptor. However, binding of ADP breaks this ionic lock, forming a continuous water channel that leads to P2Y1R activation. 相似文献
6.
Cyclopentadienyl cobalt complexes (η5‐C5H4R) CoLI2 [L = CO,R=‐COOCH2CH=CH2 (3); L=PPh3, R=‐COOCH2‐CH=CH2 (6); L=P(p‐C6H4O3)3, R = ‐COOC(CH3) = CH2 (7), ‐COOCH2C6H5 (8), ‐COOCH2CH = CH2 (9)] were prepared and characterized by elemental analyses, 1H NMR, ER and UV‐vis spectra. The reaction of complexes (η5‐C5H4R)CoLI2 [L= CO, R= ‐COOC(CH3) = CH2 (1), ‐COOCH2C6H5(2); L=PPh3, R=‐COOC (CH3) = CH2 (4), ‐COOCH2C6H5 (5)] with Na‐Hg resulted in the formation of their corresponding substituted cobaltocene (η5‐C5H4R)2 Co[R=‐COOC(CH3) = CH2 (10), ‐COOCH2C6H5 (11)]. The electrochemical properties of these complexes 1–11 were studied by cyclic voltammetry. It was found that as the ligand (L) of the cobalt (III) complexes changing from CO to PPh3 and P(p‐tolyl)3, their oxidation potentials increased gradually. The cyclic voltammetry of α,α′‐substituted cobaltocene showed reversible oxidation of one electron process. 相似文献
7.
Guoping Xue Jerald S. Bradshaw N. Kent Dalley Paul B. Savage Reed M. Izatt 《Journal of heterocyclic chemistry》2003,40(2):383-387
Two new trans‐disubstituted cyclam ligands; 1,8‐di(6‐hydroxymethylpyridin‐2‐ylmethyl)‐1,4,8,11‐tetra‐azacyclotetradecane ( 5 ) and 1,8‐dimethyl‐4, 11‐di(6‐hydroxymethylpyridin‐2‐ylmethyl)‐1,4,8,11 ‐tetraaza‐cyclotetradecane ( 6 ); have been synthesized and characterized. The crystal structures of ligand 6 and its Ni(II) and Co(II) complexes have been determined. Crystal data are given for 6 , space group, P21/c, a = 11.095 (6) Å, b = 9.467 (5) Å, c = 13.283 (8) Å; β = 106.95 (5)°, Z = 2, R = 0.0715; for [Ni 6 ](C104)2, space group P21/c, a = 9.4848 (14) Å, b = 33.941(6) Å, c = 9.793(2) A, β = 95.264(14)°, Z = 4, R = 0.0567; for [Co 6 ](C104)2, space group, P21/c, a = 9.440 (6) Å, b = 33.848 (13) Å, c = 9.820 (3) Å, β = 95.16(3)°, Z = 4, R = 0.0718. In both complexes, the metal atoms are six‐coordinate with only one of the pendants interacting with the central metal atom and the other pendant remaining uncoordinated. 相似文献
8.
Dieter Seebach Estelle Dubost Raveendra I. Mathad Bernhard Jaun Michael Limbach Markus Löweneck Oliver Flögel James Gardiner Stefania Capone Albert K. Beck Hans Widmer Daniel Langenegger Dominique Monna Daniel Hoyer 《Helvetica chimica acta》2008,91(9):1736-1786
Cyclo‐β‐tetrapeptides are known to adopt a conformation with an intramolecular transannular hydrogen bond in solution. Analysis of this structure reveals that incorporation of a β2‐amino‐acid residue should lead to mimics of ‘α‐peptidic β‐turns’ (cf. A, B, C ). It is also known that short‐chain mixed β/α‐peptides with appropriate side chains can be used to mimic interactions between α‐peptidic hairpin turns and G protein‐coupled receptors. Based on these facts, we have now prepared a number of cyclic and open‐chain tetrapeptides, 7 – 20 , consisting of α‐, β2‐, and β3‐amino‐acid residues, which bear the side chains of Trp and Lys, and possess backbone configurations such that they should be capable of mimicking somatostatin in its affinity for the human SRIF receptors (hsst1–5). All peptides were prepared by solid‐phase coupling by the Fmoc strategy. For the cyclic peptides, the three‐dimensional orthogonal methodology (Scheme 3) was employed with best success. The new compounds were characterized by high‐resolution mass spectrometry, NMR and CD spectroscopy, and, in five cases, by a full NMR‐solution‐structure determination (in MeOH or H2O; Fig. 4). The affinities of the new compounds for the receptors hsst1–5 were determined by competition with [125I]LTT‐SRIF28 or [125I] [Tyr10]‐CST14. In Table 1, the data are listed, together with corresponding values of all β‐ and γ‐peptidic somatostatin/Sandostatin® mimics measured previously by our groups. Submicromolar affinities have been achieved for most of the human SRIF receptors hsst1–5. Especially high, specific binding affinities for receptor hsst4 (which is highly expressed in lung and brain tissue, although still of unknown function!) was observed with some of the β‐peptidic mimics. In view of the fact that numerous peptide‐activated G protein‐coupled receptors (GPCRs) recognize ligands with turn structure (Table 2), the results reported herein are relevant far beyond the realm of somatostatin: many other peptide GPCRs should be ‘reached’ with β‐ and γ‐peptidic mimics as well, and these compounds are proteolytically and metabolically stable, and do not need to be cell‐penetrating for this purpose (Fig. 5). 相似文献
9.
