The bent RC  N linkage: An AB initio study of NH2CN,NF2CN and PF2CN

The ab initio energies, nuclear and electron repulsions and charge distributions have been calculated using moderately large basis sets as a function of the RC  N angle (R  NH₂, NF₂ or PF₂). The optimum RC  N angles were calculated to be 178.9°, 176.6°, and 175° for NH₂CN, NF₂CN, and PF₂CN, respectively. A rationalization of the differing bends is presented in terms of nuclear-nuclear and electron-electron repulsions.     

Reduced local energy as a criterion for the accuracy of approximate H2 wave-functions

The goodness of the local fit of an approximate wave-function, \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \psi $\end{document}, to the exact function, ψ₀, is \documentclass{article}\pagestyle{empty}\begin{document}$ |\tilde \psi - \psi _0 | $\end{document}. From this quantity the global accuracy of \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \psi $\end{document} is defined and a “working supposition” is presented, which quantitatively relates the global accuracy to the accuracy of expectation values. Two criteria based on the accuracy of the reduced local energy and the density respectively, are presented as alternatives to \documentclass{article}\pagestyle{empty}\begin{document}$ |\tilde \psi - \psi _0 | $\end{document}. The relative global accuracies of eight wave-functions for H₂ are determined using the two criteria. The ‘working supposition’ is applied and predictions are made concerning the relative accuracies of the expectation values of the following operators: z², r², x² + y², 3z² ?; r², ξ, r, r, and E_L (the reduced local energy). The success rate is high (>90%) except for those operators which are sensitive to interelectron coordinates or derivatives of the wave-function.     

Aqueous Solution Chemistry of the Mo(3)PdS(4) Cube: Substitution Reactions and the Double to Single Cube Interconversion Induced by CO, Two Phosphines, Cl(-), Br(-), and NCS(-)

The kinetics of conversion of an edge-linked double cube, in this case [{Mo(3)PdS(4)(H(2)O)(9)}(2)](8+), to the corresponding single cube [Mo(3)(PdX)S(4)(H(2)O)(9)](4+), has been studied for the first time. Reaction is induced by six reagents X = CO, two water-soluble phosphines, Cl(-), Br(-), and NCS(-), which complex at the tetrahedral Pd. The first stage of reaction is fast and is accompanied by color changes, e.g. purple to dark blue in the case of Cl(-), assigned as double to single cube conversion. With X = CO and the two phosphines, when absorbance changes are intense enough for stopped-flow monitoring with reactants at Pd-SCN. On removal of e.g. Cl(-) by chromatography or addition of Ag(+), the double cube re-forms.     

Comparison of uncoated, pyro-coated and totally pyrolytic graphite tubes for the HGA-500 electrothermal atomiser

The analytical performance of three uncoated electrographite tubes, three pyro-coated electrographite tubes, one tantalum carbide (TaC) coated electrographite tube, and three totally pyrolytic graphite (TPG) tubes has been evaluated and compared. A test programme was devised to determine the useful operational lifetime of each tube, and assess the influence of tube age on the sensitivity of lead, manganese and vanadium measurements by atomic absorption spectrometry. The TPG tubes were found to be more durable than the other types studied, but the lifetime advantage depended on the thickness of the pyrolytic graphite. The best TPG tube, of 720 μm wall-thickness, lasted 2.5 times longer than the pyro-coated tubes, and 5 times longer than the uncoated electrographite tubes.The TPG tubes gave slightly poorer AAS sensitivity for lead, equivalent sensitivity for manganese, and 4 times better sensitivity for vanadium than the pyro-coated electrographite tubes. Also, with TPG, signal magnitude was more consistent throughout the lifetime of a tube. For each of the test elements studied, poorest sensitivity was encountered with the TaC-coated electrographite tube.     

Superselection rules in quantum theory: Part I. A new proposal for state restriction violation

It is argued that preparation of a quantum state characterized by density operator not commuting with a superselection operatorQ does not by itself constitute an instance of superselection rule violation. It would, however, be an instance of state restriction violation. It is held that superselection rule violation is only possible with simultaneous observable and state restriction violations. It is shown that it is a priori conceivable to subdivide an ensemble whose satisfies[, Q] = 0 into subensembles whose density operators violate the state restrictions. The dynamics of the subdivision process is not considered.     

New information-theoretic foundations for quantum statistics

When the state of a physical system is not fully determined by available data, it should be possible nevertheless to make a systematic guess concerning the unknown state by applying the principles of information theory. The resulting theoretical blend of informational and mechanical constructs should then constitute a modern structure for statistical physics. Such a program has been attempted by a number of authors, most notably Jaynes, with seeming success. However, we demonstrated in a recent publication that the standard list of so-called mutually exclusive and exhaustive quantum states that is commonly employed by these authors is in fact not exhaustive. It follows that the information-theoretic foundations of quantum statistics must be reformulated. The present paper discusses the fundamental problems involved and establishes a format for the correct application of information theory to quantum mechanical situations.Work supported by a grant from Research Corporation.     

