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121.
Cover Picture: Molecular Origin of the Hydrolytic Activity and Fixed Regioselectivity of a ZrIV‐Substituted Polyoxotungstate as Artificial Protease (Chem. Eur. J. 31/2014) 下载免费PDF全文
122.
Unraveling the Crystal Structure of Lanthanide–Murexide Complexes: Use of an Ancient Complexometry Indicator as a Near‐Infrared‐Emitting Single‐Ion Magnet 下载免费PDF全文
Xiaohui Yi Dr. Kevin Bernot Vincent Le Corre Dr. Guillaume Calvez Dr. Fabrice Pointillart Dr. Olivier Cador Dr. Boris Le Guennic Julie Jung Dr. Olivier Maury Dr. Virginie Placide Dr. Yannick Guyot Dr. Thierry Roisnel Dr. Carole Daiguebonne Prof. Olivier Guillou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(6):1569-1576
Herein, we provide some structural evidence of the complexation color‐change of murexide solutions in presence of lanthanide, which has been used for decades in complexometric studies. For Ln=Sm to Lu and Y, the compounds crystallize as monomeric [Ln(Murex)3] ? 11 H2O with an N3O6 tricapped square‐antiprism environment, which are stable up to 250 °C. Single‐ion magnet (SIM) behavior is then observed on the YbIII derivative in an original nine‐coordinated environment. In‐field slow relaxation (Δ=(15.6±1) K; τ0=2.73×10?6 s) is observed with a very narrow distribution of the relaxation time (αmax=0.09). Magnetic and photophysical properties can be correlated. On one hand the analysis of NIR emission spectrum permits to have access to crystal field parameters and to compare them with those extracted from dc measurements. On the other hand, magnetic measurements permit to identify the nature of the M J states involved in the 2F5/2→2F7/2 luminescence spectrum. The gap between the low‐lying states is in agreement with the energy barrier obtained from magnetic slow‐relaxation measurement. 相似文献
123.
Zhen Zhao Vincent H. Crespi James D. Kubicki Daniel J. Cosgrove Linghao Zhong 《Cellulose (London, England)》2014,21(2):1025-1039
The effect of surface hydrophobicity and side-chain variation on xyloglucan adsorption onto cellulose microfibrils (CMF) is investigated via molecular dynamics simulations. A molecular model of CMF with (100), (010), (1–10), (110) and (200) crystal faces was built. We considered xylogluco-oligosaccharides (XGO) with three repeating units, namely (XXXG)3, (XXLG)3, and (XXFG)3 (where each (1,4)-β-d-glucosyl residue in the backbone is given a one-letter code according to its substituents: G = β-d-Glc; X = α-d-Xyl-(1,6)-β-d-Glc; L = β-d-Gal-(1,2)-α-d-Xyl-(1,6)-β-d-Glc; F = α-l-Fuc-(1,2)-β-d-Gal-(1,2)-α-d-Xyl-(1,6)-β-d-Glc). Our work shows that (XXXG)3 binds more favorably to the CMF (100) and (200) hydrophobic surfaces than to the (110), (010) and (1–10) hydrophilic surfaces. The origin of this behavior is attributed to the topography of hydrophobic CMF surface, which stabilizes (XXXG)3 in flat conformation. In contrast, on the rough hydrophilic CMF surface (XXXG)3 adopts a less favorable random-coil conformation to facilitate more hydrogen bonds with the surface. Extending the xyloglucan side chains from (XXXG)3 to (XXLG)3 hinders their stacking on the CMF hydrophobic surface. For (XXFG)3, the interaction with the hydrophobic surface is as strong as (XXXG)3. All three XGOs have similar binding to the hydrophilic surface. Steered molecular dynamics simulation was performed on an adhesive model where (XXXG)3 was sandwiched between two CMF hydrophobic surfaces. Our analysis suggests that this sandwich structure might help provide mechanical strength for plant cell walls. Our study relates to a recently revised model of primary cell walls in which extensibility is largely determined by xyloglucan located in limited regions of tight contact between CMFs. 相似文献
124.
Sana Jahanshahi‐Anbuhi Kevin Pennings Vincent Leung Dr. Meng Liu Carmen Carrasquilla Dr. Balamurali Kannan Prof. Dr. Yingfu Li Prof. Dr. Robert Pelton Prof. Dr. John D. Brennan Prof. Dr. Carlos D. M. Filipe 《Angewandte Chemie (International ed. in English)》2014,53(24):6155-6158
A simple and inexpensive method is reported for the long‐term stabilization of enzymes and other unstable reagents in premeasured quantities in water‐soluble tablets (cast, not compressed) made with pullulan, a nonionic polysaccharide that forms an oxygen impermeable solid upon drying. The pullulan tablets dissolve in aqueous solutions in seconds, thereby facilitating the easy execution of bioassays at remote sites with no need for special reagent handling and liquid pipetting. This approach is modular in nature, thus allowing the creation of individual tablets for enzymes and their substrates. Proof‐of‐principle demonstrations include a Taq polymerase tablet for DNA amplification through PCR and a pesticide assay kit consisting of separate tablets for acetylcholinesterase and its chromogenic substrate, indoxyl acetate, both of which are highly unstable. The encapsulated reagents remain stable at room temperature for months, thus enabling the room‐temperature shipping and storage of bioassay components. 相似文献
125.