Piotr Kowalski Jolanta Jaśkowska Andrzej J. Bojarski Beata Duszyńska 《Journal of heterocyclic chemistry》2008,45(1):209-214
10.
Bernhard Valldorf Heiko Fittler Lukas Deweid Aileen Ebenig Stephan Dickgiesser Carolin Sellmann Janine Becker Stefan Zielonka Dr. Martin Empting Dr. Olga Avrutina Prof. Dr. Harald Kolmar 《Angewandte Chemie (International ed. in English)》2016,55(16):5085-5089
Multivalent ligands of death receptors hold particular promise as tumor cell‐specific therapeutic agents because they induce an apoptotic cascade in cancerous cells. Herein, we present a modular approach to generate death receptor 5 (DR5) binding constructs comprising multiple copies of DR5 targeting peptide (DR5TP) covalently bound to biomolecular scaffolds of peptidic nature. This strategy allows for efficient oligomerization of synthetic DR5TP‐derived peptides in different spatial orientations using a set of enzyme‐promoted conjugations or recombinant production. Heptameric constructs based on a short (60–75 residues) scaffold of a C‐terminal oligomerization domain of human C4b binding protein showed remarkable proapoptotic activity (EC50=3 nm ) when DR5TP was ligated to its carboxy terminus. Our data support the notion that inter‐ligand distance, relative spatial orientation and copy number of receptor‐binding modules are key prerequisites for receptor activation and cell killing. 相似文献
11.
Reaction of Pentelidene Complexes with Diazoalkanes: Stabilization of Parent 2,3‐Dipnictabutadienes
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Dr. Michael Seidl Dr. Markus Stubenhofer Prof. Dr. Alexey Y. Timoshkin Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2016,55(45):14037-14040
The reaction of the phosphinidene complex [Cp*P{W(CO)5}2] ( 1 a ) with diphenyldiazomethane leads to [{W(CO)5}Cp*P=NN{W(CO)5}=CPh2] ( 2 ). Compound 2 is a rare example of a phosphadiazadiene ligand (R‐P=N?N=CR′R′′) complex. At temperatures above 0 °C, 2 decomposes into the complex [{W(CO)5}PCp*{N(H)N=CPh2)2] ( 3 ), among other species. The reaction of the pentelidene complexes [Cp*E{W(CO)5}2] (E=P, As) with diazomethane (CH2NN) proceeds differently. For the arsinidene complex ( 1 b ), only the arsaalkene complex 4 b [{W(CO)5}2{η1:2‐(Cp*)As=CH2}] is formed. The reaction with the phosphinidene complex ( 1 a ) results in three products, the two phosphaalkene complexes [{W(CO)5}2{η1:2‐(R)P=CH2}] ( 4 a : R=Cp*, 5 : R=H) and the triazaphosphole derivative [{W(CO)5}P(Cp*)‐CH2‐N{W(CO)5}=N‐N(N=CH2)] ( 6 a ). The phosphaalkene complex ( 4 a ) and the arsaalkene complex ( 4 b ) are not stable at room temperature and decompose to the complexes [{W(CO)5}4(CH2=E?E=CH2)] ( 7 a : E=P, 7 b : E=As), which are the first examples of complexes with parent 2,3‐diphospha‐1,3‐butadiene and 2,3‐diarsa‐1,3‐butadiene ligands. 相似文献
12.