Evaluation of Electrospun PCL-PLGA for Sustained Delivery of Kartogenin

In this study, kartogenin was incorporated into an electrospun blend of polycaprolactone and poly(lactic-co-glycolic acid) (1:1) to determine the feasibility of this system for sustained drug delivery. Kartogenin is a small-molecule drug that could enhance the outcome of microfracture, a cartilage restoration procedure, by selectively stimulating chondrogenic differentiation of endogenous bone marrow mesenchymal stem cells. Experimental results showed that kartogenin did not affect the electrospinnability of the polymer blend, and it had negligible effects on fiber morphology and scaffold mechanical properties. The loading efficiency of kartogenin into electrospun membranes was nearly 100%, and no evidence of chemical reaction between kartogenin and the polymers was detected by Fourier transform infrared spectroscopy. Analysis of the released drug using high-performance liquid chromatography–photodiode array detection indicated an abundance of kartogenin and only a small amount of its major hydrolysis product. Kartogenin displayed a typical biphasic release profile, with approximately 30% being released within 24 h followed by a much slower, constant rate of release up to 28 days. Although additional development is needed to tune the release kinetics and address issues common to electrospun scaffolds (e.g., high fiber density), the results of this study demonstrated that a scaffold electrospun from biodegradable synthetic polymers is a suitable kartogenin delivery vehicle.     

A Testable Theory for the Emergence of the Classical World

The transition from the quantum to the classical world is not yet understood. Here, we take a new approach. Central to this is the understanding that measurement and actualization cannot occur except on some specific basis. However, we have no established theory for the emergence of a specific basis. Our framework entails the following: (i) Sets of N entangled quantum variables can mutually actualize one another. (ii) Such actualization must occur in only one of the 2^N possible bases. (iii) Mutual actualization progressively breaks symmetry among the 2^N bases. (iv) An emerging “amplitude” for any basis can be amplified by further measurements in that basis, and it can decay between measurements. (v) The emergence of any basis is driven by mutual measurements among the N variables and decoherence with the environment. Quantum Zeno interactions among the N variables mediates the mutual measurements. (vi) As the number of variables, N, increases, the number of Quantum Zeno mediated measurements among the N variables increases. We note that decoherence alone does not yield a specific basis. (vii) Quantum ordered, quantum critical, and quantum chaotic peptides that decohere at nanosecond versus femtosecond time scales can be used as test objects. (viii) By varying the number of amino acids, N, and the use of quantum ordered, critical, or chaotic peptides, the ratio of decoherence to Quantum Zeno effects can be tuned. This enables new means to probe the emergence of one among a set of initially entangled bases via weak measurements after preparing the system in a mixed basis condition. (ix) Use of the three stable isotopes of carbon, oxygen, and nitrogen and the five stable isotopes of sulfur allows any ten atoms in the test protein to be discriminably labeled and the basis of emergence for those labeled atoms can be detected by weak measurements. We present an initial mathematical framework for this theory, and we propose experiments.     

Quantitative Raman Analysis of Carotenoid Protein Complexes in Aqueous Solution

Carotenoids are naturally abundant, fat-soluble pigmented compounds with dietary, antioxidant and vision protection advantages. The dietary carotenoids, Beta Carotene, Lutein, and Zeaxanthin, complexed with in bovine serum albumin (BSA) in aqueous solution, were explored using Raman spectroscopy to differentiate and quantify their spectral signatures. UV visible absorption spectroscopy was employed to confirm the linearity of responses over the concentration range employed (0.05–1 mg/mL) and, of the 4 Raman source wavelengths (785 nm, 660 nm, 532 nm, 473 nm), 532 nm was chosen to provide the optimal response. After preprocessing to remove water and BSA contributions, and correct for self-absorption, a partial least squares model with R² of 0.9995, resulted in an accuracy of the Root Mean Squared Error of Prediction for Beta Carotene of 0.0032 mg/mL and Limit of Detection 0.0106 mg/mL. Principal Components Analysis clearly differentiated solutions of the three carotenoids, based primarily on small shifts of the main peak at ~1520 cm⁻¹. Least squares fitting analysis of the spectra of admixtures of the carotenoid:protein complexes showed reasonable correlation between norminal% and fitted%, yielding 100% contribution when fitted with individual carotenoid complexes and variable contributions with multiple ratios of admixtures. The results indicate the technique can potentially be used to quantify the carotenoid content of human serum and to identify their differential contributions for application in clinical analysis.     

Formalising the Pathways to Life Using Assembly Spaces

Assembly theory (referred to in prior works as pathway assembly) has been developed to explore the extrinsic information required to distinguish a given object from a random ensemble. In prior work, we explored the key concepts relating to deconstructing an object into its irreducible parts and then evaluating the minimum number of steps required to rebuild it, allowing for the reuse of constructed sub-objects. We have also explored the application of this approach to molecules, as molecular assembly, and how molecular assembly can be inferred experimentally and used for life detection. In this article, we formalise the core assembly concepts mathematically in terms of assembly spaces and related concepts and determine bounds on the assembly index. We explore examples of constructing assembly spaces for mathematical and physical objects and propose that objects with a high assembly index can be uniquely identified as those that must have been produced using directed biological or technological processes rather than purely random processes, thereby defining a new scale of aliveness. We think this approach is needed to help identify the new physical and chemical laws needed to understand what life is, by quantifying what life does.