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141.
Dr. Lena Decuyper Katarina Magdalenić Marie Verstraete Dr. Marko Jukič Dr. Izidor Sosič Dr. Eric Sauvage Dr. Ana Maria Amoroso Olivier Verlaine Prof. Dr. Bernard Joris Prof. Dr. Stanislav Gobec Prof. Dr. Matthias D'hooghe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(70):16128-16140
Innovative monocyclic β-lactam entities create opportunities in the battle against resistant bacteria because of their PBP acylation potential, intrinsically high β-lactamase stability and compact scaffold. α-Benzylidene-substituted 3-amino-1-carboxymethyl-β-lactams were recently shown to be potent PBP inhibitors and constitute eligible anchor points for synthetic elaboration of the chemical space around the central β-lactam ring. The present study discloses a 12-step synthesis of ten α-arylmethylidenecarboxylates using a microwave-assisted Wittig olefination as the crucial reaction step. The library was designed aiming at enhanced β-lactam electrophilicity and extended electron flow after enzymatic attack. Additionally, increased β-lactamase stability and intermolecular target interaction were envisioned by tackling both the substitution pattern of the aromatic ring and the β-lactam C4-position. The significance of α-unsaturation was validated and the R39/PBP3 inhibitory potency shown to be augmented the most through decoration of the aromatic ring with electron-withdrawing groups. Furthermore, ring cleavage by representative β-lactamases was ruled out, providing new insights in the SAR landscape of monocyclic β-lactams as eligible PBP or β-lactamase inhibitors. 相似文献
142.
Giang Huong Nguyen Thomas S. Dexheimer Andrew S. Rosenthal Wai Kit Chu Dharmendra Kumar Singh Georgina Mosedale Csanád Z. Bachrati Lena Schultz Masaaki Sakurai Pavel Savitsky Mika Abu Peter J. McHugh Vilhelm A. Bohr Curtis C. Harris Ajit Jadhav Opher Gileadi David J. Maloney Anton Simeonov Ian D. Hickson 《Chemistry & biology》2013,20(1):55-62
143.
Lena Wolff Jens Flemming Reinhard Schmitz Karsten Grger Christel Müller-Goymann 《Colloids and surfaces. A, Physicochemical and engineering aspects》2008,330(2-3):116-126
Lyophilisation of an aluminum hydroxide adjuvant containing formulation for use in vaccine development has been investigated. Novel formulation approaches using disaccharides, polysaccharides, polyols and polymers have been investigated as stabilising excipients to prevent aluminum hydroxide adjuvant from aggregation during a freeze–thaw cycle or the lyophilisation process itself. Amorphous character of the lyophilisates was investigated by wide angle X-ray diffraction. Sedimentation assay, particle size analysis and optical microscopy could show that aluminum adjuvant gel character of selected formulations could be maintained within acceptable quality or stayed the same in some cases. In principle, it could be demonstrated that not less than 10% excipient is necessary to yield good results within applied analytics evaluating the excipients’ protecting qualities. Based on results obtained by this study, the formulations containing trehalose at a concentration of 15 or 20%, dextran, PVP K 25, HES 450 and 200, saccharose and sorbitole along with polysorbate 80 and buffer promise to be good candidates for the protection of aluminum adjuvanted vaccines during exposure to coldness stresses as during freezing or lyophilisation. 相似文献
144.
145.