Distinct Spatial Relationship of the Interleukin‐9 Receptor with Interleukin‐2 Receptor and Major Histocompatibility Complex Glycoproteins in Human T Lymphoma Cells
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Enikő Nizsalóczki István Csomós Dr. Péter Nagy Dr. Zsolt Fazekas Dr. Carolyn K. Goldman Dr. Thomas A. Waldmann Dr. Sándor Damjanovich Dr. György Vámosi Dr. László Mátyus Dr. Andrea Bodnár 《Chemphyschem》2014,15(18):3969-3978
13.
Treatment of GaCl3 with one equiv of Li[NC4H3(CH2NMe2)‐2] (n = 1, 2, 3) in diethyl ether at ?78 °C yields GaCl3‐n[NC4H3(CH2NMe2)‐2]n (n = 1, 1 ; n = 2, 2 ; n = 3, 3 ). Compound 1 reacts with two equiv of RLi to afford GaR2[NC4H3(CH2NMe2)‐2] ( 4a, R=Me; 4b, R=Bu ) via transmetallation. Reacting 2 with one equiv of RLi in diethyl ether, 3 and 4 are formed via ligand redistribution. Variable temperature 1H NMR spectroscopic experiments reveal that the five‐coordinate gallium compound 3 is fluxional and results in a coalescence temperature at 5 °C, at which ΔG≠ is calculated at ca. 10.4 Kcal/mole. All the new compounds have been characterized by 1H and 13C NMR spectroscopy and the structures of compounds 3 and 4a have also been determined by X‐ray crystallography. 相似文献
14.
Differential Epitope Mapping by STD NMR Spectroscopy To Reveal the Nature of Protein–Ligand Contacts
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(48):15491-15495
Saturation transfer difference (STD) NMR spectroscopy is extensively used to obtain epitope maps of ligands binding to protein receptors, thereby revealing structural details of the interaction, which is key to direct lead optimization efforts in drug discovery. However, it does not give information about the nature of the amino acids surrounding the ligand in the binding pocket. Herein, we report the development of the novel method differential epitope mapping by STD NMR (DEEP‐STD NMR) for identifying the type of protein residues contacting the ligand. The method produces differential epitope maps through 1) differential frequency STD NMR and/or 2) differential solvent (D2O/H2O) STD NMR experiments. The two approaches provide different complementary information on the binding pocket. We demonstrate that DEEP‐STD NMR can be used to readily obtain pharmacophore information on the protein. Furthermore, if the 3D structure of the protein is known, this information also helps in orienting the ligand in the binding pocket. 相似文献
15.
Protein–protein interactions, particularly weak and transient ones, are often mediated by peptide recognition domains. Characterizing
the interaction interface of domain–peptide complexes and analyzing binding specificity for modular domains are critical for
deciphering protein–protein interaction networks. In this article, we report the successful use of an integrated computational
protocol to dissect the energetic profile and structural basis of peptide binding to third PDZ domain (PDZ3) from the PSD-95
protein. This protocol employs rigorous quantum mechanics/molecular mechanics (QM/MM), semi-empirical Poisson–Boltzmann/surface
area (PB/SA), and empirical conformational free energy analysis (CFEA) to quantitatively describe and decompose systematic
energy changes arising from, respectively, noncovalent interaction, desolvation effect, and conformational entropy loss associated
with the formation of 30 affinity-known PDZ3–peptide complexes. We show that the QM/MM-, PB/SA-, and CFEA-derived energy components
can work together fairly well in reproducing experimentally measured affinity after a linearly weighting treatment, albeit
they are not compatible with each other directly. We also demonstrate that: (1) noncovalent interaction and desolvation effect
donate, respectively, stability and specificity to complex architecture, while entropy loss contributes modestly to binding;
(2) P0 and P−2 of peptide ligand are the most important positions for determining both the stability and specificity of the PDZ3–peptide
complex, P−1 and P−3 can confer substantial stability (but not specificity) for the complex, and N-terminal P−4 and P−5 have only a very limited effect on binding. 相似文献
16.
