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141.
Elise A. Dennis Alexander W. Gundlach–Graham Christie G. Enke Steven J. Ray Anthony J. Carado Charles J. Barinaga David W. Koppenaal Gary M. Hieftje 《Journal of the American Society for Mass Spectrometry》2013,24(5):690-700
Resolution in time–of–flight mass spectrometry (TOFMS) is ordinarily limited by the initial energy and space distributions within an instrument’s acceleration region and by the length of the field–free flight zone. With gaseous ion sources, these distributions lead to systematic flight–time errors that cannot be simultaneously corrected with conventional static–field ion–focusing devices (i.e., an ion mirror). It is known that initial energy and space distributions produce non–linearly correlated errors in both ion velocity and exit time from the acceleration region. Here we reinvestigate an old acceleration technique, constant–momentum acceleration (CMA), to decouple the effects of initial energy and space distributions. In CMA, only initial ion energies (and not their positions) affect the velocity ions gain. Therefore, with CMA, the spatial distribution within the acceleration region can be manipulated without creating ion–velocity error. The velocity differences caused by a spread in initial ion energy can be corrected with an ion mirror. We discuss here the use of CMA and independent focusing of energy and space distributions for both distance–of–flight mass spectrometry (DOFMS) and TOFMS. Performance characteristics of our CMA–DOFMS and CMA–TOFMS instrument, fitted with a glow–discharge ionization source, are described. In CMA–DOFMS, resolving powers (FWHM) of greater than 1000 are achieved for atomic ions with a flight length of 285 mm. In CMA–TOFMS, only ions over a narrow range of m/z values can be energy–focused; however, the technique offers improved resolution for these focused ions, with resolving powers of greater than 2000 for a separation distance of 350 mm. 相似文献
142.
A Stereoselective aldol reaction between bis(tert-butyldimethylsilyloxy) acetone and an isoxazoline-derived azaenolate is a key step in the construction of a C-ring model of sesbanimide A. 相似文献
143.
144.
Wen‐Jing Shi Dr. Mohamed E. El‐Khouly Dr. Kei Ohkubo Prof. Shunichi Fukuzumi Prof. Dennis K. P. Ng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11332-11341
An efficient functional mimic of the photosynthetic antenna‐reaction center has been designed and synthesized. The model contains a near‐infrared‐absorbing aza‐boron‐dipyrromethene (ADP) that is connected to a monostyryl boron‐dipyrromethene (BDP) by a click reaction and to a fullerene (C60) using the Prato reaction. The intramolecular photoinduced energy and electron‐transfer processes of this triad as well as the corresponding dyads BDP‐ADP and ADP‐C60 have been studied with steady‐state and time‐resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge‐separated states. Such calculations show that electron transfer from the singlet excited ADP (1ADP*) to C60 yielding ADP.+‐C60.? is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from 1BDP* to ADP in the dyad BDP‐ADP and electron transfer from 1ADP* to C60 in the dyad ADP‐C60. Sequential energy and electron transfer have also been clearly observed in the triad BDP‐ADP‐C60. By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈1011 s?1). The dynamics of electron transfer through 1ADP* has also been studied by monitoring the formation of C60 radical anion at 1000 nm. A fast charge‐separation process from 1ADP* to C60 has been detected, which gives the relatively long‐lived BDP‐ADP.+C60.? with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge‐separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP‐ADP and ADP‐C60, and the triad BDP‐ADP‐C60 are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems. 相似文献
145.
Dennis Cao Dr. Michal Juríček Zachary J. Brown Dr. Andrew C.‐H. Sue Dr. Zhichang Liu Juying Lei Anthea K. Blackburn Dr. Sergio Grunder Dr. Amy A. Sarjeant Prof. Ali Coskun Prof. Cheng Wang Prof. Omar K. Farha Prof. Joseph T. Hupp Prof. J. Fraser Stoddart 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8457-8465
We report the synthesis of two [2]catenane‐containing struts that are composed of a tetracationic cyclophane (TC4+) encircling a 1,5‐dioxynaphthalene (DNP)‐based crown ether, which bears two terphenylene arms. The TC4+ rings comprise either 1) two bipyridinium (BIPY2+) units or 2) a BIPY2+ and a diazapyrenium (DAP2+) unit. These degenerate and nondegenerate catenanes were reacted in the presence of Cu(NO3)2?2.5 H2O to yield Cu‐paddlewheel‐based MOF‐1050 and MOF‐1051. The solid‐state structures of these MOFs reveal that the metal clusters serve to join the heptaphenylene struts into grid‐like 2D networks. These 2D sheets are then held together by infinite donor–acceptor stacks involving the [2]catenanes to produce interpenetrated 3D architectures. As a consequence of the planar chirality associated with both the DNP and hydroquinone (HQ) units present in the crown ether, each catenane can exist as four stereoisomers. In the case of the nondegenerate (bistable) catenane, the situation is further complicated by the presence of translational isomers. Upon crystallization, however, only two of the four possible stereoisomers—namely, the enantiomeric RR and SS forms—are observed in the crystals. An additional element of co‐conformational selectivity is present in MOF‐1051 as a consequence of the substitution of one of the BIPY2+ units by a DAP2+ unit: only the translational isomer in which the DAP2+ unit is encircled by the crown ether is observed. The overall topologies of MOF‐1050 and MOF‐1051, and the selective formation of stereoisomers and translational isomers during the kinetically driven crystallization, provide evidence that weak noncovalent bonding interactions play a significant role in the assembly of these extended (super)structures. 相似文献
146.