Prof. Dr. Lothar Weber Jan Kahlert Dr. Regina Brockhinke Lena Böhling Dr. Andreas Brockhinke Dr. Hans‐Georg Stammler Beate Neumann Rachel A. Harder Dr. Mark A. Fox 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(27):8347-8357
Seven derivatives of 1,2‐dicarbadodecaborane (ortho‐carborane, 1,2‐C2B10H12) with a 1,3‐diethyl‐ or 1,3‐diphenyl‐1,3,2‐benzodiazaborolyl group on one cage carbon atom were synthesized and structurally characterized. Six of these compounds showed remarkable low‐energy fluorescence emissions with large Stokes shifts of 15100–20260 cm?1 and quantum yields (ΦF) of up to 65 % in the solid state. The low‐energy fluorescence emission, which was assigned to a charge‐transfer (CT) transition between the cage and the heterocyclic unit, depended on the orientation (torsion angle, ψ) of the diazaborolyl group with respect to the cage C? C bond. In cyclohexane, two compounds exhibited very weak dual fluorescence emissions with Stokes shifts of 15660–18090 cm?1 for the CT bands and 1960–5540 cm?1 for the high‐energy bands, which were assigned to local transitions within the benzodiazaborole units (local excitation, LE), whereas four compounds showed only CT bands with ΦF values between 8–32 %. Two distinct excited singlet‐state (S1) geometries, denoted S1(LE) and S1(CT), were observed computationally for the benzodiazaborolyl‐ortho‐carboranes, the population of which depended on their orientation (ψ). TD‐DFT calculations on these excited state geometries were in accord with their CT and LE emissions. These C‐diazaborolyl‐ortho‐carboranes were viewed as donor–acceptor systems with the diazaborolyl group as the donor and the ortho‐carboranyl group as the acceptor. 相似文献
146.
L Weber D Eickhoff J Kahlert L Böhling A Brockhinke HG Stammler B Neumann MA Fox 《Dalton transactions (Cambridge, England : 2003)》2012,41(34):10328-10346
Two linear π-conjugated systems with 1,3-diethyl-1,3,2-benzodiazaborolyl [C(6)H(4)(NEt)(2)B-] as a donor group and dimesitylboryl (-BMes(2)) as acceptor were synthesised with -ethynylene-phenylene- (-C[triple bond, length as m-dash]C-1,4-C(6)H(4)-, 3) and -ethynylene-thiophene- (-C[triple bond, length as m-dash]C-2,5-C(4)H(2)S-12) bridges between the boron atoms. An assembly (20) consisting of two diazaborolyl-ethynylene-phenylene-boryl units, [C(6)H(4)(NCy)(N')B-C[triple bond, length as m-dash]C-1,4-C(6)H(4)-BMes(2)] joined via a 1,4-phenylene unit at the nitrogen atoms (N') of the diazaborolyl units was also synthesised. The three push-pull systems, 3, 12 and 20, form salts on fluoride addition with the BMes(2) groups converted into (BMes(2)F)(-) anions. The molecular structures of 3, 12 and (NBu(4))(12·F) were elucidated by X-ray diffraction analyses. The borylated systems 3, 12 and 20 show intense blue luminescence in cyclohexane with quantum yields (Φ(fl)) of 0.99, 0.44 and 0.94, respectively, but weak blue-green luminescence in tetrahydrofuran (Φ(fl) = 0.02-0.05). The charge transfer nature of these transitions is supported by TD-DFT computations with the CAM-B3LYP functional. Addition of tetrabutylammonium fluoride to tetrahydrofuran solutions of 3 and 20 resulted in strong violet-blue luminescence with emission intensities up to 46 times more than the emission intensities observed prior to fluoride addition. Compounds 3 and 20 are demonstrated here as remarkable 'turn-on' fluoride sensors in tetrahydrofuran solutions. 相似文献
147.
