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991.

Rationale

The isotope delta is calculated from the isotope ratio of a sample and the absolute isotope ratio of the zero reference point defining each stable isotope international scale (Rstd). Therefore, Rstd requires accurate determination. However, the literature contains a large number of Rstd values, and selection of different Rstd may lead to inconsistency in reporting and recalculating stable isotope results.

Methods

We reviewed Rstd used in the proprietary software provided by the manufacturers of stable isotope instruments commonly employed for analyses of stable HCNOS compositions. We compared the Rstd values and assessed the potential implications of using different Rstd and the normalization versus tank working gas standard for consistency in reporting stable isotope results.

Results

Different Rstd values are used by different manufacturers of stable isotope analytical instruments. For R(2H/1H)VSMOW two different but very similar values are used, 0.00015575 and 0.00015576; for R(13C/12C)VPDB three different values are used, 0.0111802, 0.0112372 and 0.01118028; and for R(15N/14N)Air-N2 two values, 0.0036782 and 0.0036765, are used. All manufacturers are using the same value for R(18O/16O)VSMOW, 0.00200520, but three different values for R(18O/16O)VPDB, 0.002067200, 0.00208835 and 0.002088349. For R(34S/32S)VCDT four different Rstd are used, 0.0441509, 0.0441626, 0.044162589 and 0.0441520597.

Conclusions

The use of different Rstd values may lead to differences in the isotope delta values obtained if the normalization versus working standard gas is applied. For the range of Rstd used in proprietary software, the potential differences are lowest for oxygen (< 0.002 ‰) and nitrogen (< 0.001 ‰), and highest for carbon (0.107 to 0.112 ‰) and sulfur (0.023 ‰). Evaluation of the existing Rstd values and recommendations for the best estimates are highly desirable to ensure worldwide consistency in stable isotope data reporting.
  相似文献   
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Copper complexes of monodentate phosphoramidites efficiently promote asymmetric arylation of N‐azaaryl aldimines with arylboroxines. DFT calculations and experiments support an elementary step of 1,4‐insertion in the reaction pathway, a step in which an aryl‐copper species adds directly across four atoms of C=N?C=N in the N‐azaaryl aldimines.  相似文献   
994.
Light-activated polymers can undergo complex deformation in response to the combination of mechanical and optical stimuli. These materials are attractive for remote actuation and sensing applications. However, the behavior of such materials subjected to photomechanical patterning is not well understood. In this paper we consider a polymer that operates by photoactivated stress relaxation; at the molecular level, photoinitiation of residual initiator molecules generate free radicals that break and then reform in-chain functionalities of stretched chains in an elastomeric network, which results in macroscopic stress relaxation. We carry out experiments and finite element calculations that demonstrate the sequence of deformation events culminating in the formation of a buckled spot as a result of biaxially stretching the elastomeric film then irradiating a circular region followed by releasing the mechanical constraint. In order to better understand the photomechanics, we analyze a simpler model problem wherein a linear elastic, stress relaxing disk is subjected to (i) radial extension, (ii) irradiation of a concentric circular region, and (iii) release of the applied displacements in (i), which results in deformation and stress redistribution. In the final step, the deformation may transition from planar to buckling out of the plane depending on system parameters. Companion finite element calculations are performed against which our analytical results are in good agreement. Although not directly comparable, the analytic model qualitatively agrees with the experiments. The results of this work provide a useful foundation from which to explore more interesting behavior of periodically photo-mechanically patterned films and other more challenging actuation problems.  相似文献   
995.
We apply the Wigner function formalism from quantum optics via two approaches, Wootters' discrete Wigner function and the generalized Wigner function, to detect quantum phase transitions in critical spin-12 systems. We develop a general formula relating the phase space techniques and the thermodynamical quantities of spin models, which we apply to single, bipartite and multi-partite systems governed by the XY and the XXZ models. Our approach allows us to introduce a novel way to represent, detect, and distinguish first-, second- and infinite-order quantum phase transitions. Furthermore, we show that the factorization phenomenon of the XY model is only directly detectable by quantities based on the square root of the bipartite reduced density matrix. We establish that phase space techniques provide a simple, experimentally promising tool in the study of many-body systems and we discuss their relation with measures of quantum correlations and quantum coherence.  相似文献   
996.
Structural Chemistry - (MY)6 clusters, with M = Zn and Cd and Y = O, S, Se, form double-layer drum-like structures containing M–Y covalent bonds. The positive regions near the M atoms attract...  相似文献   
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Straightforward methods for detecting adenosine-to-inosine (A-to-I) RNA editing are key to a better understanding of its regulation, function, and connection with disease. We address this need by developing a novel reagent, N-(4-ethynylphenyl)acrylamide (EPhAA), and illustrating its ability to selectively label inosine in RNA. EPhAA is synthesized in a single step, reacts rapidly with inosine, and is “click”-compatible, enabling flexible attachment of fluorescent probes at editing sites. We first validate EPhAA reactivity and selectivity for inosine in both ribonucleosides and RNA substrates, and then apply our approach to directly monitor in vitro A-to-I RNA editing activity using recombinant ADAR enzymes. This method improves upon existing inosine chemical-labeling techniques and provides a cost-effective, rapid, and non-radioactive approach for detecting inosine formation in RNA. We envision this method will improve the study of A-to-I editing and enable better characterization of RNA modification patterns in different settings.  相似文献   
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