Hongzhi Du Dr. Aldrik H. Velders Dr. Pieter J. Dijkstra Dr. Jingru Sun Dr. Zhiyuan Zhong Prof. Dr. Xuesi Chen Prof. Dr. Jan Feijen Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(38):9836-9845
Synthetic routes to aluminium ethyl complexes supported by chiral tetradentate phenoxyamine (salan‐type) ligands [Al(OC6H2(R‐6‐R‐4)CH2)2{CH3N(C6H10)NCH3}‐C2H5] ( 4 , 7 : R=H; 5 , 8 : R=Cl; 6 , 9 : R=CH3) are reported. Enantiomerically pure salan ligands 1–3 with (R,R) configurations at their cyclohexane rings afforded the complexes 4 , 5 , and 6 as mixtures of two diastereoisomers ( a and b ). Each diastereoisomer a was, as determined by X‐ray analysis, monomeric with a five‐coordinated aluminium central core in the solid state, adopting a cis‐(O,O) and cis‐(Me,Me) ligand geometry. From the results of variable‐temperature (VT) 1H NMR in the temperature range of 220–335 K, 1H–1H NOESY at 220 K, and diffusion‐ordered spectroscopy (DOSY), it is concluded that each diastereoisomer b is also monomeric with a five‐coordinated aluminium central core. The geometry is intermediate between square pyramidal with a cis‐(O,O), trans‐(Me,Me) ligand disposition and trigonal bipyramidal with a trans‐(O,O) and trans‐(Me,Me) disposition. A slow exchange between these two geometries at 220 K was indicated by 1H–1H NOESY NMR. In the presence of propan‐2‐ol as an initiator, enantiomerically pure (R,R) complexes 4 – 6 and their racemic mixtures 7 – 9 were efficient catalysts in the ring‐opening polymerization of lactide (LA). Polylactide materials ranging from isotactically biased (Pm up to 0.66) to medium heterotactic (Pr up to 0.73) were obtained from rac‐lactide, and syndiotactically biased polylactide (Pr up to 0.70) from meso‐lactide. Kinetic studies revealed that the polymerization of (S,S)‐LA in the presence of 4 /propan‐2‐ol had a much higher polymerization rate than (R,R)‐LA polymerization (kSS/kRR=10.1). 相似文献
17.
《中国化学会会志》2017,64(7):843-850
The organic salts 1‐(2‐pyridylmethyl)‐3‐alkylbenzimidazolium halide (pm‐RbH +X−) and 1‐(2‐pyridylmethyl)‐3‐alkylimidazolium halide (pm‐R′iH +X′−) were prepared (where R = 4‐, 3‐, 2‐fluorobenzyl ( 4f , 3f , and 2f , respectively), 4‐, 3‐, 2‐chlorobenzyl ( 4c , 3c , and 2c , respectively); 4‐methoxybenzyl (4mo); 2,3,4,5,6‐pentafluorobenzyl (f5); benzyl (b); and methyl (m)); X = Cl and Br; R′ = benzyl (b) and methyl (m); and X′ = Cl and I. From these salts, heteroleptic Ir(III ) complexes containing one N ‐heterocyclic carbene (NHC ) ligand [Ir(κ2‐ppy)2(κ2‐(pm‐Rb))]PF6 (R = 4f, 1 (PF6 ); 3f, 2 (PF6 ); 2f, 3 (PF6 ); f5b, 4 (PF6 ); 4c, 5 (PF6 ); 3c, 6 (PF6 ); 2c, 7 (PF6 ); 4mo, 8 (PF6 ); b, 9 (PF6 ); m, 10 (PF6 )) and [Ir(κ2‐ppy)2(κ2‐(pm‐R′i))]PF6 (R = b, 11 (PF6 ); m, 12 (PF6 )), were synthesized, and the crystal structures of 1 (PF6 ), 2 (PF6 ), 3 (PF6 ), 5 (PF6 ), 6 (PF6 ), 7 (PF6 ), 9 (PF6 ), 10 (PF6 ), and 12 (PF6 ) were determined by X‐ray diffraction. The neutral NHC ligands 1‐(2‐pyridylmethyl)‐3‐alkylbenzimidazolin‐2‐ylidene (pm‐Rb) and 1‐(2‐pyridylmethyl)‐3‐alkylimidazolin‐2‐ylidene (pm‐R′i) of all cations were found to be involved in the intermolecular π−π stacking interactions with the surrounding cations in the solid state, thereby probably influencing the photophysical behavior in the solid state and in solution. The absorption and emission properties of all the complexes show only small variations. 相似文献
18.