Daumann LJ Dalle KE Schenk G McGeary RP Bernhardt PV Ollis DL Gahan LR 《Dalton transactions (Cambridge, England : 2003)》2012,41(6):1695-1708
Analogues of the ligand 2,2'-(2-hydroxy-5-methyl-1,3-phenylene)bis(methylene)bis((pyridin-2-ylmethyl)azanediyl)diethanol (CH(3)H(3)L1) are described. Complexation of these analogues, 2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol (CH(3)HL2), 4-bromo-2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)phenol (BrHL2), 2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-nitrophenol (NO(2)HL2) and 4-methyl-2,6-bis(((2-phenoxyethyl)(pyridin-2-ylmethyl)amino)methyl)phenol (CH(3)HL3) with zinc(II) acetate afforded [Zn(2)(CH(3)L2)(CH(3)COO)(2)](PF(6)), [Zn(2)(NO(2)L2)(CH(3)COO)(2)](PF(6)), [Zn(2)(BrL2)(CH(3)COO)(2)](PF(6)) and [Zn(2)(CH(3)L3)(CH(3)COO)(2)](PF(6)), in addition to [Zn(4)(CH(3)L2)(2)(NO(2)C(6)H(5)OPO(3))(2)(H(2)O)(2)](PF(6))(2) and [Zn(4)(BrL2)(2)(PO(3)F)(2)(H(2)O)(2)](PF(6))(2). The complexes were characterized using (1)H and (13)C NMR spectroscopy, mass spectrometry, microanalysis, and X-ray crystallography. The complexes contain either a coordinated methyl- (L2 ligands) or phenyl- (L3 ligand) ether, replacing the potentially nucleophilic coordinated alcohol in the previously reported complex [Zn(2)(CH(3)HL1)(CH(3)COO)(H(2)O)](PF(6)). Functional studies of the zinc complexes with the substrate bis(2,4-dinitrophenyl) phosphate (BDNPP) showed them to be competent catalysts with, for example, [Zn(2)(CH(3)L2)](+), k(cat) = 5.70 ± 0.04 × 10(-3) s(-1) (K(m) = 20.8 ± 5.0 mM) and [Zn(2)(CH(3)L3)](+), k(cat) = 3.60 ± 0.04 × 10(-3) s(-1) (K(m) = 18.9 ± 3.5 mM). Catalytically relevant pK(a)s of 6.7 and 7.7 were observed for the zinc(II) complexes of CH(3)L2(-) and CH(3)L3(-), respectively. Electron donating para-substituents enhance the rate of hydrolysis of BDNPP such that k(cat)p-CH(3) > p-Br > p-NO(2). Use of a solvent mixture containing H(2)O(18)/H(2)O(16) in the reaction with BDNPP showed that for [Zn(2)(CH(3)L2)(CH(3)COO)(2)](PF(6)) and [Zn(2)(NO(2)L2)(CH(3)COO)(2)](PF(6)), as well as [Zn(2)(CH(3)HL1)(CH(3)COO)(H(2)O)](PF(6)), the (18)O label was incorporated in the product of the hydrolysis suggesting that the nucleophile involved in the hydrolysis reaction was a Zn-OH moiety. The results are discussed with respect to the potential nucleophilic species (coordinated deprotonated alcohol versus coordinated hydroxide). 相似文献
148.
Beyeh NK Weimann DP Kaufmann L Schalley CA Rissanen K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(18):5552-5557
The non-covalent interactions of different upper-rim-substituted C(2)-resorcinarenes with tetramethylammonium salts were analyzed in the gas phase in an Electrospray Ionization Fourier-transform ion-cyclotron-resonance (ESI-FTICR) mass spectrometer and by (1)H NMR titrations. The order of binding strengths of the hosts towards the tetramethylammonium cation in the gas phase reflects the electronic nature of the substituents on the upper rim of the resorcinarene. In solution, however, a different trend with particularly high binding constants for halogenated resorcinarenes has been observed. This trend can be explained by a synergetic effect originating from the interaction of the halogenated resorcinarenes with the counter anions through hydrogen bonding. This study highlights the importance of weak interactions in recognition processes and points out the benefits of comparing the gas-phase data with results obtained from solution experiments. 相似文献
149.
150.
Chemical trapping of metal-bound oligomeric chains during the MAO-activated, metallocene-catalyzed polymerization of ethylene identify the two observed chain-bearing species to be alkylzirconocenium species and higher alkyl aluminiums, consistent with a proposed mechanism. 相似文献