Metal sheet forming processes like deep drawing are applied in order to produce carriage parts in mass production. Therefore, forming tools are required that are well protected against wear. For such forming tools, wear resistant surfaces are, e.g., produced by thermal spraying of hard material coatings. The thermal spraying process itself is a highly transient thermo-mechanical process. In order to gain a better understanding of the heat input and transfer during thermal spraying, a simulation framework for thermal spraying processes is presented. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
147.
Dennis Schnfeld Dilip Chalissery Franziska Wenz Marius Specht Chris Eberl Thorsten Pretsch 《Molecules (Basel, Switzerland)》2021,26(3)
For soft robotics and programmable metamaterials, novel approaches are required enabling the design of highly integrated thermoresponsive actuating systems. In the concept presented here, the necessary functional component was obtained by polymer syntheses. First, poly(1,10-decylene adipate) diol (PDA) with a number average molecular weight Mn of 3290 g·mol−1 was synthesized from 1,10-decanediol and adipic acid. Afterward, the PDA was brought to reaction with 4,4′-diphenylmethane diisocyanate and 1,4-butanediol. The resulting polyester urethane (PEU) was processed to the filament, and samples were additively manufactured by fused-filament fabrication. After thermomechanical treatment, the PEU reliably actuated under stress-free conditions by expanding on cooling and shrinking on heating with a maximum thermoreversible strain of 16.1%. Actuation stabilized at 12.2%, as verified in a measurement comprising 100 heating-cooling cycles. By adding an actuator element to a gripper system, a hen’s egg could be picked up, safely transported and deposited. Finally, one actuator element each was built into two types of unit cells for programmable materials, thus enabling the design of temperature-dependent behavior. The approaches are expected to open up new opportunities, e.g., in the fields of soft robotics and shape morphing. 相似文献
148.
The present Letter demonstrates a pop-in event that is caused by a nanoindentation-induced phase transformation in GaAs, and not accompanied by any dislocation nucleation. Our computer simulations reveal the appearance of the new phase, documented by the structural correlation functions and visualization of the atomic positions. This challenges the orthodox view that the initial pop-in event reflects nucleation of dislocations or their movement, and has a bearing on materials where dislocation activity is not present. 相似文献
149.
Dennis Oprych Prof. Dr. Bernd Strehmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(13):4297-4301
NIR and UV exposure of systems comprising upconversion nanoparticles ( UCNP ) based on NaYF4:Tm/Yb@NaYF4, a sensitizer absorbing either in the blue or UV region, and an onium salt with weak coordinating anion resulted in formation of conjugate acid (con-H+). That was namely Ivocerin (di(4-methoxybenzoyl)diethylgermane), ITX (2-iso-propyl thioxanthone), anthracene, pyrene, rubrene, camphore quinone, and a strong fluorescent coumarin (1,1,6,6,8-pentamethyl-2,3,5,6-tetrahyhdro-1H,4H-11-oxa-3a-aza-benzo[de]anthracene-10-one). Quantification occurred by treatment with Rhodamine B lactone whose color switched to intensive red after photolytic formation of con-H+. Exposure with a NIR laser at 980 nm resulted in less con-H+ compared to 395 nm where all sensitizers absorb radiation. UCNP did not mainly interfered formation of con-H+. The different rates obtained in both experiments responsibly explain the failure and success to initiate polymerization of epoxides applying ether 980 nm or 395 nm excitation, respectively. 相似文献
150.
Dr. Dennis Rottschäfer Beate Neumann Dr. Hans-Georg Stammler Dr. Tetiana Sergeieva Dr. Diego M. Andrada Dr. Rajendra S. Ghadwal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(9):3055-3064
Herein, we report the first 1,4-diphosphinine-1,4-diide compound [(ADCPh)P]2 ( 5-Ph ) (ADCPh=PhC{(NDipp)C}2; Dipp=2,6-iPr2C6H3) derived from an anionic dicarbene (ADCPh) as a red crystalline solid. Compound 5-Ph containing a 16π-electron planar fused-tricyclic ring system was obtained by the 4e reduction of [(ADCPh)PCl2]2 ( 4-Ph ) with Mg (or KC8) in a quantitative yield. Experimental and computational results imply that the central 8π-electrons C4P2 ring of 5-Ph , which is fused between two 6π-electrons C3N2 aromatic rings, is antiaromatic. Thus, each of the phosphorus atoms of 5-Ph has two electron-lone-pairs, one in a p-type orbital is in conjugation with the C=C bonds of the C4P2 ring, while the second resides in a σ-symmetric orbital. This can be shown with the gold complex [(ADCPh)P(AuCl)2]2 ( 6-Ph ) obtained by reacting 5-Ph with (Me2S)AuCl. A mixture of 5-Ph and 4-Ph undergoes comproportionation in the presence of MgCl2 to form the intermediate oxidation state compound [(ADCAr)P]2(MgCl4) ( 7-Ph ), which is an aromatic species. 相似文献