Ion-molecule reactions and collision-activated dissociation of C4H 4 +. isomers: A case study in the use of the MS3 capabilities of a pentaquadrupole mass spectrometer

Isomeric C₄H ₄ ^+. radical cations vinylacetylene (a), butatriene (b), methylene cyclopropene (c), and the nonaromatic cyclobutadiene (d), generated, respectively, from the neutral precursors 3-butyn-1-ol (1), 1,4-dichloro-2-butyne (2), benzene (3), and 7,8-benzotricyclo [4.2.2.0^2,5]deca-3,7,9-triene (4), undergo diagnostically different ion-molecule reactions with allene, isoprene, furan, and thiophene. It is speculated that adducts are generated by [2 + 2] cycloadditions with the first reagent and [4 + 2] Dials-Alder cycloadditions with isoprene, furan, and thiophene. The initially formed cycloaddition adducts fragment rapidly, isomerize, or undergo further addition of neutral reagent to yield a complex set of products. With a pentaquadrupole mass spectrometer, MS³ experiments that employ three stages of ion mass analysis are used to help elucidate the ion-molecule reactions and to distinguish the isomeric C⁴H ₄ ^+. ions. Among these experiments, the reaction intermediate spectrum reveals the nature of the intermediates connecting the reactant to a selected product while the sequential product spectrum provides mechanistic and structural information on the adducts and other ion-molecule products. The unique combination of ion-molecule reactions with collision-activated dissociation employed here provides valuable information on the chemistry of ionized cyclobutadiene, including its proclivity to undergo [2 + 2] and [4 + 2] cyc1oadditions.     

Polar [4+2+] diels-alder cycloaddition to nitrilium and immonium ions in the gas phase: Applications of multiple stage mass spectrometry in a pentaquadrupole instrument

Multiple stage MS² and MS³ mass spectrometric experiments, performed using a pentaquadrupole instrument, are employed to explore the gas-phase ion-molecule chemistry of several nitrilium [R-C≡N⁺-H (1), R-C≡N⁺-CH₃ (2), and H-C≡N⁺-C₂H₅ (3)] as well as immonium ions RR¹C=N⁺R²R³ (4) with the neutral diene isoprene. Polar [4+2⁺] Diels-Alder cycloaddition is observed for nitrilium ions when the energy gap between the lowest unoccupied molecular orbital (LUMO) of the ion and the highest occupied molecular orbital (HOMO) of the isoprene is small and the competing proton transfer reaction is endothermic. Thus, C-protonated methyl isonitrile H-C≡N⁺-CH₃ (2a) and its higher homolog H-C≡N⁺-C₂H₅ (3a) form abundant [4+2⁺] cycloadducts with isoprene, but several protonated nitriles 1 do not; instead they show exothermic proton transfer as the main ion-molecule reaction. Replacement of the methyne hydrogen in 2a by a methyl, ethyl, or phenyl group (2b–d) raises the LUMO-HOMO gap, which greatly decreases the total yield of ion-molecule products and precludes cycloaddition. On the other hand, the electron-withdrawing acetyl and bromine substituents in 2e and 2f substantially lower the LUMO energy of the ions and cycloaddition reaction occurs readily. The simplest member of the immonium ion series, CH₂=NH ₂ ⁺ (4a), reacts readily by cycloaddition, whereas alkyl substitution on either the carbon or nitrogen (4b–f) dramatically lowers the overall reactivity, which substantially decreases or even precludes cycloaddition. In strong contrast, the N-phenyl (4g) and N-acetyl (4h) ions and the N-vinyl-substituted immonium ion, N-protonated 2-aza-butadiene (4i), react extensively with isoprene, mainly by [4+2⁺] cycloaddition. However, the isomeric C-vinyl-substituted ion (4j) displays only modest reactivity in both the proton-transfer and the cycloaddition channels. Collision-induced dissociation (CID) of the cycloadducts performed by on-line MS³ experiments demonstrates that they are covalently bound and supports their assignments as cycloaddition products. Retro Diels-Alder fragmentation is a major process for cycloadducts of both the immonium and the nitrilium ions, but other fragmentation processes also are observed. The cycloadduct of 4a with butadiene displays CID fragmentation identical to that of the authentic ion produced by protonation of 1,2,3,6-tetrahydropyridine, which thus strengthens the [4+2⁺] cycloaddition proposal. AM1 calculations also support the formation of the [4+2⁺] cycloadducts, which are shown in several cases to be much more stable than the products of simple addition, that is, the ring-open isomers.     