Skeleton Decoration of NHCs by Amino Groups and its Sequential Booster Effect on the Palladium‐Catalyzed Buchwald–Hartwig Amination 下载免费PDF全文
Yin Zhang Dr. Vincent César Golo Storch Dr. Noël Lugan Dr. Guy Lavigne 《Angewandte Chemie (International ed. in English)》2014,53(25):6482-6486
A challenging synthetic modification of PEPPSI‐type palladium pre‐catalysts consisting of a stepwise incorporation of one and two amino groups onto the NHC skeleton was seen to exert a sequential enhancement of the electronic donor properties. This appears to be positively correlated with the catalytic performances of the corresponding complexes in the Buchwald–Hartwig amination. This is illustrated, for example, by the quantitative amination of 4‐chloroanisole by morpholine within 2 h at 25 °C with a 2 mol % catalyst/substrate ratio or by a significant reduction of catalytic loading (down to 0.005 mol %) for the coupling of aryl chlorides with anilines (max TON: 19 600). 相似文献
126.
Back Cover: Assessment of DNA Binding to Human Rad51 Protein by using Quartz Crystal Microbalance and Atomic Force Microscopy: Effects of ADP and BRC4‐28 Peptide Inhibitor (ChemPhysChem 17/2014) 下载免费PDF全文
127.
TiO2-mediated photocatalysis is widely used in a variety of applications and products in the environmental and energy fields, including photoelectrochemical conversion, self-cleaning surfaces, and especially water purification systems. The dimensionality of the structure of a TiO2 material can affect its properties, functions, and more specifically, its photocatalytic performance. In this work, the photocatalytic inactivation of Gram-negative Escherichia coli using three photocatalysts, differing in their structure and other characteristics, was studied in a batch reactor under UVA light. The aim was to establish the disinfection efficiency of solid TiO2 compared with that of suspended catalysts, widely considered as reference cases for photocatalytic water disinfection. The bacterial inactivation profiles obtained showed that: (1) the photoinactivation was exclusively related to the quantity of photons retained per unit of treated volume, irrespective of the characteristics of the photocatalyst and the emitted light flux densities; (2) across the whole UV light range studied, each of the photocatalytic solids was able to achieve more than 2 log bacterial inactivation with less than 2 h UV irradiation; (3) none of the used catalysts achieved a total bacterial disinfection during the treatment time. For each of the catalysts the quantum yield has been assessed in terms of disinfection efficiency, the 2D material showed almost the same performance as those of suspended catalysts. This catalyst is promising for supported photocatalysis applications. 相似文献
128.
Felix C. Raps Dr. Vincent C. Fäseke Prof. Dr. Daniel Häussinger Prof. Dr. Christof Sparr 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18548-18552
The biomimetic synthesis of aromatic polyketides from macrocyclic substrates by means of catalyst-controlled transannular cyclization cascades is described. The macrocyclic substrates, which feature increased stability and fewer conformational states, were thereby transformed into several distinct polyketide scaffolds. The catalyst-controlled transannular cyclizations selectively led to aromatic polyketides with a defined folding and oxygenation pattern, thus emulating β-keto-processing steps of polyketide biosynthesis. 相似文献
129.
Jingxuan Ren Songfeng Han Ashley R. Proctor Danielle E. Desa Gabriel A. Ramirez Vincent Ralph D. Ching-Roa Joseph B. Majeski Irfaan A. Dar Nathaniel E. Barber Amanda M. Forti Danielle S.W. Benoit Regine Choe 《Photochemistry and photobiology》2020,96(2):380-387
Noninvasive monitoring of vascularization can potentially diagnose impaired bone healing earlier than current radiographic methods. In this study, a noncontact diffuse correlation tomography (DCT) technique was employed to measure longitudinal blood flow changes during bone healing in a murine femoral fracture model. The three-dimensional distribution of the relative blood flow was quantified from one day pre-fracture to 48 days post-fracture. For three mice, frequent DCT measurements were performed every other day for one week after fracture, and then weekly thereafter. A decrease in blood flow was observed in the bone fracture region at one day post-fracture, followed by a monotonic increase in blood flow beyond the pre-injury baseline until five to seven days post-fracture. For the remaining 12 mice, only weekly DCT measurements were performed. Data collected on a weekly basis show the blood flow for most mice was elevated above baseline during the first two post-fracture weeks, followed by a subsequent decrease. Torsional strength of the excised femurs was measured for all 15 mice after 7 weeks of healing. A metric based on the early blood flow changes shows a statistically significant difference between the high strength group and the low strength group. 相似文献
130.
Dr. Julien Gasnot Clément Botella Dr. Sébastien Comesse Dr. Sami Lakhdar Dr. Carole Alayrac Prof. Annie-Claude Gaumont Prof. Vincent Dalla Dr. Catherine Taillier 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(29):11867-11871
Advances in the field of phosphorus chemistry are documented, by revealing the synthetic utility of previously underutilized quaternary phosphiranium salts (QPrS) as three-chain-atom electrophilic building blocks. Notably, control of their challenging C-centered electrophilicity is disclosed with an expedient synthesis of tertiary β-anilino phosphines as a proof-of-concept. 相似文献