Peptides modified by pyridoxal‐5′‐phosphate (PLP), linked to a lysine residue via reductive amination, exhibit distinct spectral characteristics in the collision‐induced dissociation (CID) tandem mass (MS/MS) spectra that are described here. The MS/MS spectra typically display two dominant peaks whose m/z values correspond to neutral losses of [H3PO4] (?98 Da) and the PLP moiety as [C8H10NO5P] (?231 Da) from the precursor peptide ion, respectively. Few other peaks are observed. Recognition of this distinct fragmentation behavior is imperative since determining sequences and sites of modifications relies on the formation of amide backbone cleavage products for subsequent interpretation via proteome database searching. Additionally, PLP‐modified peptides exhibit suppressed precursor ionization efficiency which diminishes their detection in complex mixtures. Presented here is a protocol which describes an enrichment strategy for PLP‐modified peptides combined with neutral loss screening and peptide mass fingerprinting to map the PLP‐bonding site in a known PLP‐dependent protein. This approach represents an efficient alternative to site‐directed mutagenesis which has been the traditional method used for PLP‐bonding site localization in proteins. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
19.
Vinyl polymerizations of norbornene catalyzed by nickel complexes with acetoacetamide ligands
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On the basis of a remote effect, a series of acetoacetamide ligands and corresponding nickel complexes N‐(R‐phenyl) acetoacetamide Ni(CH2Ph) (PMe3) (R = H, 1 ; R = 2‐methyl, 2 ; R = 2,6‐dimethyl, 3 ; R = 2,6‐diisopropyl, 4 ; R = 4‐NO2, 5 ) were synthesized and characterized. The solid structure of complex 3 was confirmed by X‐ray single‐crystal analysis to be of cis form. 1H and 31P NMR spectroscopy confirmed that cis and trans isomers of nickel complexes were present in solution. Norbornene polymerizations with acetoacetamide nickel complexes activated with modified methylaluminoxane (MMAO) were investigated in detail. Remote steric and electronic effects of acetoacetamide ligand on catalytic activity and molecular weight of polynorbornenes (PNBs) were observed. Characterizations of the obtained PNBs show that the obtained polymer products are non‐crystalline vinylic‐addition polynorbornenes. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
20.
Gan-Yin Yuan Lei Zhang Meng-Jie Wang Kou-Lin Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(12):939-946
Much attention has been paid by chemists to the construction of supramolecular coordination compounds based on the multifunctional ligand 5‐sulfosalicylic acid (H3SSA) due to the structural and biological interest of these compounds. However, no coordination compounds have been reported for the multifunctional amino‐substituted sulfobenzoate ligand 2‐amino‐5‐sulfobenzoic acid (H2asba). We expected that H2asba could be a suitable building block for the assembly of supramolecular networks due to its interesting structural characteristics. The reaction of cadmium(II) nitrate with H2asba in the presence of the auxiliary flexible dipyridylamide ligand N,N′‐bis[(pyridin‐4‐yl)methyl]oxamide (4bpme) under ambient conditions formed a new mixed‐ligand coordination compound, namely bis(3‐amino‐4‐carboxybenzenesulfonato‐κO1)diaquabis{N,N′‐bis[(pyridin‐4‐yl)methyl]oxamide‐κN}cadmium(II)–N,N′‐bis[(pyridin‐4‐yl)methyl]oxamide–water (1/1/4), [Cd(C7H6NO5S)2(C14H14N4O2)2(H2O)2]·C14H14N4O2·4H2O, (1), which was characterized by single‐crystal and powder X‐ray diffraction analysis (PXRD), FT–IR spectroscopy, thermogravimetric analysis (TG), and UV–Vis and photoluminescence spectroscopic analyses in the solid state. The central CdII atom in (1) occupies a special position on a centre of inversion and exhibits a slightly distorted octahedral geometry, being coordinated by two N atoms from two monodentate 4bpme ligands, four O atoms from two monodentate 4‐amino‐3‐carboxybenzenesulfonate (Hasba−) ligands and two coordinated water molecules. Interestingly, complex (1) further extends into a threefold polycatenated 0D→2D (0D is zero‐dimensional and 2D is two‐dimensional) interpenetrated supramolecular two‐dimensional (4,4) layer through intermolecular hydrogen bonding. The interlayer hydrogen bonding further links adjacent threefold polycatenated two‐dimensional layers into a three‐dimensional network. The optical properties of complex (1) indicate that it may be used as a potential indirect band gap semiconductor material. Complex (1) exhibits an irreversible dehydration–rehydration behaviour. The fluorescence properties have also been investigated in the solid state at room temperature. 相似文献