The Las-Vegas Processor Identity Problem (How and When to Be Unique)

We study the classical problem of assigning unique identifiers to identical concurrent processes. In this paper, we consider the asynchronous shared memory model, and the correctness requirement is that upon termination of the algorithm, the processes must have unique IDs always. Our results include tight characterization of the problem in several respects. We call a protocol solving this task Las Vegas if it has finite expected termination time. Our main positive result is the first Las-Vegas protocol that solves the problem. The protocol terminates in O(log n) expected asychronous rounds, using O(n) shared memory space, where n is the number of participating processes. The new protocol improves on all previous solutions simultaneously in running time (exponentially), probability of termination (to 1), and space requirement. The protocol works under the assumption that the asynchronous schedule is oblivious, i.e., independent of the actual unfolding execution. On the negative side, we show that there is no finite-state Las-Vegas protocol for the problem if the schedule may depend on the history of the shared memory (an adaptive schedule). We also show that any Las-Vegas protocol must know n in advance (which implies that crash faults cannot be tolerated) and that the running time is Ω(log n). For the case of an arbitrary (nonoblivious) adversarial schedule, we present a Las-Vegas protocol that uses O(n) unbounded registers. For the read-modify-write model, we present a constant-space deterministic algorithm.     

Palladium‐Mediated Direct Disulfide Bond Formation in Proteins Containing S‐Acetamidomethyl‐cysteine under Aqueous Conditions

One of the applied synthetic strategies for correct disulfide bond formation relies on the use of orthogonal Cys protecting groups. This approach requires purification before and after the deprotection steps, which prolongs the entire synthetic process and lowers the yield of the reaction. A major challenge in using this approach is to be able to apply one‐pot synthesis under mild conditions and aqueous media. In this study, we report the development of an approach for rapid disulfide bond formation by employing palladium chemistry and S‐acetamidomethyl‐cysteine [Cys(Acm)]. Oxidation of Cys(Acm) to the corresponding disulfide bond is achieved within minutes in a one‐pot operation by applying palladium and diethyldithiocarbamate. The utility of this reaction was demonstrated by the synthesis of the peptide oxytocin and the first total chemical synthesis of the protein thioredoxin‐1. Our investigation revealed a critical role of the Acm protecting group in the disulfide bond formation, apparently due to the generation of a disulfiram in the reaction pathway, which significantly assists the oxidation step.     

Strain-gage stability measurements for three years at 150°C in air

The zero shifts of nickel-chromium foil strain gages (modified Karma) were measured over a period of three years at a constant temperature of 150°C in air. Three gage lengths were included—1.585 mm (1/16 in.), 3.170 mm (1/8 in.), and 6.340 mm (1/4 in.). The strain gages were bonded to constant-stress cantilever beams which were subjected to nomial mechanical strain levels of 0, ±780 μm/m, and ± 1350 μm/m. Each strian gage was connected by threewire leads to a Wheatstone-bridge circuit for the test duration. The data support two general observations: (1) short gage lengths suffer larger zero shifts than longer gage lengths, and (2) gages in compression suffer large zero shifts than gages in tension. On the assumption that the major cause of the zero shifts is a combination of corrosion of the foil and creep of the gage/epoxy/beam system, the author suggests a possible way to correct for the zero shift by experimentally determining the combined corrosion/creep effect and substracting it from the strain-gage readings. Some of the data appear to be consistent with this assumption, but some of the data do not.     

Bridging the Two Worlds: A Universal Interface between Enzymatic and DNA Computing Systems

Molecular computing based on enzymes or nucleic acids has attracted a great deal of attention due to the perspectives of controlling living systems in the way we control electronic computers. Enzyme‐based computational systems can respond to a great variety of small molecule inputs. They have the advantage of signal amplification and highly specific recognition. DNA computing systems are most often controlled by oligonucleotide inputs/outputs and are capable of sophisticated computing as well as controlling gene expressions. Here, we developed an interface that enables communication of otherwise incompatible nucleic‐acid and enzyme‐computational systems. The enzymatic system processes small molecules as inputs and produces NADH as an output. The NADH output triggers electrochemical release of an oligonucleotide, which is accepted by a DNA computational system as an input. This interface is universal because the enzymatic and DNA computing systems are independent of each other in composition and complexity.     

HDL设计和验证与System Generator相结合

Xilinx System Generator for DSP是用来协助系统设计的MATLAB Simulink模块集。System Generator for DSP在熟悉的MATLAB环境中引入Xilinx FPGA对象,让您能够对设计进行功能仿真,并且使用MATLAB环境对照理想参考结果验证位精度和时序精度模型。这些参考结果可以在MATLAB环境外部生成,也可以在其内部生成,在这两种情况下您均可从MATLAB环境中引用Xilinx FPGA硬件平台。     

Engineering of SiO2-Au-SiO2 sandwich nanoaggregates using a building block: single, double, and triple cores for enhancement of near infrared fluorescence

We have developed a simple and flexible chemical method to synthesize orderly metallic nanoaggregates using a designed SiO 2-Au core-shell building block. The number of the building blocks in a nanoaggregate is tunable from one to three. These metal nanostructures can generate an enlarged localized electromagnetic field through surface plasmon resonance and enhance the optical signals of the photoactive molecules within this electromagnetic field. Aggregates of metallic nanoparticles provide a higher signal enhancement than well-dispersed nanoparticles combined. The level of signal enhancement is determined by the number of building blocks in a nanoaggregate. The signal enhancement of the nanoaggregates has been verified with a near-infrared (NIR) dye. In the NIR region, biological samples have low background signals and deeper penetration of radiation. The application of these NIR enhanced metal nanostructures will open a significant approach for sensitive detection of biological samples.     

Two-scale structure of the electron dissipation region during collisionless magnetic reconnection

Particle-in-cell simulations of collisionless magnetic reconnection are presented that demonstrate that reconnection remains fast in very large systems. The electron dissipation region develops a distinct two-scale structure along the outflow direction. Consistent with fast reconnection, the length of the electron current layer stabilizes and decreases with decreasing electron mass, approaching the ion inertial length for a proton-electron plasma. Surprisingly, the electrons form a super-Alfvénic outflow jet that remains decoupled from the magnetic field and extends large distances downstream from the x line.     

Second-order finite difference solutions for the flow between rotating concentric spheres

This paper describes a second-order method to calculate approximate solutions to flow of viscous incompressible fluid between rotating concentric spheres. The governing partial differential equations are presented in the stream–vorticity formulation and are written as a series of second-order equations. The technique employed makes use of second-order approximations for all terms in the governing equations and is dependent upon the direction of flow at a given point. This upwind technique has allowed us to generate approximate solutions with larger Reynolds numbers than has generally been possible for second and higher-order techniques. Solutions have been obtained with Reynolds numbers as large as 3000 and with grids as fine as a 40 × 40 mesh. Results are displayed in the form of level curves for both the stream and vorticity functions. A dimensionless quantity related to the torque acting on both spheres has been calculated from the approximate solution and compared with other results. Results with smaller Reynolds numbers such as 100 and 1000 are in excellent agreement with other published results.